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Sample records for detrital chromian spinels

  1. Chromian spinel-rich black sands from eastern shoreline of ...

    Indian Academy of Sciences (India)

    Chromian spinel; detrital sand; ophiolites; Andaman Island; India. J. Earth Syst. .... (olivine: ol) inclusion; (e) peridotitic spinel with extensive fracturing; and (f) heavily altered rim of a peridotitic spinel. ..... The authors acknowledge the financial.

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

    Science.gov (United States)

    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+# 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.

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

    Science.gov (United States)

    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

  4. Cr diffusion in MgAl2O4 synthetic spinels: preliminary results

    Science.gov (United States)

    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

  5. Sediment unmixing using detrital geochronology

    Science.gov (United States)

    Sharman, Glenn R.; Johnstone, Samuel A.

    2017-11-01

    Sediment mixing within sediment routing systems can exert a strong influence on the preservation of provenance signals that yield insight into the effect of environmental forcing (e.g., tectonism, climate) on the Earth's surface. Here, we discuss two approaches to unmixing detrital geochronologic data in an effort to characterize complex changes in the sedimentary record. First, we summarize 'top-down' mixing, which has been successfully employed in the past to characterize the different fractions of prescribed source distributions ('parents') that characterize a derived sample or set of samples ('daughters'). Second, we propose the use of 'bottom-up' methods, previously used primarily for grain size distributions, to model parent distributions and the abundances of these parents within a set of daughters. We demonstrate the utility of both top-down and bottom-up approaches to unmixing detrital geochronologic data within a well-constrained sediment routing system in central California. Use of a variety of goodness-of-fit metrics in top-down modeling reveals the importance of considering the range of allowable that is well mixed over any single best-fit mixture calculation. Bottom-up modeling of 12 daughter samples from beaches and submarine canyons yields modeled parent distributions that are remarkably similar to those expected from the geologic context of the sediment-routing system. In general, mixture modeling has the potential to supplement more widely applied approaches in comparing detrital geochronologic data by casting differences between samples as differing proportions of geologically meaningful end-member provenance categories.

  6. Detrital Zircons Split Sibumasu in East Gondwana

    Science.gov (United States)

    Zhang, X.; Chung, S. L.

    2017-12-01

    It is widely accepted that Sibumasu developed as a united terrane and originated from NW Australian margin in East Gondwana. Here we report new detrital zircon U-Pb-Hf isotopic data from Sumatra that, in combination with literature data, challenge and refute the above long-held view. In particular, the East and West Sumatra terranes share nearly identical Precambrian to Paleozoic detrital zircon age distributions and Hf isotopes, indicating a common provenance/origin for them. The Sumatra detrital zircons exhibit a prominent population of ca. 1170-1070 Ma, indistinguishable from those of the Lhasa and West Burma terranes, with detritus most probably sourcing from western Australia. By contrast, Sibuma (Sibumasu excluding Sumatra) detrital zircons display a prevailing population of ca. 980-935 Ma, strongly resembling those of the western Qiangtang terrane, with detrital materials most likely derived from Greater India and Himalayas. Such markedly distinct detrital zircon age profiles between Sumatra and Sibuma require disparate sources/origin for them, provoking disintegration of the widely-adopted, but outdated, term Sibumasu and thus inviting a new configuration of East Gondwana in the early Paleozoic, with Sumatra and West Burma lying outboard the Lhasa terrane in the NW Australian margin and Sibuma situated in the northern Greater Indian margin. More future investigations are needed to establish the precise rifting and drifting histories of Sumatra and Sibuma, as two separated terranes, during the breakup of Gondwana.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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 (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, A. (2004), Composition of the depleted mantle. Geochem. Geophys. Geosys. 5 (2003GC000597)]. The results suggest that Gorgona komatiite and picrite magmas were derived from volatile-rich sources. CO2

  9. Low Temperature Synthesis of Magnesium Aluminate Spinel

    International Nuclear Information System (INIS)

    Lebedovskaya, E.G.; Gabelkov, S.V.; Litvinenko, L.M.; Logvinkov, D.S.; Mironova, A.G.; Odejchuk, M.A.; Poltavtsev, N.S.; Tarasov, R.V.

    2006-01-01

    The low-temperature synthesis of magnesium-aluminum spinel is carried out by a method of thermal decomposition in combined precipitated hydrates. The fine material of magnesium-aluminium spinel with average size of coherent dispersion's area 4...5 nanometers is obtained. Magnesium-aluminum spinel and initial hydrates were investigated by methods of the differential thermal analysis, the x-ray phase analysis and measurements of weight loss during the dehydration and thermal decomposition. It is established that synthesis of magnesium-aluminum spinel occurs at temperature 300 degree C by method of the x-ray phase analysis

  10. Petrogenetic importance of Cr - spinel metaperidotite

    International Nuclear Information System (INIS)

    Snarska, B.

    2010-01-01

    The research is ultramafic body Komarovce the site, which represents the spinel metaperidotit. In recent works dealing with the problems of genesis and tectonic ultramafic rocks placement consideration, Cr - spinel, which is considered an important petrogenetic indicator. Based on its chemical composition can further characterize the origin of peridotite.

  11. Cosmogenic 3He in detrital gold

    Science.gov (United States)

    Stuart, Finlay; Yakubovich, Olga; Caracedo, Ana; Nesterenok, Alexander

    2017-04-01

    Since the measurement of cosmogenic He in an alluvial diamond by McConville and Reynolds (1996) the application of cosmogenic noble gases to individual detrital grains to quantify surface processes has not been vigorously pursued. The likely low rate of diffusion of cosmogenic He in native metals, and their resistance to weathering and disintegration during erosion and transport, makes them a potential record of long-term Earth surface processes. In an effort to assess the extent that detrital refractory metals record the exposure history during transport and storage we have undertaken a reconnaissance study of the He isotope composition in 18 grains (2-200 mg) of native gold, copper, silver, and PtPd, Pt3Fe and OsIr alloys from alluvial placer deposits from around the world. 4He is dominantly the result of U and Th decay within the grains, or decay of 190Pt in the Pt-rich alloys. 3He is measurable in 13 grains, concentrations range up to 2.7E+6 atoms/g. 3He/4He are always in excess of the crustal radiogenic ratio, up to 306 Ra. Although nucleogenic 3He produced by (n,α) reactions on 6Li, and 3He from trapped hydrothermal fluids, are present, the majority of the 3He is cosmogenic in origin. Using newly calculated cosmogenic 3He production rates in heavy metals, and a determination of the effect of implantation based on the stopping distances of spallogenic 3He and 3H, the grains have 3Hecos concentrations that are equivalent to 0.35 to 1.5 Ma exposure at Earth's surface. In a study of detrital gold grains from several sites in Scotland we have found that 10 % have 3He concentrations that are significantly in excess of that generated since the Last Glacial Maximum. These studies demonstrate that, with refinement, cosmogenic 3He in refractory detrital minerals can be used to quantify sediment transport and storage on the 1-10 Ma timescale. P. McConville & J.H. Reynolds (1989). Geochim. Cosmochim. Acta, 53, 2365-75.

  12. Synthesis on spinel behaviour under irradiation

    International Nuclear Information System (INIS)

    Chauvin, N.; Dodane, C.; Noirot, J.; Konings, R.J.M.; Matzke, H.J.; Wiss, T.; Conrad, R.

    2001-01-01

    The spinel MgAl 2 O 4 is one of the materials able to be used in reactor for the transmutation of the minor actinides stemming from the back-end of the fuel cycle. It has been studied under irradiation since many years. Indeed, one of the first uses considered is to be employed as material for fusion reactors. Otherwise, it was shown that spinel presents nuclear and physico-chemical properties suitable for an utilization as nuclear inert matrix that loaded with an actinide phase constitutes a target devoted to the heterogeneous recycling in reactor. In order to improve the knowledge on spinel behaviour under irradiation, an assessment of the former studies must be done. The objective of this paper is to gather all the results of the spinel irradiations and to take out synthetic conclusion on the opportunity to use this material for the transmutation programme. (author)

  13. Magnetic behavior of the oxide spinels:

    Indian Academy of Sciences (India)

    Magnetic behavior of the oxide spinels: Li0.5Fe2.5−2xAlxCrxO4. U N TRIVEDI, K B MODI and H H JOSHI. Department of Physics, Saurashtra University, Rajkot 360 005, India. Abstract. In order to study the effect of substitution of Fe3+ by Al3+ and Cr3+ in Li0.5Fe2.5O4 on its structural and magnetic properties, the spinel ...

  14. Identification of Detrital Carbonate in East Cepu High

    Science.gov (United States)

    Sari, R.; Andika, I. K.; Haris, A.; Miftah, A.

    2018-03-01

    East Cepu High is a part of horst – graben series which formed by extensional tectonic processes during Paleogene in North East Java Basin. Due to excellent paleogeography position, the carbonate build-up was growth very well and as the main reservoir in East Cepu High. Sea level change have important factor to provide variation of facies in each carbonate buildup, one of emerging facies is detrital carbonate. Detrital carbonate indicated by onlap horizon featured with carbonate build up body. Based on paleogeography, fluctuation of sea level change and sediment source, detrital carbonate formed in leeward area in lowstand or highstand phases. Distinguish between detrital carbonate facies with other facies, advanced seismic processing performed by using continuous wavelet transform (CWT) and seismic inversion. CWT is one method of spectral decomposition used to find the frequency that represent a facies. The result from seismic inversion will support the interpretation for facies distribution. As the result, seismic data which have interval frequency 10 – 45 Hz and Acoustic Impedance (AI) value above 35000 (from cross plot between acoustic impedance and gamma ray) can be interpreted as detrital carbonate. Based on seismic interpretation, detrital carbonate facies distributed along leeward area with geometrical spreading. The lateral facies change from detrital carbonate to shale was identified which causing this facies become potential as hydrocarbon reservoir with stratigraphic trap. Based on the earlier studies, North East Java Basin have a strong hydrocarbon migration to fill the reservoir, therefore the detrital carbonate have high chance to be a new hydrocarbon prospect in this area.

  15. Lithium manganese oxide spinel electrodes

    Science.gov (United States)

    Darling, Robert Mason

    Batteries based oil intercalation eletrodes are currently being considered for a variety of applications including automobiles. This thesis is concerned with the simulation and experimental investigation of one such system: spinel LiyMn2O4. A mathematical model simulating the behavior of an electrochemical cell containing all intercalation electrode is developed and applied to Li yMn2O4 based systems. The influence of the exchange current density oil the propagation of the reaction through the depth of the electrode is examined theoretically. Galvanostatic cycling and relaxation phenomena on open circuit are simulated for different particle-size distributions. The electrode with uniformly sized particles shows the best performance when the current is on, and relaxes towards equilibrium most quickly. The impedance of a porous electrode containing a particle-size distribution at low frequencies is investigated with all analytic solution and a simplified version of the mathematical model. The presence of the particle-size distribution leads to an apparent diffusion coefficient which has all incorrect concentration dependence. A Li/1 M LiClO4 in propylene carbonate (PC)/ LiyMn 2O4 cell is used to investigate the influence of side reactions oil the current-potential behavior of intercalation electrodes. Slow cyclic voltammograms and self-discharge data are combined to estimate the reversible potential of the host material and the kinetic parameters for the side reaction. This information is then used, together with estimates of the solid-state diffusion coefficient and main-reaction exchange current density, in a mathematical model of the system. Predictions from the model compare favorably with continuous cycling results and galvanostatic experiments with periodic current interruptions. The variation with respect to composition of' the diffusion coefficient of lithium in LiyMn2O4 is estimated from incomplete galvanostatic discharges following open-circult periods. The

  16. Magnetic behavior of the oxide spinels

    Indian Academy of Sciences (India)

    ... Refresher Courses · Symposia · Live Streaming. Home; Journals; Pramana – Journal of Physics; Volume 58; Issue 5-6. Magnetic behavior of the oxide spinels: Li0.5Fe2.5-2AlCrO4. U N Trivedi K B Modi H H Joshi. Colossal Magnetoresistance & Other Materials Volume 58 Issue 5-6 May-June 2002 pp 1031-1034 ...

  17. Detrital carbon pools in temperate forests: magnitude and potential for landscape-scale assessment

    Science.gov (United States)

    John Bradford; Peter Weishampel; Marie-Louise Smith; Randall Kolka; Richard A. Birdsey; Scott V. Ollinger; Michael G. Ryan

    2009-01-01

    Reliably estimating carbon storage and cycling in detrital biomass is an obstacle to carbon accounting. We examined carbon pools and fluxes in three small temperate forest landscapes to assess the magnitude of carbon stored in detrital biomass and determine whether detrital carbon storage is related to stand structural properties (leaf area, aboveground biomass,...

  18. Detection of Mg spinel lithologies on central peak of crater ...

    Indian Academy of Sciences (India)

    identified Fe bearing Mg-spinel-rich rock types are defined by their strong 2-μm ... The Modified Gaussian Modeling (MGM) analysis ... study the deep crustal and/or upper mantle composition and may lead to a fresh ... Lunar surface; Mg-spinel; central peak; Theophilus; remote sensing. .... The explanation of these spec-.

  19. Petrology of spinel lherzolite xenoliths in alkali basalts from Liri ...

    African Journals Online (AJOL)

    Al2O3), and Al-rich spinel occur in alkali basalts from Liri, South of the ... these spinel lherzolite xenoliths are reported, along with the analyses of ...... erupted in the Liri region. .... and temperatures with controlled activities of water, carbon.

  20. Synthesis of magnesium aluminate spinel by periclase and alumina chlorination

    International Nuclear Information System (INIS)

    Orosco, Pablo; Barbosa, Lucía; Ruiz, María del Carmen

    2014-01-01

    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 2 –N 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 2 O 3 (alumina) in chlorine atmosphere was developed and the results were compared with those 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 2 atmosphere of the MgO–Al 2 O 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

  1. Electrochemically synthesized nanocrystalline spinel thin film for high performance supercapacitor

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Vinay [Carbon Technology Unit, Engineering Materials Division, National Physical Laboratory, New-Delhi, 110012 (India); Art, Science and Technology Center for Cooperative Research, Kyushu University, Kasuga-shi, Fukuoka, 816-8580 (Japan); Japan Science and Technology Agency, Kawaguchi-shi, Saitama, 332-0012 (Japan); Gupta, Shubhra; Miura, Norio [Art, Science and Technology Center for Cooperative Research, Kyushu University, Kasuga-shi, Fukuoka, 816-8580 (Japan)

    2010-06-01

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

  2. Micro-XANES measurements on experimental spinels and the oxidation state of vanadium in coexisting spinel and silicate melt

    International Nuclear Information System (INIS)

    Righter, K.; Sutton, S.R.; Newville, M.; Le, L.; Schwandt, C.S.

    2006-01-01

    We show that experimental spinels coexisting with silicate melt always have lower valence vanadium, and that spinels typically have 3+, whereas the coexisting melt has 4+ or 5+. Implications of these results for planetary basalts will be discussed. Spinel can be a significant host phase for V which has multiple oxidation states V 2+ , V 3+ , V 4+ or V 5+ at oxygen fugacities relevant to natural systems. The magnitude of D(V) spinel/melt is known to be a function of composition, temperature and fO 2 , 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-Al 2 O 3 -SiO 2 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 build on our previous work in more oxidized systems, we have carried out experiments at relatively reducing conditions from the FMQ buffer to 2 log fO 2 units below the IW buffer. These spinel-melt pairs, where V is present in the spinel at natural levels (∼300 ppm V), were analyzed using an electron microprobe at NASA-JSC and mi-cro-XANES at the Advanced Photon Source at Argonne National Laboratory. The new results will be used together with previous results to understand the valence of V in spinel-melt systems across 12 orders of magnitude of oxygen fugacity, and with application to natural systems.

  3. Thermal expansion of spinel-type Si3N4

    DEFF Research Database (Denmark)

    Paszkowics, W.; Minkikayev, R.; Piszora, P.

    2004-01-01

    The lattice parameter and thermal expansion coefficient (TEC) for the spinel-type Si3N4 phase prepared under high-pressure and high-temperature conditions are determined for 14 K......The lattice parameter and thermal expansion coefficient (TEC) for the spinel-type Si3N4 phase prepared under high-pressure and high-temperature conditions are determined for 14 K...

  4. Structural changes of manganese spinel at elevated temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Li, Guohua; Iijima, Yukiko; Azuma, Hideto [Nishi Battery Laboratories, Sony Corporation, 4-16-1 Okata, Kanagawa 243-0021 Atsugi (Japan); Kudo, Yoshihiro [Technical Support Center, Sony Corporation, 4-16-1 Okata, Kanagawa 243-0021 Atsugi (Japan)

    2002-01-01

    A chemical synthesis route to Cr-doped and undoped Mn spinel was developed for the purpose of detailed structural analysis for elucidating the relationship between storage performance and structural changes at elevated temperatures. We identified a two-phase segregation in the lithium compositional range of 0.6spinel in the lithium compositional range of 0.4spinel decreased after storage at elevated temperatures. X-ray absorption fine structure (XAFS) analysis revealed that the Cr-doped samples showed less change in the local structure after storage than the undoped spinel samples. These results suggest that the Cr-doped spinel has higher structural stability at elevated temperatures than the undoped spinel.

  5. Micromagnetic simulations of spinel ferrite particles

    International Nuclear Information System (INIS)

    Dantas, Christine C.; Gama, Adriana M.

    2010-01-01

    This paper presents the results of simulations of the magnetization field ac response (at 2-12 GHz) of various submicron ferrite particles (cylindrical dots). The ferrites in the present simulations have the spinel structure, expressed here by M 1 - n Zn n Fe 2 O 4 (where M stands for a divalent metal), and the parameters chosen were the following: (a) for n=0: M={Fe, Mn, Co, Ni, Mg, Cu }; (b) for n=0.1: M = {Fe, Mg} (mixed ferrites). These runs represent full 3D micromagnetic (one-particle) ferrite simulations. We find evidences of confined spin waves in all simulations, as well as a complex behavior nearby the main resonance peak in the case of the M = {Mg, Cu} ferrites. A comparison of the n=0 and n=0.1 cases for fixed M reveals a significant change in the spectra in M = Mg ferrites, but only a minor change in the M=Fe case. An additional larger scale simulation of a 3 by 3 particle array was performed using similar conditions of the Fe 3 O 4 (magnetite; n=0, M = Fe) one-particle simulation. We find that the main resonance peak of the Fe 3 O 4 one-particle simulation is disfigured in the corresponding 3 by 3 particle simulation, indicating the extent to which dipolar interactions are able to affect the main resonance peak in that magnetic compound.

  6. Structural modifications of spinels under radiation

    International Nuclear Information System (INIS)

    Quentin, A.

    2010-12-01

    This work is devoted to the study of spinel structure materials under radiation. For that purpose, samples of polycrystalline ZnAl 2 O 4 and monocrystalline MgAl 2 O 4 were irradiated by different heavy ions with different energies. Samples of ZnAl 2 O 4 were studied par electron transmission microscopy, and by grazing incidence X-Ray diffraction and Rietveld analysis. Samples of MgAl 2 O 4 were studied by optical spectroscopy. Most of the results concern amorphization and crystalline structure modification of ZnAl 2 O 4 especially the inversion. We were able to determine a stopping power threshold for amorphization, between 11 keV/nm and 12 keV/nm, and also the amorphization process, which is a multiple impacts process. We studied the evolution of the amorphous phase by TEM and showed a nano-patterning phenomenon. Concerning the inversion, we determined that it did happen by a single impact process, and the saturation value did not reach the random cation distribution value. Inversion and amorphization have different, but close, stopping power threshold. However, amorphization seems to be conditioned by a pre-damage of the material which consists in inversion. (author)

  7. Utilization of detrital complexes by the oyster, Crassostrea virginica (Gmelin)

    International Nuclear Information System (INIS)

    Crosby, M.P.

    1987-01-01

    The contribution of bacteria and nonliving particulate organic matter of detrital complexes to the nutrition of the American oyster, Crassostrea virginica, was investigated in the laboratory under normal feeding conditions. Results indicate the oysters were capable of assimilating crude fiber extracted from 14 C-Spartina alterniflora with an efficiency of approximately 3% and that enteric bacteria did not enhance this process. Less than 1% of an oyster's energetic demands could be met by direct utilization of this substrate, in the Choptank River subestuary of the Chesapeake Bay. The potential contribution of refractory organics to oysters in large salt marshes having crude fiber concentration greater than in the Choptank system, are discussed. The ability of the oyster to utilize 14 C and 15 N from cellulolytic marine bacteria, isolated from a S. alterniflora dominated salt marsh, was also studied

  8. In situ detrital zircon (U-Th)/He thermochronology

    Science.gov (United States)

    Tripathy, A.; Monteleone, B. D.; van Soest, M. C.; Hodges, K.; Hourigan, J. K.

    2010-12-01

    Detrital studies of both sand and rock are relevant to many problems, ranging from the climate and tectonics feedback debate to the long-term record of orogenic evolution. When applying the conventional (U-Th)/He technique to such studies, two important issues arise. Often, only euhedral grains are permissible for analysis in order to make simple geometric corrections for α-recoil. In detrital samples, this is problematic because euhedral grains can be scarce due to mechanical abrasion during transport, and potentially introduce bias in favour of more proximally sourced grains. Second, inherent to detrital studies is the need to date many grains (>100) per sample to ensure a representative sampling of the sediment source region, thus making robust conventional detrital studies both expensive and time-consuming. UV laser microprobes can improve this by permitting careful targeting of the grain interior away from the α-ejection zone, rendering the α-recoil correction unnecessary, thus eliminating bias toward euhedral grains. In the Noble Gas, Geochemistry, and Geochronology Laboratory at ASU, apatite and zircon have been successfully dated using in situ methods. For this study, the conventional and in situ techniques are compared by dating zircons from a modern river sand that drains a small catchment in the Mesozoic-Cenozoic Ladakh Batholith in NW India. This sample has a simple provenance, which allows us to demonstrate the robustness of the in situ method. Moreover, different microbeam techniques will be explored to establish the most efficient approach to obtain accurate and precise U-Th concentrations using synrock, which is our powdered, homogenized, and reconstituted zircon-rock standard. Without this, such in situ U-Th data would be difficult to obtain. 117 zircons were dated using the conventional (U-Th)/He method, revealing dates ranging from 9.70±0.35 to 106.6±3.5 Ma (2σ) with the major mode at 26 Ma. For comparison, 44 grains were dated using the in

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

    Science.gov (United States)

    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

  10. Spin Filtering in Epitaxial Spinel Films with Nanoscale Phase Separation

    KAUST Repository

    Li, Peng

    2017-05-08

    The coexistence of ferromagnetic metallic phase and antiferromagnetic insulating phase in nanoscaled inhomogeneous perovskite oxides accounts for the colossal magnetoresistance. Although the model of spin-polarized electron transport across antiphase boundaries has been commonly employed to account for large magnetoresistance (MR) in ferrites, the magnetic anomalies, the two magnetic phases and enhanced molecular moment, are still unresolved. We observed a sizable MR in epitaxial spinel films (NiCo2O4-δ) that is much larger than that commonly observed in spinel ferrites. Detailed analysis reveals that this MR can be attributed to phase separation, in which the perfect ferrimagnetic metallic phase and ferrimagnetic insulating phase coexist. The magnetic insulating phase plays an important role in spin filtering in these phase separated spinel oxides, leading to a sizable MR effect. A spin filtering model based on Zeeman effect and direct tunneling is developed to account for MR of the phase separated films.

  11. Preparation of the electrochemically formed spinel-lithium manganese oxides

    Energy Technology Data Exchange (ETDEWEB)

    Katakura, Katsumi; Wada, Kohei; Kajiki, Yoshiyuki; Yamamoto, Akiko [Department of Chemical Engineering, Nara National College of Technology, 22 Yata-cho Yamotokoriyama, Nara 639-1080 (Japan); Ogumi, Zempachi [Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)

    2009-04-01

    Electrochemically formed spinel-lithium manganese oxides were synthesized from manganese hydroxides prepared by a cathodic electrochemical precipitation from various concentrations of manganese nitrate solutions. Two types of manganese hydroxides were formed from diluted and concentrated Mn(NO{sub 3}){sub 2} aqueous solutions. Uniform and equi-sized disk shaped Mn(OH){sub 2} crystals of 0.2-5 {mu}m in diameter were obtained on a Pt substrate after the electrochemical precipitation from lower concentration of ranging from 2 mmol dm{sup -3} to 2 mol dm{sup -3} Mn(NO{sub 3}){sub 2} aq., while the grass blade-like precipitate which is ascribed to manganese hydroxide with 20-80 {mu}m long and 1-5 {mu}m wide were formed from concentrated Mn(NO{sub 3}){sub 2} aq. Both manganese hydroxides gave the electrochemically formed spinel-LiMn{sub 2}O{sub 4} onto a Pt sheet, which is ready for electrochemical measurement, after calcination of the Li incorporated precipitate at 750 C without any additives. While the shape and size of the secondary particle frameworks (aggregates) of the electrochemically formed spinel-LiMn{sub 2}O{sub 4} can be controlled by the electrolysis conditions, the nanostructured primary crystals of 200 nm in diameter were obtained in all cases except that the fiber-like nanostructured spinel-LiMn{sub 2}O{sub 4} crystals with 200 nm in diameter were obtained from concentrated Mn(NO{sub 3}){sub 2} aq. Though these two types of electrochemically formed spinel-LiMn{sub 2}O{sub 4} showed well-shaped CVs even in higher scan rates, it would be suitable for high power density battery applications. These behaviors are assumed to be ascribed to the crystal size and shape of the processed spinel-LiMn{sub 2}O{sub 4}. (author)

  12. Detrital zircon study along the Tsangpo River, SE Tibet

    Science.gov (United States)

    Liang, Y.; Chung, S.; Liu, D.; O'Reilly, S. Y.; Chu, M.; Ji, J.; Song, B.; Pearson, N. J.

    2004-12-01

    The interactions among tectonic uplift, river erosion and alluvial deposition are fundamental processes that shape the landscape of the Himalayan-Tibetan orogen since its creation from early Cenozoic time. To better understand these processes around the eastern Himalayan Syntaxis, we conducted a study by systematic sampling riverbank sediments along the Tsangpo River, SE Tibet. Detrital zircons separated from the sediments were subjected to U-Pb dating by the SHRIMP II at the Beijing SHRIMP Center and then in-situ measurements of Hf isotope ratios using LA-MC-ICPMS at GEMOC. These results, together with U-Pb ages and Hf isotope data that we recently obtained for the Transhimalayan plutonic and surrounding basement rocks, allow a more quantitative examination of the provenance or protosource areas for the river sediments. Consequently, the percentage inputs from these source areas can be estimated. Our study indicates that, before the Tsangpo River flows into the Namche Barwa Syntaxis of the eastern Himalayas where the River forms a 180° Big Bend gorge and crosscuts the Himalayan sequences, the Gangdese batholith that crops out just north of the River appear to be an overwhelming source accounting for ˜50 % of the bank sediments. The Tethyan Himalayan sequences south of the River are the second important source, with an input of ˜25 %. The proportion of sediment supply changes after the River enters the Big Bend gorge and turns to south: ˜25 % of detrital zircons are derived from the Greater Himalayas so that the input from the Tethyan Himalayas decreases (< 10 %) despite those from the Gangdese batholith remains high ( ˜40 %). Comparing with the sediment budget of the Brahmaputra River in the downstream based on literature Sr, Nd and Os isotope information, which suggests dominant ( ˜90-60 %) but subordinate ( ˜10-40 %) contributions by the (Greater and Lesser) Himalayan and Tibetan (including Tethyan Himalayan) rocks, respectively, the change is interpreted

  13. Lithofacies control in detrital zircon provenance studies: Insights from the Cretaceous Methow basin, southern Canadian Cordillera

    Science.gov (United States)

    DeGraaff-Surpless, K.; Mahoney, J.B.; Wooden, J.L.; McWilliams, M.O.

    2003-01-01

    High-frequency sampling for detrital zircon analysis can provide a detailed record of fine-scale basin evolution by revealing the temporal and spatial variability of detrital zircon ages within clastic sedimentary successions. This investigation employed detailed sampling of two sedimentary successions in the Methow/Methow-Tyaughton basin of the southern Canadian Cordillera to characterize the heterogeneity of detrital zircon signatures within single lithofacies and assess the applicability of detrital zircon analysis in distinguishing fine-scale provenance changes not apparent in lithologic analysis of the strata. The Methow/Methow-Tyaughton basin contains two distinct stratigraphic sequences of middle Albian to Santonian clastic sedimentary rocks: submarine-fan deposits of the Harts Pass Formation/Jackass Mountain Group and fluvial deposits of the Winthrop Formation. Although both stratigraphic sequences displayed consistent ranges in detrital zircon ages on a broad scale, detailed sampling within each succession revealed heterogeneity in the detrital zircon age distributions that was systematic and predictable in the turbidite succession but unpredictable in the fluvial succession. These results suggest that a high-density sampling approach permits interpretation of finescale changes within a lithologically uniform turbiditic sedimentary succession, but heterogeneity within fluvial systems may be too large and unpredictable to permit accurate fine-scale characterization of the evolution of source regions. The robust composite detrital zircon age signature developed for these two successions permits comparison of the Methow/Methow-Tyaughton basin age signature with known plutonic source-rock ages from major plutonic belts throughout the Cretaceous North American margin. The Methow/Methow-Tyaughton basin detrital zircon age signature matches best with source regions in the southern Canadian Cordillera, requiring that the basin developed in close proximity to the

  14. Effect of mulitivalent cation dopants on lithium manganese spinel cathodes

    CSIR Research Space (South Africa)

    De Kock, A

    1998-02-01

    Full Text Available The aim of this investigation is to determine optimised spinel cathode compositions that can be used in lithium cells. The cycling stability of 4 V LixMn2O4 electrodes in lithium, flooded electrolyte glass cells has been improved by the addition...

  15. Effect of lapping slurry on critical cutting depth of spinel

    International Nuclear Information System (INIS)

    Wang, Zhan-kui; Wang, Zhuan-kui; Zhu, Yong-wei; Su, Jian-xiu

    2015-01-01

    Highlights: • Measured spinel wafers’ hardness and crack length in different slurries. • Evaluated the softened layer thickness in different slurries. • Discussed the effect of slurries on critical cutting depth of spinel. - Abstract: The critical cutting depth for lapping process is very important because it influences the mode of material removal. In this paper, a serial of microscopic indentation experiments were carried out for measuring spinel wafers’ hardness and crack length in different lapping slurries. Their critical cutting depth and fracture toughness were calculated. X-ray photoelectron spectroscopy (XPS) was also employed to study the surface chemical composition and softened layer thickness of wafers in different slurries. Experimental results indicate that the softened layers of spinel wafers are formed due to the corrosion of lapping slurries, which leads to a lower hardness and a larger fracture toughness of samples, and increases the critical cutting depth. Among them, the critical cutting depth in ethylene glycol solution is the largest and up to 21.8 nm. The increase of critical cutting depth is helpful to modify the surface quality of the work-piece being lapped via ductile removal mode instead of brittle fracture mode

  16. Nanocrystalline spinel ferrites by solid state reaction route

    Indian Academy of Sciences (India)

    Wintec

    Nanocrystalline spinel ferrites by solid state reaction route. T K KUNDU* and S MISHRA. Department of Physics, Visva-Bharati, Santiniketan 731 235, India. Abstract. Nanostructured NiFe2O4, MnFe2O4 and (NiZn)Fe2O4 were synthesized by aliovalent ion doping using conventional solid-state reaction route. With the ...

  17. Identification of Spinel Iron Oxide Nanoparticles by 57Fe NMR

    Directory of Open Access Journals (Sweden)

    SangGap Lee

    2011-12-01

    Full Text Available We have synthesized and studied monodisperse iron oxide nanoparticles of smaller than 10 nm to identify between the two spinel phases, magnetite and maghemite. It is shown that 57Fe NMR spectroscopy is a promising tool for distinguishing between the two phases.

  18. Complex Effects of Ecosystem Engineer Loss on Benthic Ecosystem Response to Detrital Macroalgae.

    Directory of Open Access Journals (Sweden)

    Francesca Rossi

    Full Text Available Ecosystem engineers change abiotic conditions, community assembly and ecosystem functioning. Consequently, their loss may modify thresholds of ecosystem response to disturbance and undermine ecosystem stability. This study investigates how loss of the bioturbating lugworm Arenicola marina modifies the response to macroalgal detrital enrichment of sediment biogeochemical properties, microphytobenthos and macrofauna assemblages. A field manipulative experiment was done on an intertidal sandflat (Oosterschelde estuary, The Netherlands. Lugworms were deliberately excluded from 1× m sediment plots and different amounts of detrital Ulva (0, 200 or 600 g Wet Weight were added twice. Sediment biogeochemistry changes were evaluated through benthic respiration, sediment organic carbon content and porewater inorganic carbon as well as detrital macroalgae remaining in the sediment one month after enrichment. Microalgal biomass and macrofauna composition were measured at the same time. Macroalgal carbon mineralization and transfer to the benthic consumers were also investigated during decomposition at low enrichment level (200 g WW. The interaction between lugworm exclusion and detrital enrichment did not modify sediment organic carbon or benthic respiration. Weak but significant changes were instead found for porewater inorganic carbon and microalgal biomass. Lugworm exclusion caused an increase of porewater carbon and a decrease of microalgal biomass, while detrital enrichment drove these values back to values typical of lugworm-dominated sediments. Lugworm exclusion also decreased the amount of macroalgae remaining into the sediment and accelerated detrital carbon mineralization and CO2 release to the water column. Eventually, the interaction between lugworm exclusion and detrital enrichment affected macrofauna abundance and diversity, which collapsed at high level of enrichment only when the lugworms were present. This study reveals that in nature the

  19. Complex Effects of Ecosystem Engineer Loss on Benthic Ecosystem Response to Detrital Macroalgae.

    Science.gov (United States)

    Rossi, Francesca; Gribsholt, Britta; Gazeau, Frederic; Di Santo, Valentina; Middelburg, Jack J

    2013-01-01

    Ecosystem engineers change abiotic conditions, community assembly and ecosystem functioning. Consequently, their loss may modify thresholds of ecosystem response to disturbance and undermine ecosystem stability. This study investigates how loss of the bioturbating lugworm Arenicola marina modifies the response to macroalgal detrital enrichment of sediment biogeochemical properties, microphytobenthos and macrofauna assemblages. A field manipulative experiment was done on an intertidal sandflat (Oosterschelde estuary, The Netherlands). Lugworms were deliberately excluded from 1× m sediment plots and different amounts of detrital Ulva (0, 200 or 600 g Wet Weight) were added twice. Sediment biogeochemistry changes were evaluated through benthic respiration, sediment organic carbon content and porewater inorganic carbon as well as detrital macroalgae remaining in the sediment one month after enrichment. Microalgal biomass and macrofauna composition were measured at the same time. Macroalgal carbon mineralization and transfer to the benthic consumers were also investigated during decomposition at low enrichment level (200 g WW). The interaction between lugworm exclusion and detrital enrichment did not modify sediment organic carbon or benthic respiration. Weak but significant changes were instead found for porewater inorganic carbon and microalgal biomass. Lugworm exclusion caused an increase of porewater carbon and a decrease of microalgal biomass, while detrital enrichment drove these values back to values typical of lugworm-dominated sediments. Lugworm exclusion also decreased the amount of macroalgae remaining into the sediment and accelerated detrital carbon mineralization and CO2 release to the water column. Eventually, the interaction between lugworm exclusion and detrital enrichment affected macrofauna abundance and diversity, which collapsed at high level of enrichment only when the lugworms were present. This study reveals that in nature the role of this

  20. Correlation of Brunhes detrital-layer stratigraphy into the North Atlantic from Orphan Knoll (Labrador Sea)

    Science.gov (United States)

    Channell, J. E.; Hodell, D. A.; Romero, O. E.; Hillaire-Marcel, C.; de Vernal, A.; Stoner, J. S.; Mazaud, A.; Roehl, U.

    2011-12-01

    IODP Site U1302-U1303, on the SE flank of Orphan Knoll (Labrador Sea), has a record of detrital layers that extends through most of the Brunhes Chron. The age model is built by tandem matching of relative paleointensity (RPI) and oxygen isotope data (δ18O) from Neogloboquadrina pachyderma (sin.) to reference records, indicating a mean Brunhes sedimentation rate of 14 cm/kyr. Sedimentation back to marine isotope stage (MIS) 18 is characterized by detrital layers that are detected by higher than background gamma-ray attenuation (GRA) density, peaks in X-ray fluorescence (XRF) indicators for detrital carbonate (Ca/Sr) and detrital silicate (Si/Sr), an ice-rafted debris (IRD) proxy (>106 μm), magnetic susceptibility, and magnetic grain-size peaks. The age model enables correlation of Site U1302/03 to IODP Site U1308 (re-drill of DSDP Site 609) in the heart of the central Atlantic IRD belt where an age model and a similar set of detrital-layer proxies have already been derived. Ages of Heinrich layers H1, H2, H4, H5 and H6 are within ~2 kyr at the two sites (H0, H3 and H5a are not observed at Site U1308), and agree with previous work at Orphan Knoll within ~3 kyr. At Site U1308, Brunhes detrital layers are restricted to peak glacials and glacial terminations back to MIS16, however, these same proxies at Site U1302/03 indicate detrital layers distributed throughout the record in both glacial and most interglacial stages. At Site U1302/03, we distinguish Heinrich-type layers in glacial stages, which are associated with IRD (some of which have near-synchronous analogues at Site U1308), from detrital layers within interglacial stages manifested by multiple detrital layer proxies (including Ca/Sr) but usually not associated with IRD, that may be attributed to a distinct depositional process, namely drainage and debris-flow events funneled down the nearby NAMOC (North Atlantic Mid-Ocean Channel).

  1. A method for evaluating basement exhumation histories from closure age distributions of detrital minerals

    International Nuclear Information System (INIS)

    Lovera, Oscar M.; Grove, Marty; Kimbrough, David L.; Abbott, Patrick L.

    1999-01-01

    We have developed a two-dimensional, thermokinetic model that predicts the closure age distributions of detrital minerals from pervasively intruded and differentially exhumed basement. Using this model, we outline a method to determine the denudation history of orogenic regions on the basis of closure age distributions in synorogenic to postorogenic forearc strata. At relatively high mean denudation rates of 0.5 km m.y.-1 sustained over millions of years, magmatic heating events have minimal influence upon the age distributions of detrital minerals such as K-feldspar that are moderately retentive of radiogenic Ar. At lower rates, however, the effects of batholith emplacement may be substantial. We have applied the approach to detrital K-feldspars from forearc strata derived from the deeply denuded Peninsular Ranges batholith (PRB). Agreement of the denudation history deduced from the detrital K-feldspar data with thermochronologic constraints from exposed PRB basement lead us to conclude that exhumation histories of magmatic arcs should be decipherable solely from closure age distributions of detrital minerals whose depositional age is known. (c) 1999 American Geophysical Union

  2. Moessbauer study of iron-cobalt-rhodium spinels

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, C D; Smith, P A; Karnes, C M; Shepard, W A [Ithaca Coll., NY (USA). Dept. of Physics

    1980-01-01

    Moessbauer source and absorber studies have been carried out on the spinel system CoFesub(x)Rhsub(2-x)O/sub 4/ for x 0.005, 0.3, 0.5, 1.0, 1.2 and 1.5. For 0.005 =< x =< 1.2, the cation distribution is normal with Co/sup 2 +/ on A sites. At x = 1.5, the distribution is nearly inverse. In the cases x = 0.005 and 0.3, iron on the B sites does not produce a quadrupole doublet indicating that the B sites are cubic which is contrary to the usual case in spinels.

  3. Origin of the low compressibility in hard nitride spinels

    DEFF Research Database (Denmark)

    Mori-Sánchez, P.; Marqués, M.; Beltrán, A.

    2003-01-01

    A microscopic investigation of first-principles electron densities of gamma-A(3)N(4) (A:C,Si,Ge) spinels reveals a clear relationship between the compressibility and the chemical bonding of these materials. Three striking findings emanate from this analysis: (i) the chemical graph is governed...... by a network of highly directional strong bonds with covalent character in gamma-C3N4 and different degrees of ionic polarization in gamma-Si3N4 and gamma-Ge3N4, (ii) nitrogen is the lowest compressible atom controlling the trend in the bulk modulus of the solids, and (iii) the group-IV counterions show strong...... site dependent compressibilities enhancing the difficulty in the synthesis of the spinel phases of these nitrides....

  4. Thermobarometry for spinel lherzolite xenoliths in alkali basalts

    Science.gov (United States)

    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

  5. Spinel-structured surface layers for facile Li ion transport and improved chemical stability of lithium manganese oxide spinel

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Hae Ri [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Department of Chemical and Biological Engineering, Korea University, 145, Anam-ro, Seongbuk-gu, Seoul 136-701 (Korea, Republic of); Seo, Hyo Ree; Lee, Boeun; Cho, Byung Won [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Lee, Kwan-Young [Department of Chemical and Biological Engineering, Korea University, 145, Anam-ro, Seongbuk-gu, Seoul 136-701 (Korea, Republic of); Oh, Si Hyoung, E-mail: sho74@kist.re.kr [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of)

    2017-01-15

    Graphical abstract: Strategically-designed spinel-structured nano-scale surface layer, LiM{sub x}Mn{sup IV}{sub 1−x}O{sub 4}, featuring a high Li{sup +} ion conductivity and a good chemical stability was applied on Al-doped LiMn{sub 2}O{sub 4} spinel for the drastic improvement of the electrochemical performance at the elevated temperature as a promising cathode material for lithium rechargeable batteries. - Highlights: • Spinel-structured surface layer with a high Li-ion conductivity and a good chemical stability was prepared. • Simple wet process was developed to apply nano-scale surface layer on aluminum doped lithium manganese oxide spinel. • The properties of nano-scale surface layer were characterized by analytical tools including GITT, HR-TEM and XAS. • Materials with surface coating layer exhibit an excellent electrochemical performance at the elevated temperature. - Abstract: Li-ion conducting spinel-structured oxide layer with a manganese oxidation state close to being tetravalent was prepared on aluminum-doped lithium manganese oxide spinel for improving the electrochemical performances at the elevated temperatures. This nanoscale surface layer provides a good ionic conduction path for lithium ion transport to the core and also serves as an excellent chemical barrier for protecting the high-capacity core material from manganese dissolution into the electrolyte. In this work, a simple wet process was employed to prepare thin LiAlMnO{sub 4} and LiMg{sub 0.5}Mn{sub 1.5}O{sub 4} layers on the surface of LiAl{sub 0.1}Mn{sub 1.9}O{sub 4}. X-ray absorption studies revealed an oxidation state close to tetravalent manganese on the surface layer of coated materials. Materials with these surface coating layers exhibited excellent capacity retentions superior to the bare material, without undermining the lithium ion transport characteristics and the high rate performances.

  6. Synthesis and magnetic properties of Zn Spinel ceramics

    Czech Academy of Sciences Publication Activity Database

    Huber, Š.; Sofer, Z.; Nádherný, L.; Jankovský, O.; Šimek, P.; Sedmidubský, D.; Maryško, Miroslav

    2013-01-01

    Roč. 57, č. 2 (2013), s. 162-166 ISSN 0862-5468 R&D Projects: GA ČR GA13-17538S; GA MŠk(CZ) 7AMB12FR019 Institutional support: RVO:68378271 Keywords : Zn spinel * synthesis * magnetic properties * antiferromagnet * bulk ZnO Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.434, year: 2013

  7. Cation disorder in high-dose, neutron-irradiated spinel

    International Nuclear Information System (INIS)

    Sickafus, K.E.; Larson, A.C.; Yu, N.; Nastasi, M.; Hollenberg, G.W.; Garner, F.A.; Bradt, R.C.

    1994-08-01

    The objective of this effort is to determine whether MgAl 2 O 4 spinel is a suitable ceramic for fusion applications. Here, the crystal structures of MgAl 2 O 4 spinel single crystals irradiated to high neutron fluences [>5·10 26 n/m 2 (E n > 0.1 MeV)] were examined by neutron diffraction. Crystal structure refinement of the highest dose sample indicated that the average scattering strength of the tetrahedral crystal sites decreased by ∼ 20% while increasing by ∼ 8% on octahedral sites. Since the neutron scattering length for Mg is considerably larger than for Al, this results is consistent with site exchange between Mg 2+ ions on tetrahedral sites and Al 3+ ions on octahedral sites. Least-squares refinements also indicated that, in all irradiated samples, at least 35% of Mg 2+ and Al 3+ ions in the crystal experienced disordering replacements. This retained dpa on the cation sublattices is the largest retained damage ever measured in an irradiated spinel material

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

    Science.gov (United States)

    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 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. On primitive mantle normalized diagrams the Arc Group Cr-spinels are characterized by a fractionated

  9. Cation distribution in spinels and its effect on activity pick-up and passivation behaviour

    International Nuclear Information System (INIS)

    Subramanian, H.; Velmurugan, S.; Narasimhan, S.V.

    2000-01-01

    Spinels are found to be the major corrosion products in the primary heat transport system or nuclear reactors. These corrosion products are activated in the core and are picked up on the deposited corrosion product oxides, which lead to the radiation field buildup on out of core surfaces. In order to mitigate this phenomenon, it is extremely important to understand the structural changes that take place in a spinel in the primary heat transport system. Most of the spinels found in reactor systems are mixed spinels. Cation distribution in tetrahedral and octahedral sites of these spinels, which is temperature dependent, will affect the pickup of active metal ions from solution into these spinels. Distribution of cations in simple spinels was estimated by minimising the Gibbs energy change for the migration of ions between tetrahedral and octahedral sites, based on the assumption that it is the configurational entropy change for the process that dominates the distribution. Cation distribution for mixed spinels was also calculated using the same method. Energy demand for the exchange of an aqueous ion with these spinels has been estimated. (author)

  10. A comparison between the irradiation damage response of spinel and zirconia due to Xe ion bombardment

    International Nuclear Information System (INIS)

    Sickafus, K.E.; Wetteland, C.J.; Baker, N.P.; Yu Ning; Devanathan, R.; Nastasi, M.; Bordes, N.

    1998-01-01

    The mechanical properties of Xe-implanted spinel and cubic zirconia surfaces, as determined by nano-indentation measurements, are distinct and the differences can be related to their microstructures. Upon Xe 2+ ion irradiation to high dose at cryogenic temperature (120 K), the Young's modulus of irradiated spinel falls dramatically until the modulus is only about 3/4 the un-irradiated value. The maximum modulus occurs concurrent with the formation of a metastable crystalline phase of spinel. The subsequent elastic softening at higher Xe 2+ doses is an indication of the onset of amorphization of the spinel. Xe-implanted zirconia surfaces behave differently, in all cases showing almost no change in elastic modulus with increasing Xe 2+ ion dose. This is consistent with microstructural observations of Xe-implanted zirconia crystals which, unlike spinel, show no change in crystal structure with increasing ion dose. The hardness of both spinel and zirconia increases slightly for low Xe 2+ ion doses. At higher doses, zirconia shows little change in hardness, while the hardness of the implanted spinel falls by more than a factor of two. The initial increase in hardness of both spinel and zirconia is consistent with point defect accumulation and the precipitation of small interstitial clusters, while the drop in hardness of spinel at high Xe 2+ ion doses is due to the formation of an amorphous phase. (orig.)

  11. Thermal decomposition of chromite spinel with chlorite admixture

    Energy Technology Data Exchange (ETDEWEB)

    Sanchez-Ramos, S. [Department of Analytical Chemistry, Faculty of Chemistry, University of Valencia, C/Doctor Moliner 50, 46100-Burjassot, Valencia (Spain); Escuela Superior de Ceramica, C/Ceramista A. Blat 22, 46940 Manises, Valencia (Spain); Domenech-Carbo, A. [Department of Analytical Chemistry, Faculty of Chemistry, University of Valencia, C/Doctor Moliner 50, 46100-Burjassot, Valencia (Spain); Gimeno-Adelantado, J.V. [Department of Analytical Chemistry, Faculty of Chemistry, University of Valencia, C/Doctor Moliner 50, 46100-Burjassot, Valencia (Spain)], E-mail: jose.v.gimeno@uv.es; Peris-Vicente, J.; Valle-Algarra, F.M. [Department of Analytical Chemistry, Faculty of Chemistry, University of Valencia, C/Doctor Moliner 50, 46100-Burjassot, Valencia (Spain)

    2008-09-30

    The behaviour of minerals in a South African chromite ore during the increasing of the temperature has been studied. Firstly, the changes produced during the ignition process have been examined by means of thermal and differential analysis (TGA-DTA) until 1200 deg. C. The characterization of the initial mineral and those obtained after heating at several temperatures in room atmosphere has been performed by X-ray diffraction (XRD). Moreover, voltammetric analyses have allowed to determine the variation of the iron oxidation degree in the studied materials. Light microscopy was applied to find more information about the different phases by their colour. During the heating, a wide range of complex exothermic and endothermic transformations take place. Decomposition compounds were identified, which were produced by heat decomposition, loss of structural water, element substitutions and oxygen absorptions and desorptions, caused mainly by the variation of the iron oxidation degree. The spinels of the chromite ore decompose in other spinels, with a partial change of the iron oxidation degree. From nearly 800 deg. C, chrome oxide (Cr{sub 2}O{sub 3}) comes off from the chromite forming another phase, and almost at 1000 deg. C, a slow decrease of weight was detected, caused among others to the formation of a magnetite phase. Simultaneously, the silicates undergo strong modifications, including decompositions and incorporation of iron (II) in their structure and producing other silicates stable at high temperatures, which modify the behaviour of the pure spinels. Moreover, at 1200 deg. C these silicates decompose to cristobalite (SiO{sub 2})

  12. Ceramic compositions based on nano forsterite/nano magnesium aluminate spinel powders

    International Nuclear Information System (INIS)

    Khattab, R.M.; Wahsh, M.M.S.; Khalil, N.M.

    2015-01-01

    According to the wide applications in the field of chemical and engineering industries, forsterite (Mg_2SiO_4)/spinel (MgAl_2O_4) ceramic compositions were the matter of interest of several research works during the last three decades. This work aims at preparation and characterization of improved ceramic bodies based on forsterite and spinel nano powders through controlling the forsterite and spinel contents in the prepared mixes. These prepared ceramic compositions have been investigated through measuring the densification parameters, cold crushing strength as well as volume resistively. Nano spinel was added from 0 to 30 mass% on expense of nano forsterite matrix and fired at 1550 °C for 2 h. The phase composition of the fired samples was examined using x-ray diffraction (XRD) technique. The microstructure of some selected samples was shown using scanning electron microscope (SEM). A pronounced improvement in the sintering, mechanical properties and volume resistively were achieved with increasing of nano spinel addition up to 15 mass%. This is due to the improvement in the matrix of the prepared forsterite/spinel bodies as a result of well distribution of spinel in the forsterite matrix as depicted by SEM analysis. - Highlights: • Ceramic compositions based on nano forsterite/nano-MgAl_2O_4 spinel were synthesized. • CCS was improved (333.78 MPa) through 15 mass% of nano-MgAl_2O_4 spinel addition. • Volume resistivity was enhanced to 203*10"1"3 Ohm cm with 15 mass% of spinel addition. • Beyond 15 mass% spinel, CCS and volume resistivity were decreased.

  13. Thermoluminescence of Stoichiometric Magnesium-Aluminium Spinel Defects

    International Nuclear Information System (INIS)

    Kobyakov, V.A.; Gritsina, V.T.; Kazarinov, Yu.G.; Volokitin, V.N.

    2005-01-01

    The investigations of thermoluminescence of spinel single crystals MgAl 2 O 4 after UV- and X-ray irradiation was provided by using method of self consisting heating. It was shown, that observed maxima at temperatures of ∼360 and ∼530 K in UV- and green ranges of spectra, respectively, are complex and consist of several strongly overlapping partial maxima. By using method of self consisting heating we have revealed the approximate position of partial maxima, which are included in maxima of ∼360 and ∼530 K, and for some partial maxima there was obtained the order of kinetics, activation energies, and frequency factors

  14. Determination of ferrous and total iron in refractory spinels

    Energy Technology Data Exchange (ETDEWEB)

    Amonette, J.E. [Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA 99352 (United States); Matyáš, J. [Material Science Department, Pacific Northwest National Laboratory, Richland, WA 99352 (United States)

    2016-03-03

    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 series 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 recommended 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. 0.03 wt% Fe) and total Fe values higher than obtained by ICP-AES analysis after decomposition by lithium metaborate/tetraborate fusion. 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. Formal comparisons of accuracy and precision were made with 13 existing methods. Accuracy for Fe(II) and total Fe was at or near the top of the group. Precision varied with the parameter used to measure it but was generally in the middle to upper part of the group for Fe(II) while that for total Fe ranged from the bottom of the group to near the top. - Highlights: • Refractory samples, such as spinels, are the most difficult for Fe redox analysis. • Oxidimetric(Ag{sup +})/colorimetric (phen) method allows analysis of a single

  15. Biogenic magnetite, detrital hematite, and relative paleointensity in Quaternary sediments from the Southwest Iberian Margin

    Science.gov (United States)

    Channell, J. E. T.; Hodell, D. A.; Margari, V.; Skinner, L. C.; Tzedakis, P. C.; Kesler, M. S.

    2013-08-01

    Magnetic properties of late Quaternary sediments on the SW Iberian Margin are dominated by bacterial magnetite, observed by transmission electron microscopy (TEM), with contributions from detrital titanomagnetite and hematite. Reactive hematite, together with low organic matter concentrations and the lack of sulfate reduction, lead to dissimilatory iron reduction and availability of Fe(II) for abundant magnetotactic bacteria. Magnetite grain-size proxies (κARM/κ and ARM/IRM) and S-ratios (sensitive to hematite) vary on stadial/interstadial timescales, contain orbital power, and mimic planktic δ18O. The detrital/biogenic magnetite ratio and hematite concentration are greater during stadials and glacial isotopic stages, reflecting increased detrital (magnetite) input during times of lowered sea level, coinciding with atmospheric conditions favoring hematitic dust supply. Magnetic susceptibility, on the other hand, has a very different response being sensitive to coarse detrital multidomain (MD) magnetite associated with ice-rafted debris (IRD). High susceptibility and/or magnetic grain-size coarsening, mark Heinrich stadials (HS), particularly HS2, HS3, HS4, HS5, HS6 and HS7, as well as older Heinrich-like detrital layers, indicating the sensitivity of this region to fluctuations in the position of the polar front. Relative paleointensity (RPI) records have well-constrained age models based on planktic δ18O correlation to ice-core chronologies, however, they differ from reference records (e.g. PISO) particularly in the vicinity of glacial maxima, mainly due to inefficient normalization of RPI records in intervals of enhanced hematite input.

  16. A new estimate of detrital redox-sensitive metal concentrations and variability in fluxes to marine sediments

    Science.gov (United States)

    Cole, Devon B.; Zhang, Shuang; Planavsky, Noah J.

    2017-10-01

    The enrichment and depletion of redox sensitive trace metals in marine sediments have been used extensively as paleoredox proxies. The trace metals in shale are comprised of both detrital (transported or particulate) and authigenic (precipitated, redox-driven) constituents, potentially complicating the use of this suite of proxies. Untangling the influence of these components is vital for the interpretation of enrichments, depletions, and isotopic signals of iron (Fe), chromium (Cr), uranium (U), and vanadium (V) observed in the rock record. Traditionally, a single crustal average is used as a cutoff for detrital input, and concentrations above or below this value are interpreted as redox derived authigenic enrichment or depletion, while authigenic isotopic signals are frequently corrected for an assumed detrital contribution. Building from an extensive study of soils across the continental United States - which upon transport will become marine sediments - and their elemental concentrations, we find large deviations from accepted crustal averages in redox-sensitive metals (Fe, Cr, U, V) compared to typical detrital tracers (Al, Ti, Sc, Th) and provide new estimates for detrital contributions to the ocean. The variability in these elemental ratios is present over large areas, comparable to the catchment-size of major rivers around the globe. This heterogeneity in detrital flux highlights the need for a reevaluation of how the detrital contribution is assessed in trace metal studies, and the use of confidence intervals rather than single average values, especially in local studies or in the case of small authigenic enrichments.

  17. Enhancement photocatalytic activity of spinel oxide (Co, Ni3O4 by combination with carbon nanotubes

    Directory of Open Access Journals (Sweden)

    Kahdum Bashaer J.

    2017-09-01

    Full Text Available In this study, some types of composites consisting of multi-walled carbon nanotubes (MWCNTs and spinel oxide (Co, Ni3O4 were synthesized by simple evaporation method. These composites were characterized by UV–Vis diffuse reflectance spectroscopy, X-rays diffraction(XRD, Scanning electron microscopy (SEM and specific surface area(SBET. The photocatalytic activity of the prepared composites was investigated by the following removal of Bismarck brown G (BBG dye from its aqueous solutions. The obtained results showed that using MWCNTs in combination with spinel oxide to produced composites (spinel/MWCNTs which succeeded in increasing the activity of spinel oxide and exhibited higher photocatalytic activity than spinel oxide alone. Also it was found that, multiwalled carbon nanotubes were successful in increasing the adsorption and improving the activity of photocatalytic degradation of Bismarck brown G dye(BBG. The obtained results showed that spinel/MWCNTs was more active in dye removal in comparison with each of spinel oxide and MWCNTs alone under the same reaction conditions. Also band gap energies for the prepared composites showed lower values in comparison with neat spinel. This point represents a promising observation as these composites can be excited using a lower energy radiation sources.

  18. On the use of spinel-based nuclear fuels for the transmutation of actinides

    International Nuclear Information System (INIS)

    Konings, R.J.M.; Bakker, K.; Boshoven, J.G.; Hein, H.; Huntelaar, M.E.; Zhang, H.; Meeldijk, J.D.; Woensdregt, C.F.

    1997-01-01

    The properties of spinel-based nuclear fuels for the transmutation of actinides are investigated. The results of laboratory experiments, thermodynamic calculations and irradiations in the High Flux Reactor (HFR) at Petten are presented, and allow us to evaluate the potential of spinel as an inert matrix for fuels and targets for transmutation. (author)

  19. Corundum-to-spinel structural phase transformation in alumina

    Energy Technology Data Exchange (ETDEWEB)

    Adachi, Shogo [Department of Materials Science and Engineering, Kyushu Institute of Technology, Fukuoka 804-8550 (Japan); Ishimaru, Manabu, E-mail: ishimaru@post.matsc.kyutech.ac.jp [Department of Materials Science and Engineering, Kyushu Institute of Technology, Fukuoka 804-8550 (Japan); Sina, Younes; McHargue, Carl J.; Sickafus, Kurt E. [Materials Science and Engineering Department, University of Tennessee, Knoxville, TN 37996-2200 (United States); Alves, Eduardo [Unit of Physics and Accelerators, Ion Beam Laboratory, Instituto Superior Técnico/Instituto Tecnológico e Nuclear, EN. 10 2686-953 Sacavém (Portugal)

    2015-09-01

    Several polymorphs exist in alumina (Al{sub 2}O{sub 3}), and they transform to a stable α-phase with a hexagonal corundum structure on thermal annealing. This structural change is irreversible as a function of temperature, and transformation of corundum to another metastable crystalline phase has never been observed by heat treatments. In this study, we irradiated single crystals of Al{sub 2}O{sub 3} with Zr ions and obtained an irradiated microstructure consisting of a buried α-Al{sub 2}O{sub 3} layer surrounded on top and bottom by layers of a defect cubic spinel Al{sub 2}O{sub 3} phase. We examined the thermal stability of this microstructure using transmission electron microscopy and X-ray diffraction. We found that the corundum phase completely transforms to the spinel phase following annealing at 1173 K for 1 h: the thermodynamically stable phase transforms to the metastable phase by heat treatments. We discuss this unusual structural change within the context of our results as well as previous observations.

  20. Evaluation of thermobarometry for spinel lherzolite fragments in alkali basalts

    Science.gov (United States)

    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

  1. Structural investigation of the spinel phase formed in fuel CRUD before and after zinc injection

    International Nuclear Information System (INIS)

    Chen, J.

    2002-01-01

    Spinel phase is an important constituent of fuel CRUD. Since it can accommodate 60 Co in its crystal structure, its stability in reactor water environment is crucial for the radioactivity control in LWR plants. With increasing curiosity about zinc injection technology, the mechanism of the interaction of zinc with the spinel has drawn much attention. This paper describes the crystal and microstructures of spinel phase in the fuel CRUD collected on four fuel rods of 1- and 5-cycle, respectively, from Barsebaeck 2 BWR before and after zinc injection operation. High precision X-ray powder diffraction technique has been applied to identify the phase compositions of fuel CRUD and to measure the cell length of the spinel phase formed. The results show that, after about 1-cycle zinc injection operation, the tenacious CRUD formed on the fresh fuel rod contains defective zinc oxide, in addition to hematite and spinel as commonly seen. Moreover, the phase ratio of spinel to hematite is much increased. The cell length of the spinel is increased accordingly, which is the direct evidence for the presence of zinc in the spinel structure. For the 5-cycle rod, however, neither zinc oxide nor any change in the phase ratio has been detected. The cell length of the spinel has been increased, in a less degree, however, as compared to that for the 1-cycle rod. The cell lengths of spinel are similar in both tenacious and loose CRUD layers, indicating that zinc was able to easily penetrate through the tenacious CRUD layer. (authors)

  2. Detrital zircon ages from southern Norway - implications for the Proterozoic evolution of the southwestern Baltic Shield

    Science.gov (United States)

    Knudsen, T.-L.; Andersen, T.; Whitehouse, M. J.; Vestin, J.

    An ion-microprobe (SIMS) U-Pb zircon dating study on four samples of Precambrian metasediments from the high-grade Bamble Sector, southern Norway, gives the first information on the timing of discrete crust-forming events in the SW part of the Baltic Shield. Recent Nd and Pb studies have indicated that the sources of the clastic metasediments in this area have crustal histories extending back to 1.7 to 2.1Ga, although there is no record of rocks older than 1.6Ga in southern Norway. The analysed metasediments are from a sequence of intercalated, centimetre to 10-metre wide units of quartzites, semi-metapelites, metapelites and mafic granulites. The zircons can be grouped in two morphological populations: (1) long prismatic; (2) rounded, often flattened. The BSE images reveal that both populations consist of oscillatory zoned, rounded and corroded cores (detrital grains of magmatic origin), surrounded by homogeneous rims (metamorphic overgrowths). The detrital zircons have 207Pb/206Pb ages between 1367 and 1939Ma, with frequency maxima in the range 1.85 to 1.70Ga and 1.60 to 1.50Ga. There is no correlation between crystal habit and age of the zircon. One resorbed, inner zircon core in a detrital grain is strongly discordant and gives a composite inner core-magmatic outer core 207Pb/206Pb age of 2383 Ma. Two discrete, unzoned zircons have 207Pb/206Pb ages of 1122 and 1133Ma, representing zircon growth during the Sveconorwegian high-grade metamorphism. Also the μm wide overgrowths, embayments in the detrital cores and apparent ``inner cores'' which represent secondary metamorphic zircon growth in deep embayments in detrital grains, are of Sveconorwegian age. The composite-detrital-metamorphic zircon analyses give generally discordant 206Pb/238U versus 207Pb/235U ratios and maximum 207Pb/206Pb ages of 1438Ma. These data demonstrate the existence of a protocrust of 1.7 to 2.0Ga in the southwestern part of the Baltic Shield, implying a break in the overall westward

  3. Detrital K-feldspar thermochronology of the Nanaimo Group: Characterization of Basement and Extraregional Basin Contributions

    Science.gov (United States)

    Isava, V.; Grove, M.; Mahoney, J. B.; Kimbrough, D. L.

    2016-12-01

    The Late Cretaceous-Early Paleogene Nanaimo Group covers the contact between Triassic basement Wrangellia terrane and the Jurassic-Cretaceous Coast Plutonic Complex (CPC) in southern British Columbia. Prior detrital zircon U-Pb and Hf studies indicate a change in sediment source for the Nanaimo basin, from the primitive CPC in Santonian-Early Campanian time to an isotopically evolved continental extraregional source during the late Campanian/Maastrictian. Two notably different areas have been proposed as potential source regions: (1) the Idaho/Boulder batholith and Belt Supergroup, and (2) the Mojave/Salinia segment of structurally disrupted late Cretaceous southern California margin. Single crystal 40Ar/39Ar laser fusion of ca. 100-200 grains apiece from seven detrital K-feldspar samples from Santonian-Maastrichtian strata of the northern Nanaimo Group constrain the history of the sediments' source regions. The two oldest samples, from the K-feldspar poor Comox and Extension Fms., display a monotonic increasing distribution of cooling ages 80-125 Ma that reflects shallow erosion of the CPC. In contrast, Late Campanian strata of the Cedar District and De Courcy Fms. exhibit a more pronounced cluster of cooling ages 80-95 Ma as well as a greater proportion of Jurassic ages that represent progressively deeper erosion of the CPC. Evidence for an extraregional sediment source appears abruptly in the Geoffrey Fm. by 72 Ma, matching the time of local-to-extraregional shift indicated in detrital zircon U-Pb studies. Over 90% of the detrital K-feldspars from these arkosic sandstones yield cooling ages of 70-80 Ma, with sparse older ages associated with the CPC. Samples from the successively younger Spray and Gabriola Fms. also yield >90% K-feldspar ages younger than 80 Ma and exhibit age maxima of 68 Ma and 65 Ma, respectively. These results are distinct from detrital zircon U-Pb and K-feldspar 40Ar/39Ar ages of the southern Sierra Nevada, Mojave/Salina, and northern

  4. Black and green pigments based on chromium-cobalt spinels

    Energy Technology Data Exchange (ETDEWEB)

    Eliziario, Sayonara A., E-mail: sayonaraea@iq.unesp.br [Departamento de Fisico-Quimica, Instituto de Quimica, UNESP - Univ Estadual Paulista, Araraquara, SP (Brazil); Departamento de Quimica, CCEN, Universidade Federal da Paraiba, Campus I, Joao Pessoa, PB (Brazil); Andrade, Jeferson M. de [Departamento de Quimica, CCEN, Universidade Federal da Paraiba, Campus I, Joao Pessoa, PB (Brazil); Lima, Severino J.G. [Departamento de Engenharia Mecanica, CT, Universidade Federal da Paraiba, Campus I, Joao Pessoa, PB (Brazil); Paskocimas, Carlos A. [Universidade Federal do Rio Grande do Norte, CT, Natal, RN (Brazil); Soledade, Luiz E.B. [Departamento de Quimica, CCEN, Universidade Federal da Paraiba, Campus I, Joao Pessoa, PB (Brazil); Hammer, P.; Longo, E. [Departamento de Fisico-Quimica, Instituto de Quimica, UNESP - Univ Estadual Paulista, Araraquara, SP (Brazil); Souza, Antonio G.; Santos, Ieda M.G. [Departamento de Quimica, CCEN, Universidade Federal da Paraiba, Campus I, Joao Pessoa, PB (Brazil)

    2011-09-15

    Highlights: {yields} Co(Co{sub 2-x}Cr{sub x})O{sub 4} powders with different chromium concentrations (x = 0, 0.25 and 1) were prepared by the polymeric precursor method. {yields} Co(CoCr)O{sub 4} and Co(Co{sub 1.75}Cr{sub 0.25})O{sub 4} displayed a dark color and CoCr{sub 2}O{sub 4} was green. {yields} The colors were related to the different oxidation states of Cr and Co. {yields} Cobalt enrichment result in an increasing presence of Co(III) and a decrease amount of Cr(VI). - Abstract: Chromium and cobalt oxides are widely used in the manufacture of industrial pigments. In this work, the Co(Co{sub 2-x}Cr{sub x})O{sub 4} powders with different chromium concentrations (x = 0, 0.25 and 1) were synthesized by the polymeric precursor method, heat treatment between 600 and 1000 deg. C. These powders were characterized by X-ray diffraction, infrared spectroscopy, colorimetry, UV-vis absorption and X-ray photoelectron spectroscopies. Even with the addition of chromium, the XRD patterns revealed that all powders crystallize in a single spinel cubic structure. The spinels with higher cobalt amount, Co(CoCr)O{sub 4} and Co(Co{sub 1.75}Cr{sub 0.25})O{sub 4}, displayed a dark color, without the Co{sup 3+} reduction observed in Co{sub 3}O{sub 4} between 900 and 950 deg. C. The spinel with higher chromium amount, CoCr{sub 2}O{sub 4}, was green. The colors were directly related to the occupation of tetrahedral and octahedral sites by the chromophores, as well as to the different oxidation states of chromium and cobalt. The different optical band gap values estimated from UV-vis spectra suggested the existence of intermediary energy levels within the band gap. X-ray photoelectron spectroscopy confirmed an increasing presence of Co(III) and a decreasing amount of Cr(VI) with cobalt enrichment.

  5. Detrital zircon geochronology and provenance of the Chubut Group in the northeast of Patagonia, Argentina

    Science.gov (United States)

    Navarro, Edgardo L.; Astini, Ricardo A.; Belousova, Elena; Guler, M. Verónica; Gehrels, George

    2015-11-01

    The Chubut Group constitutes the most widespread sedimentary unit in NE Patagonia, characterized by variable-energy fluvial deposits. U-Pb analysis of detrital zircons from two sections of the Chubut Group constraint the age of the oldest sedimentary rocks in the northeast of the Somuncurá - Cañadón Asfalto Basin. In the Cañadón Williams area, at San Jorge section, 20 km NW of Telsen locality, dating of 56 detrital zircons from a medium to coarse sandstone indicated a maximum depositional age of 109 ± 1 Ma (n = 4). These sandstones were interpreted to represent shallow channels, associated with a lacustrine system. In the Telsen locality, a laser ablation analysis of 115 detrital zircons from a medium to coarse-grained sandstone, from fluvial channel facies, yielded a maximum depositional age of ca. 106 ± 1 Ma (n = 8). Both ages are consistent with volcanic events of the Barremian to Albian age in the central Patagonian Andes Region. Cathodoluminescence images of zircons from the San Jorge sample suggest an igneous origin, which is further supported by Th/U values above 0.5 in most of the grains. The distribution of the statistical modes of the main age populations of detrital zircons for the two samples [182, 185 and 189 Ma for Telsen sample (T2S) and 181 ± 1 Ma for San Jorge sample (SJS)] matches the age of the volcanic Marifil Formation. The rocks of the Marifil Formation of these ages are exposed NE to SE of the study area. The abundance of zircons of similar Jurassic ages (n = 52 for SJS and n = 105 for T2S) and the external morphology of the zircons in the sample SJS, implies a close proximity of the source area. Suggestion that the Marifil Formation was the main provenance source is also supported by northeast-southeasterly paleocurrents measured at the San Jorge and Telsen sections.

  6. Detrital illite crystals identified from crystallite thickness measurements in siliciclastic sediments

    Science.gov (United States)

    Aldega, L.; Eberl, D.D.

    2005-01-01

    Illite crystals in siliciclastic sediments are heterogeneous assemblages of detrital material coming from various source rocks and, at paleotemperatures >70 ??C, of superimposed diagenetic modification in the parent sediment. We distinguished the relative proportions of 2M1 detrital illite and possible diagenetic 1Md + 1M illite by a combined analysis of crystal-size distribution and illite polytype quantification. We found that the proportions of 1Md + 1M and 2M1 illite could be determined from crystallite thickness measurements (BWA method, using the MudMaster program) by unmixing measured crystallite thickness distributions using theoretical and calculated log-normal and/or asymptotic distributions. The end-member components that we used to unmix the measured distributions were three asymptotic-shaped distributions (assumed to be the diagenetic component of the mixture, the 1Md + 1M polytypes) calculated using the Galoper program (Phase A was simulated using 500 crystals per cycle of nucleation and growth, Phase B = 333/cycle, and Phase C = 250/ cycle), and one theoretical log-normal distribution (Phase D, assumed to approximate the detrital 2M1 component of the mixture). In addition, quantitative polytype analysis was carried out using the RockJock software for comparison. The two techniques gave comparable results (r2 = 0.93), which indicates that the unmixing method permits one to calculate the proportion of illite polytypes and, therefore, the proportion of 2M1 detrital illite, from crystallite thickness measurements. The overall illite crystallite thicknesses in the samples were found to be a function of the relative proportions of thick 2M1 and thin 1Md + 1M illite. The percentage of illite layers in I-S mixed layers correlates with the mean crystallite thickness of the 1Md + 1M polytypes, indicating that these polytypes, rather than the 2M1 polytype, participate in I-S mixed layering.

  7. Groundwater budgets for Detrital, Hualapai, and Sacramento Valleys, Mohave County, Arizona, 2007-08

    Science.gov (United States)

    Garner, Bradley D.; Truini, Margot

    2011-01-01

    The United States Geological Survey, in cooperation with the Arizona Department of Water Resources, initiated an investigation of the hydrogeology and water resources of Detrital, Hualapai, and Sacramento Valleys in northwestern Arizona in 2005, and this report is part of that investigation. Water budgets were developed for Detrital, Hualapai, and Sacramento Valleys to provide a generalized understanding of the groundwater systems in this rural area that has shown some evidence of human-induced water-level declines. The valleys are within the Basin and Range physiographic province and consist of thick sequences of permeable alluvial sediment deposited into basins bounded by relatively less permeable igneous and metamorphic rocks. Long-term natural recharge rates (1940-2008) for the alluvial aquifers were estimated to be 1,400 acre-feet per year (acre-ft/yr) for Detrital Valley, 5,700 acre-ft/yr for Hualapai Valley, and 6,000 acre-ft/yr for Sacramento Valley. Natural discharge rates were assumed to be equal to natural recharge rates, on the basis of the assumption that all groundwater withdrawals to date have obtained water from groundwater storage. Groundwater withdrawals (2007-08) for the alluvial aquifers were less than 300 acre-ft/yr for Detrital Valley, about 9,800 acre-ft/yr for Hualapai Valley, and about 4,500 acre-ft/yr for Sacramento Valley. Incidental recharge from leaking water-supply pipes, septic systems, and wastewater-treatment plants accounted for about 35 percent of total recharge (2007-08) across the study area. Natural recharge and discharge values in this study were 24-50 percent higher than values in most previously published studies. Water budgets present a spatially and temporally "lumped" view of water resources and incorporate many sources of uncertainty in this study area where only limited data presently are available.

  8. The Origin of DIRT (Detrital Input and Removal Treatments): the Legacy of Dr. Francis D. Hole

    Science.gov (United States)

    Townsend, K. L.; Lajtha, K.; Caldwell, B.; Sollins, P.

    2007-12-01

    Soil organic matter (SOM) plays a key role in the cycling and retention of nitrogen and carbon within soil. Both above and belowground detrital inputs determine the nature and quantity of SOM. Studies on detrital impacts on SOM dynamics are underway at several LTER, ILTER and LTER-affiliated sites using a common experimental design, Detrital Input and Removal Treatments (DIRT). The concept for DIRT was originally based on experimental plots established at the University of Wisconsin Arboretum by Dr. Francis D. Hole in 1956 to study the effects of detrital inputs on pedogenesis. These plots are located on two forested sites and two prairie sites within the arboretum. Manipulations of the forested sites include double litter, no litter and removal of the O and A horizons. Manipulations of the prairie sites include harvest, mulch, bare and burn. These original treatments have largely been maintained since 1956. After 40 years of maintenance, there were significant differences in soil carbon between the double and no litter plots. The double litter plots had increased by nearly 30% while the no litter plots had decreased over 50%. The original DIRT plots are now 50 years old and have been re-sampled, where possible, for total carbon and nitrogen, labile and recalcitrant carbon fractions, net and gross nitrogen mineralization rates, and SOM bioavailability through CO2 respiration. The soils were fractionated by density to examine the role of carbon in each density fraction. The mean age of carbon in each fraction was determined by radiocarbon dating. This sampling and analysis is of special significance because it provides a glimpse into the future SOM trajectories for the new DIRT sites: Harvard Forest (MA), Bousson (PA), Andrews Experimental Forest (OR) and Sikfokut (Hungary).

  9. Macroalgal-dominated coastal detritic communities from the Western Mediterranean and the Northeastern Atlantic

    Directory of Open Access Journals (Sweden)

    S. JOHER

    2016-07-01

    Full Text Available This is a qualitative comparison of the distribution of macroalgal-dominated coastal detritic communities from the Western Mediterranean and the Northeastern Atlantic, based on our own data from the Balearic Islands (Western Mediterranean and available data from literature. The macroalgal-dominated coastal detritic bottoms from both regions could be distinguished by the presence of a high number of regional exclusive non-carbonated species, and the presence of a high number of maërl-forming species in the Mediterranean. Further, regional differences in the distribution of some exclusive species allowed the distinction of three zones in the Northeastern Atlantic (United Kingdom, French Brittany and Galicia, while no differences were found within the Western Mediterranean. However, the algal communities considered in the selected literature could not be qualitatively distinguished, and all the samples should be considered as maërl beds. Lithothamnion corallioides and Phymatolithon calcareum were the most widespread maërl forming species in the two regions, while in the Western Mediterranean Spongites fruticulosus was also very frequent. According to the differences in the species composition of the basal and erect strata of these beds, and also in their species richness, five different morphologies of macroalgal-dominated detritic bottoms could be distinguished. Their main characteristic species and their biogeographical distribution are detailed.

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

    Science.gov (United States)

    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.

  11. Some Spinel Oxide Compounds as Reducing Gas Sensors

    Directory of Open Access Journals (Sweden)

    Nicolae Rezlescu

    2007-04-01

    Full Text Available Four spinel ferrites, MFe2O4 (M = Cu, Cd, Zn and Ni, having various grain sizes (100 – 700 nm were prepared by sol-gel-selfcombustion and their sensing properties to reducing gases were investigated. The gas sensing characteristics were obtained by measuring the sensitivity as a function of various controlling factors, like operating temperature, composition and concentration of the gas, and finally the response time. The sensitivity of four ferrites to reducing gases like acetone, ethanol and LPG was been compared. It was revealed that CuFe2O4 is the most sensitive to LPG and ZnFe2O4 can be used as a sensor to selectively detect ethanol vapors in air. The strong interaction between ethanol and porous ZnFe2O4 can explain the selective sensitivity to ethanol and negligible sensitivity to the other reducing gases.

  12. Local probing spinel and perovskite complex magnetic systems

    CERN Document Server

    De Pinho Oliveira, Goncalo; Lima Lopes, Armandina Maria

    Materials with multifunctional physical properties are crucial for the modern society, especially those which display a strong coupling between magnetic, lattice and polar degrees of freedom. This by far unexploited capability promises new paradigm-shift technologies for cooling technologies, magnetic data storage, high-frequency magnetic devices, spintronics, and micro-electromechanical systems. Alongside with the understanding of the properties of these materials, the need to improve them and to make them smaller and more efficient is a current goal. Device miniaturization towards very high-density data storage stands also as a trend in modern science and technology. Here, the integration of several functions into one material system has become highly desirable. Research in this area has already highlighted complex magnetic materials with po- tential for multifunctional applications based on spinel type structures like CdMn2O4 or multiferroic CdCr2S4 or even RCrO3 with orthorhombically distorted perovskite ...

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

    Science.gov (United States)

    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 (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.

  14. The effect of Y2O3 addition on thermal shock behavior of magnesium aluminate spinel

    Directory of Open Access Journals (Sweden)

    Pošarac Milica

    2009-01-01

    Full Text Available The effect of yttria additive on the thermal shock behavior of magnesium aluminate spinel has been investigated. As a starting material we used spinel (MgAl2O4 obtained by the modified glycine nitrate procedure (MGNP. Sintered products were characterized in terms of phase analysis, densities, thermal shock, monitoring the damaged surface area in the refractory specimen during thermal shock and ultrasonic determination of the Dynamic Young modulus of elasticity. It was found that a new phase between yttria and alumina is formed, which improved thermal shock properties of the spinel refractories. Also densification of samples is enhanced by yttria addition.

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

    Science.gov (United States)

    Duty, Chad E.; Jellison, Jr., Gerald E.; Love, Lonnie J.; Moon, Ji Won; Phelps, Tommy J.; Ivanov, Ilia N.; Kim, Jongsu; Park, Jehong; Lauf, Robert

    2018-01-16

    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.

  16. Seawater and Detrital Marine Pb Isotopes as Monitors of Antarctic Weathering Following Ice Sheet Development

    Science.gov (United States)

    Fenn, C.; Martin, E. E.; Basak, C.

    2011-12-01

    Comparisons of seawater and detrital Pb isotopes from sites proximal to Antarctica at the Eocene/Oligocene transition (EOT) are being used to understand variations in continental weathering associated with the development of the East Antarctic Ice Sheet (EAIS). Previous work has shown that seawater and detrital archives yield similar isotopic values during Eocene warmth, which is interpreted to record congruent chemical weathering of the continent. In contrast, distinct isotopic values for the two phases at the EOT represents increased incongruent mechanical weathering during growth of the ice sheet. For this study we expanded beyond the initial glaciation at the EOT to determine whether less dramatic changes in ice volume and climate also produce variations in weathering and intensity that are recorded by seawater and detrital Pb isotopes. We collected Nd and Pb isotope data from extractions of Fe-Mn oxide coatings of bulk decarbonated marine sediments, which preserve seawater isotopic values, and from complete dissolutions of the remaining silicate fraction for Ocean Drilling Program Site 748 on Kerguelen Plateau (1300 m modern water depth). The data spans an interval of deglaciation from ~23.5-27 Ma documented by δ18O that has been equated to a ~30% decrease in ice volume on Antarctica (Pekar and Christie-Blick, 2008, Palaeogeogr., Palaeoclim., Palaeoecol.). Initial results from Site 748 include the first ɛNd values for intermediate waters in the Oligocene Southern Ocean and reveal a value of ~-8 over the entire 3.5 my interval, which is consistent with values reported for deep Indian Ocean sites at this time and similar to deeper Southern Ocean sites. Corresponding detrital ɛNd values are less radiogenic and decrease from -9 to -13 during the study interval. Detrital 206Pb/204Pb values also decrease during the warming interval, while seawater 206Pb/204Pb values increase. The decrease in detrital values indicates the composition of source materials entering

  17. Synthesis of high surface area spinel-type MgAl2O4 nanoparticles by

    Indian Academy of Sciences (India)

    68

    Spinel-type magnesium aluminate, MgAl2O4, is an effective refractory ceramic for ... such as good mechanical strength at high temperatures, high resistance to ... Materials. The starting chemicals with laboratory grade purity were provided ...

  18. Znx-1CuxMn2O4 spinels; synthesis, structural characterization and electrical evaluation

    International Nuclear Information System (INIS)

    Mendez M, F.; Lima, E.; Bosch, P.; Pfeiffer, H.; Gonzalez, F.

    2010-01-01

    This work presents the structural characterization and electrical evaluation of Zn x-1 Cu x Mn 2 O 4 spinels, which are materials presented as secondary phases into the vari stor ceramic systems. Samples were analyzed by X-ray diffraction, solid-state nuclear magnetic resonance, infrared spectroscopy, scanning electron microscopy and impedance spectroscopy. Although, the addition of copper to the ZnMn 2 O 4 spinel did not produce morphological changes, the structure and electrical behaviors changed considerably. Structurally, copper addition induced the formation of partial inverse spinels, and its addition increases significantly the electrical conductivity. Therefore, the formation of Zn x-1 Cu x Mn 2 O 4 spinels, as secondary phases into the vari stor materials, may compromise significantly the vari stor efficiency. (Author)

  19. Contributions of detrital subsidies to aboveground spiders during secondary succession, revealed by radiocarbon and stable isotope signatures.

    Science.gov (United States)

    Haraguchi, Takashi F; Uchida, Masao; Shibata, Yasuyuki; Tayasu, Ichiro

    2013-04-01

    Prey subsidies originating from detritus add nutrients and energy to arboreal communities. Measurement of this subsidy is required in the understanding of how food web dynamics respond to changes in surrounding environments. Shrub spiders are one of the key predators involved in food web coupling. We evaluate the effects of potential changes in prey availabilities during secondary succession on the contribution of subsidy from detrital food webs to shrub spiders and how different spider feeding guilds used the subsidy of prey from detrital food webs. We measured the relative importance of the subsidy for the spider feeding guilds, using the ratios of stable isotopes of C (δ(13)C), and N (δ(15)N) and C isotope discrimination (Δ(14)C). Diet age was calculated from Δ(14)C values, because old diet ages of spiders indicate that the spiders consume prey from detrital food sources. Dominant aerial prey (Diptera) had a distinctively old diet age compared with arboreal prey, which indicates that aerial prey were subsidized from detrital food webs. Sit-and-wait spiders tended to have an older diet age than active hunting spiders, which indicates that sit-and-wait spiders depended more on subsidies. Diet age varied only slightly for spiders in stands of different ages, indicating that rates at which spiders use grazing and detrital prey are probably determined more by foraging strategies and not by stand age. A dominance of sit-and-wait predators will lead to higher detrital subsidy inputs in shrub habitats. This study highlights the effect of shrub spider community structure (feeding guild composition) on the volume of the subsidy received from the detrital food web.

  20. Influence of graphite contamination on the optical properties of transparent spinel obtained by spark plasma sintering

    International Nuclear Information System (INIS)

    Bernard-Granger, G.; Benameur, N.; Guizard, C.; Nygren, M.

    2009-01-01

    The optical properties of transparent spinel sintered by spark plasma sintering have been investigated for incident electromagnetic radiations with wavelengths in the range 0.2-2 μm. It is shown that residual porosities and second-phase graphite particles have a strong influence on the in-line transmittance. Because of the graphite particles, the in-line transmittance measured does not approach that of monocrystalline spinel for wavelengths above 1 μm

  1. Degradation of polychlorinated biphenyls using mesoporous iron-based spinels

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Linyan; Su, Guijin, E-mail: gjsu@rcees.ac.cn; Zhang, Aiqian; Shi, Yali; Xia, Chaobo; Lu, Huijie; Li, Liewu; Liu, Sha; Zheng, Minghui

    2013-10-15

    Highlights: • The NiFe{sub 2}O{sub 4} had the highest activity in degradation of CB-209, followed by Fe{sub 3}O{sub 4}. • Hydroxyl species, organic acids, PCBs and chlorobenzenes were identified as products. • Three degradation reactions and one combination reaction competitively occurred. • Hydrodechlorination of CB-209 was more favored over Fe{sub 3}O{sub 4} than NiFe{sub 2}O{sub 4}. • Oxidation reaction of CB-209 was more favored over NiFe{sub 2}O{sub 4} than Fe{sub 3}O{sub 4}. -- Abstract: A series of mesoporous iron-based spinel materials were synthesized to degrade polychlorinated biphenyls (PCBs), with CB-209 being used as a model compound. The materials were characterized by X-ray powder diffraction (XRD), pore structure analysis, and X-ray photoelectron spectroscopy (XPS). A comparison of the dechlorination efficiencies (DEs) of the materials revealed that NiFe{sub 2}O{sub 4} had the highest DE, followed by Fe{sub 3}O{sub 4}. Newly produced polychlorinated biphenyls, chlorinated benzenes, hydroxyl species and organic acids were detected by gas chromatography–mass spectrometry, high performance liquid chromatography–mass spectrometry and ion chromatograph. Identification of the intermediate products indicates that three degradation pathways, hydrodechlorination, the breakage of C-C bridge bond and oxidative reaction, accompanied by one combination reaction, are competitively occurring over the iron-based spinels. The relative amounts of produced three NoCB isomers were illustrated by the C-Cl BDEs of CB-209 at meta-, para- and ortho-positions, and their energy gap between HOMO and LUMO. The consumption of the reactive oxygen species caused by the transformation of Fe{sub 3}O{sub 4} into Fe{sub 2}O{sub 3} in the Fe{sub 3}O{sub 4} reaction system, and the existence of the highly reactive O{sub 2}{sup −}· species in the NiFe{sub 2}O{sub 4} reaction system, could provide a reason why the oxidation reaction was more favored over NiFe{sub 2}O

  2. Detrital rutile geochemistry and thermometry from the Dabie orogen: Implications for source-sediment links in a UHPM terrane

    Science.gov (United States)

    Liu, Lei; Xiao, Yilin; Wörner, G.; Kronz, A.; Simon, K.; Hou, Zhenhui

    2014-08-01

    This study explores the potential of detrital rutile geochemistry and thermometry as a provenance tracer in rocks from the Central Dabie ultrahigh-pressure metamorphic (UHPM) zone in east-central China that formed during Triassic continental collision. Trace element data of 176 detrital rutile grains selected from local river sediments and 91 rutile grains from distinct bedrocks in the Shuanghe and Bixiling areas, obtained by both electron microprobe (EMP) and in situ LA-ICP-MS analyses, suggest that geochemical compositions and thermometry of detrital rutiles are comparable to those from their potential source rocks. After certification of the Cr-Nb discrimination method for the Central Dabie UHPM zone, we show that 29% of the detrital rutiles in the Shuanghe area were derived from metamafic sources whereas in the Bixiling area that it is up to 76%. Furthermore, the proportion of distinct types of detrital rutiles combined with modal abundances of rutile in metapelites and metamafic bedrocks can be used to estimate the proportion of different source lithologies. Based on this method the proportion of mafic source rocks was estimated to ∼10% at Shuanghe and >60% at Bixiling, respectively, which is consistent with the proportions of eclogite (the major rutile-bearing metamafic rock) distribution in the field. Therefore, the investigation of detrital rutiles is a potential way to evaluate the proportion of metamafic rocks and even to prospect for metamafic bodies in UHPM terranes. Zr-in-rutile temperatures were calculated at different pressures and compared with temperatures derived from rock-in rutiles and garnet-clinopyroxene Fe-Mg thermometers. Temperatures calculated for detrital rutiles range from 606 °C to 707 °C and 566 °C to 752 °C in Shuanghe and Bixiling, respectively, at P = 3 GPa with an average temperatures of ca. 630 °C for both areas. These temperature averages and ranges are similar to those calculated for rutiles from surrounding source rocks

  3. Inhomogeneous magnetic phase in Co–Al–O spinel nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Sato, K., E-mail: sato.koichi@nims.go.jp [National Institute for Materials Science, 2-1-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan); Naka, T., E-mail: naka.takashi@nims.go.jp [National Institute for Materials Science, 2-1-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan); Nakane, T. [National Institute for Materials Science, 2-1-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan); Rangappa, D. [International Advanced Research Centre for Powder Metallurgy and New Materials, Balapur PO, Hyderabad 500-005 (India); Takami, S. [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, Miyagi 980-8577 (Japan); Ohara, S. [Joining and Welding Research Institute, Osaka University, 11-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan); Adschiri, T. [WPI, Advanced Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, Miyagi 980-8577 (Japan)

    2014-01-15

    We report on the crystallographic structure and magnetism of 5-nm Co–Al–O spinel nanocrystals synthesized under supercritical hydrothermal conditions. Structural examination using powder X-ray diffraction and chemical analysis showed the composition of the sample to be Co{sub 0.47}Al{sub 2.36}O{sub 4} rather than the stoichiometric composition of CoAl{sub 2}O{sub 4}. The site occupancy of Co on the A-site forming the diamond lattice was 0.47, which is slightly larger than the site percolation limit. Magnetization measurements showed that magnetic clusters emerged below 40 K. At temperatures below 40 K, a Griffiths-phase-like inhomogeneous state appeared in the sample in which magnetic clusters and paramagnetic spins coexisted. The dc-paramagnetic and ac-susceptibilities exhibited an anomaly below 7 K. - Highlights: • The synthesized sample had an Al-rich structure described by Co{sub 0.47}Al{sub 2.36}O{sub 4}. • The site occupancy of Co at the A-site is larger than the site percolation limit of the A-site. • The non-linearity of the magnetization appeared at T<40 K. • The paramagnetic component showed a peak at 7 K. • An inhomogeneous state is established in our Co–Al oxide nanocrystals.

  4. Synthesis and magnetic properties of tin spinel ferrites doped manganese

    Science.gov (United States)

    El Moussaoui, H.; Mahfoud, T.; Habouti, S.; El Maalam, K.; Ben Ali, M.; Hamedoun, M.; Mounkachi, O.; Masrour, R.; Hlil, E. K.; Benyoussef, A.

    2016-05-01

    In this work we report the synthesis, the microstructural characterization and the magnetic properties of tin spinel ferrites doped manganese (Sn1-xMnxFe2O4 with x=0.25, 0.5, 0.75, and 1) nanoparticles prepared by co-precipitation method. The effect of annealing temperature on the structure, morphology and magnetic properties of Sn0.5Mn0.5Fe2O4 has been investigated. The synthesized nanoparticle sizes have been controlled between 4 and 9 nm, with uniform spherical morphology as confirmed by transmission electron microscopy (TEM). All the samples prepared possess single domain magnetic. The nanoparticles of Sn0.5Mn0.5Fe2O4 with 4 nm in diameter have a blocking temperature close to 100 K. In addition, the cation distribution obtained from the X-ray diffraction of this sample was confirmed by magnetic measurement. For the Sn1-xMnxFe2O4; (0≤x≤1) samples, the magnetization and coercive fields increase when the augmentation of Mn content increases. For x=0.5, such parameters decrease when the calcination temperature increases.

  5. Swelling of spinel after low-dose neutron irradiation

    International Nuclear Information System (INIS)

    Coghlan, W.A.; Clinard, F.W. Jr.; Itoh, N.; Greenwood, L.R.

    1986-01-01

    Swelling was determined in samples of single-crystal MgAl 2 O 4 spinel, irradiated to doses as high as 8 x 10 22 n/m 2 (E > 0.1 MeV) at approx. =50 0 C in the Omega West Reactor. Swelling effectively saturated at approx. =2 x 10 22 n/m 2 which corresponds to a damage level of only approx. =2 x 10 -3 dpa. In addition subsequent measurements after irradiation have revealed that the samples continued swelling for several weeks. These results imply that irradiation defects begin to interact by recombination and aggregation at low damage levels in this material at 50 0 C and perhaps continue to cluster at room temperature after irradiation. Rate equations have been employed to determine defect concentrations at saturation. Results to date show that the observed swelling is consistent with the number of surviving defects if swelling per Frenkel defect pair is taken to be one atomic volume

  6. Synthesis and optical property of zinc aluminate spinel cryogels

    Directory of Open Access Journals (Sweden)

    Lifen Su

    2016-06-01

    Full Text Available Zinc aluminate spinel cryogels with various molar ratio of Al/Zn are synthesized by sol–gel technology followed by vacuum freeze drying. The structures and optical properties are both found to be affected by the molar ratios of Al/Zn and annealed temperatures. The peaks of zinc oxide (ZnO and zinc dialuminum oxide (ZnAl2O4 are both obtained for the samples with more Zn content annealed at 750 °C or upward. The composites have a large surface area (137 m2/g with mesoporous structure after annealing at 750 °C. The SEM images reveal that the ZnAl2O4 crystals formed a multilayer structure with redundant ZnO particles which deposited on it. Furthermore, the maximum infrared reflectance is about 80% with an improvement of 35% in the infrared region after annealing at 950 °C compared with that of 450 °C, which indicates that these porous cryogels have a potential application as thermal insulating materials at a high temperature.

  7. Quantifying the influence of sediment source area sampling on detrital thermochronometer data

    Science.gov (United States)

    Whipp, D. M., Jr.; Ehlers, T. A.; Coutand, I.; Bookhagen, B.

    2014-12-01

    Detrital thermochronology offers a unique advantage over traditional bedrock thermochronology because of its sensitivity to sediment production and transportation to sample sites. In mountainous regions, modern fluvial sediment is often collected and dated to determine the past (105 to >107 year) exhumation history of the upstream drainage area. Though potentially powerful, the interpretation of detrital thermochronometer data derived from modern fluvial sediment is challenging because of spatial and temporal variations in sediment production and transport, and target mineral concentrations. Thermochronometer age prediction models provide a quantitative basis for data interpretation, but it can be difficult to separate variations in catchment bedrock ages from the effects of variable basin denudation and sediment transport. We present two examples of quantitative data interpretation using detrital thermochronometer data from the Himalaya, focusing on the influence of spatial and temporal variations in basin denudation on predicted age distributions. We combine age predictions from the 3D thermokinematic numerical model Pecube with simple models for sediment sampling in the upstream drainage basin area to assess the influence of variations in sediment production by different geomorphic processes or scaled by topographic metrics. We first consider a small catchment from the central Himalaya where bedrock landsliding appears to have affected the observed muscovite 40Ar/39Ar age distributions. Using a simple model of random landsliding with a power-law landslide frequency-area relationship we find that the sediment residence time in the catchment has a major influence on predicted age distributions. In the second case, we compare observed detrital apatite fission-track age distributions from 16 catchments in the Bhutan Himalaya to ages predicted using Pecube and scaled by various topographic metrics. Preliminary results suggest that predicted age distributions scaled

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

    Energy Technology Data Exchange (ETDEWEB)

    Liao, Chang-Zhong [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Department of Civil Engineering, The University of Hong Kong, Pokfulam Road, Hong Kong Special Administrative Region (China); Tang, Yuanyuan [School of Environmental Science and Engineering, South University of Science and Technology of China, Shenzhen 518055 (China); Lee, Po-Heng [Department of Civil & Environmental Engineering, The Hong Kong Polytechnic University, Hong Kong Special Administrative Region (China); Liu, Chengshuai, E-mail: csliu@soil.gd.cn [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550009 (China); Shih, Kaimin, E-mail: kshih@hku.hk [Department of Civil Engineering, The University of Hong Kong, Pokfulam Road, Hong Kong Special Administrative Region (China); Li, Fangbai [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China)

    2017-01-05

    Graphical abstract: Schematic illustration of detoxification and immobilization of chromite ore processing residue in spinel-based glass-ceramic matrix. All Cr(VI) species is reduced to Cr(III) and most chromium contents are incorporated into spinel structure where the residual chromium are resided in the glass networks. - Highlights: • COPR was detoxified and immobilized in a spinel-based glass-ceramic matrix. • Cr-rich crystalline phase was determined to be MgCr{sub 1.32}Fe{sub 0.19}Al{sub 0.49}O{sub 4} spinel. • The partitioning ratio of Cr into spinel in the glass-ceramic can be up to 77%. • No Cr(VI) was observed after conversion of COPR into a glass-ceramic. • TCLP results demonstrate the superiority of the final product in immobilizing Cr. - Abstract: 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{sub 1.32}Fe{sub 0.19}Al{sub 0.49}O{sub 4}. Using Rietveld quantitative X-ray diffraction analysis, we identified this final product is with the phases of spinel (3.5 wt.%), diopside (5.2 wt.%), and some amorphous contents (91.2 wt.%). 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{sub 2}O{sub 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

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

    International Nuclear Information System (INIS)

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

    2017-01-01

    Graphical abstract: Schematic illustration of detoxification and immobilization of chromite ore processing residue in spinel-based glass-ceramic matrix. All Cr(VI) species is reduced to Cr(III) and most chromium contents are incorporated into spinel structure where the residual chromium are resided in the glass networks. - Highlights: • COPR was detoxified and immobilized in a spinel-based glass-ceramic matrix. • Cr-rich crystalline phase was determined to be MgCr 1.32 Fe 0.19 Al 0.49 O 4 spinel. • The partitioning ratio of Cr into spinel in the glass-ceramic can be up to 77%. • No Cr(VI) was observed after conversion of COPR into a glass-ceramic. • TCLP results demonstrate the superiority of the final product in immobilizing Cr. - Abstract: 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 (3.5 wt.%), diopside (5.2 wt.%), and some amorphous contents (91.2 wt.%). 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

  10. Synthesis and magnetic properties of tin spinel ferrites doped manganese

    Energy Technology Data Exchange (ETDEWEB)

    El Moussaoui, H., E-mail: elmoussaoui.hassan@gmail.com [Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco); Mahfoud, T.; Habouti, S. [Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco); El Maalam, K.; Ben Ali, M. [Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco); Laboratoire of Magnetism and the Physics of the high Energies, URAC 12, Departement of physique, B.P. 1014, Faculty of science, Mohammed V University, Rabat (Morocco); Hamedoun, M.; Mounkachi, O. [Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco); Masrour, R. [Laboratory of Materials, Processes, Environment and Quality, Cady Ayyed University, National School of Applied Sciences, Route Sidi Bouzid – BP 63, 46000 Safi (Morocco); Hlil, E.K. [Institut Néel, CNRS-UJF, B.P. 166, 38042 Grenoble Cedex (France); Benyoussef, A. [Institute of Nanomaterials and Nanotechnologies, MAScIR, Rabat (Morocco); Laboratoire of Magnetism and the Physics of the high Energies, URAC 12, Departement of physique, B.P. 1014, Faculty of science, Mohammed V University, Rabat (Morocco); Hassan II Academy of Science and Technology, Rabat (Morocco)

    2016-05-01

    In this work we report the synthesis, the microstructural characterization and the magnetic properties of tin spinel ferrites doped manganese (Sn{sub 1−x}Mn{sub x}Fe{sub 2}O{sub 4} with x=0.25, 0.5, 0.75, and 1) nanoparticles prepared by co-precipitation method. The effect of annealing temperature on the structure, morphology and magnetic properties of Sn{sub 0.5}Mn{sub 0.5}Fe{sub 2}O{sub 4} has been investigated. The synthesized nanoparticle sizes have been controlled between 4 and 9 nm, with uniform spherical morphology as confirmed by transmission electron microscopy (TEM). All the samples prepared possess single domain magnetic. The nanoparticles of Sn{sub 0.5}Mn{sub 0.5}Fe{sub 2}O{sub 4} with 4 nm in diameter have a blocking temperature close to 100 K. In addition, the cation distribution obtained from the X-ray diffraction of this sample was confirmed by magnetic measurement. For the Sn{sub 1−x}Mn{sub x}Fe{sub 2}O{sub 4}; (0≤x≤1) samples, the magnetization and coercive fields increase when the augmentation of Mn content increases. For x=0.5, such parameters decrease when the calcination temperature increases. - Highlights: • We have studied the microstructural and the magnetic properties of Sn{sub 1-x}MnxFe{sub 2}O{sub 4}. • The nanoparticles of Sn{sub 0.5}Mn{sub 0.5}Fe{sub 2}O{sub 4} have a blocking temperature around 100 K. • The Ms and Hc increase with the augmentation of Mn content.

  11. Syndeformation Chrome Spinels Inclusions in the Plastically Deformed Olivine Aggregates (Kraka Ophiolites, the Southern Urals

    Directory of Open Access Journals (Sweden)

    D. E. Saveliev

    2015-12-01

    Full Text Available This article presents the results of structural, petrographic, mineralogical and chemical studies of dunite veinlets in spinel peridotite from the Kraka ophiolites. It is demonstrated that plastic deformation of polycrystalline olivine, which form dunite, was accompanied by precipitation of impurities (aluminum and chrome as newly formed chrome spinels. The thinnest acicular inclusions of 0.3-0.5 micron thick are aligned in olivine grains along [010] axis. Bigger elongated irregular chrome spinel grains usually occur along grain and sub-grain olivine boundaries, and, occasionally, inside the grains along [100] axis. Alteration from the fine xenomorphic grains of chrome spinels to the bigger idiomorphic crystals was observed. Analogically to dynamic ageing (dispersion hardening in metals, the structural and chemical alterations in dunites are interpreted as deformation induced segregation of impurities. It is suggested that the euhedral chrome spinel grains typical for ophiolitic dunites were formed by coalescence and spheroidization. This process may be a key factor in the formation of ophiolitic chrome ore deposits.

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

    Science.gov (United States)

    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.

  13. U-Pb ages of detrital zircon from Pegasus Group, Stewart Island

    International Nuclear Information System (INIS)

    Walker, N.; Tulloch, A.J.; Allibone, A.

    1998-01-01

    Stewart Island (New Zealand) is relatively unaffected by Cenozoic deformation related to the present-day plate boundary and has thus been a locale of investigations that focus on the relationship between Mesozoic continental margin magmatic rocks and the Western Province (WP) of NZ. Pegasus Group metasedimentary rocks represent the only candidate for WP equivalents on Stewart Island. We measured U-Pb and 207 Pb / 206 Pb ages of detrital zircons from the Pegasus Group in an effort to validate the correlation with the WP. On SI, Pegasus Group is exposed over a small area in the southern Tin Range where it forms amphibolite facies roof pendants and screens among plutons of mid Paleozoic to mid Cretaceous age. Mica schists predominate, with lesser amounts of psammite and metaquartzite and rare calcareous schist and amphibolite. Zircons were extracted from metaquarzite and 24 grains were chosen on the basis of morphology for geochronologic investigation. Sixteen single crystals were dated by U-Pb TIMS; 8 additional grains were studied by the total evaporation method described by Kober. Despite vigorous air abrasion prior to processing, the 16 grains measured by conventional U-Pb TIMS yielded slightly normally discordant ages that we interpret to reflect minor Pb-loss. The 8 grains studied by the total evaporation method yielded more than four analytically identical /sup 207 Pb / 206 Pb ages within each grain at progressively higher temperatures (1515-1580 degrees C) of evaporation. The results permit the following general conclusions: 1) the age range of 420-2700 Ma is grossly similar to that reported from the Greenland Group/Victoria Paragneiss (Ireland 1992) of the Buller Terrane, WP; 2) the zircon population is dominantly 530-680 Ma but a subsidiary population is 900-1100 Ma; 3) no zircons with ages that match the timing of the Ross Orogen (530-480 Ma) were identified; 4) two grains of 420 Ma and a 453 Ma are probably too young for the paleontogically

  14. Provenance of the lower Miocene of the Gulf of Mexico from detrital zircon double dating

    Science.gov (United States)

    xu, J.

    2013-12-01

    The lower Miocene interval of the Gulf of Mexico (GOM) has recently gained increasing attention from oil and gas industry due to its hydrocarbon potential below the salt canopy. However, it has been less well studied than both the underlying Oligocene and overlying middle Miocene strata. The lower Miocene worldwide is a transitional period of tectonic, climatic, and oceanographic change. In particular, it is a period of major tectonic reorganization in the western interior of North America (Rocky Mountains), involving a shift from the Oligocene thermal phase, with abundant volcanic activity recorded in the thick Frio/Vicksburg succession of the GOM, to the Miocene Basin-Range extensional phase. Climatic conditions also changed from a relatively arid Oligocene to wetter Miocene, resulting in increased sediment yields from exhumed tectonic structures. Previous provenance studies used proportions of quartz, feldspar and lithic fragments and consideration of likely river courses through known paleogeomorphological elements. Only limited detrital zircon (DZ) U-Pb studies on Paleocene strata have been undertaken and there has been no previous U-Pb and (U-Th)/He double dating in the GOM. In this study we apply the latest analytical approaches, such as DZ U-Pb dating to gain robust source terranes ages and more fully elucidate the complex sediment provenance and dispersal history of GOM. We also employ DZ (U-Th)/He (ZHe) dating, combined with DZ U-Pb, to not only define sedimentary provenance but also the exhumation histories of detrital source regions. Samples of lower Miocene outcrop exposures in Texas and Louisiana have been collected to discriminate the varied tectonic and drainage system changes across the basin in lateral. In addition, samples from the Eocene, Oligocene and middle Miocene have been obtained to reveal vertical shift of source terranes contributions. Our initial age data show detrital zircons of lower Miocene sediments come from a wide range of source

  15. Spinels as cathodes for the electrochemical reduction of O2 and NO

    DEFF Research Database (Denmark)

    Simonsen, Vibe Louise Ernlund; Find, D.; Lilliedal, M.

    2007-01-01

    the largest difference in activity between reduction of oxygen and the reduction of nitric oxide, the activity being highest for the reduction of nitric oxide. The material is probably not stable when polarised cathodically. However it seems that the electrode material can be regenerated upon oxidation. NiFe2......Spinels were synthesised and investigated as electro-catalyst for the electrochemical reduction of oxygen and nitric oxide using cyclic voltammetry and cone shaped electrodes. The following four spinels were investigated; CoFe2O4, NiFe2O4, CuFe2O4 and Co3O4. The composition CuFe2O4 revealed......O4 is also more active for the reduction of nitric oxide than for the reduction of oxygen, whereas the cobalt containing spinels have a higher activity for the reduction of oxygen than for the reduction of nitric oxide....

  16. Chemical synthesis of nanocrystalline magnesium aluminate spinel via nitrate-citrate combustion route

    International Nuclear Information System (INIS)

    Saberi, Ali; Golestani-Fard, Farhad; Sarpoolaky, Hosein; Willert-Porada, Monika; Gerdes, Thorsten; Simon, Reinhard

    2008-01-01

    Nanocrystalline magnesium aluminate spinel (MgAl 2 O 4 ) was synthesized using metal nitrates, citric acid and ammonium solutions. The precursor and the calcined powders at different temperatures were characterized by X-ray diffraction (XRD), simultaneous thermal analysis (STA), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The combustion mechanism was also studied by a quadrupole mass spectrometer (QMS) which coupled to STA. The generated heat through the combustion of the mixture of ammonium nitrate and citrate based complexes decreased the synthesis temperature of MgAl 2 O 4 spinel. The synthesized MgAl 2 O 4 spinel at 900 deg. C has faced shape with crystallite size in the range of 18-24 nm

  17. Spatial distribution of detrital resources determines the outcome of competition between bacteria and a facultative detritivorous worm

    NARCIS (Netherlands)

    Van Nugteren, P.; Herman, P.M.J.; Moodley, L.; Middelburg, J.J.; Vos, M.; Heip, C.H.R.

    2009-01-01

    Macrobenthic deposit feeders and bacteria compete for the same detrital food resources. We hypothesize that the spatial scale at which food is distributed in the sediment is an important factor determining the outcome of this competition. Macrobenthic deposit feeders are better adapted for fast

  18. Bacterial traits, organism mass, and numerical abundance in the detrital soil food web of Dutch agricultural grasslands

    NARCIS (Netherlands)

    Mulder, C.; Cohen, J.E.; Setälä, H.; Bloem, J.; Breure, A.M.

    2005-01-01

    This paper compares responses to environmental stress of the ecophysiological traits of organisms in the detrital soil food webs of grasslands in the Netherlands, using the relationship between average body mass M and numerical abundance N. The microbial biomass and biodiversity of belowground fauna

  19. Storage and export of organic matter in a headwater stream: responses to long-term detrital manipulations

    Science.gov (United States)

    Sue L. Eggert; J. Bruce Wallace; Judy L. Meyer; Jackson R. Webster

    2012-01-01

    Riparian habitats provide organic matter inputs that influence stream biota and ecosystem processes in forested watersheds. Over a 13-yr period, we examined the effects of litter exclusion, small- and large-wood removal, and the addition of leaf species of varying detrital quality on organic matter standing crop and export of organic and inorganic particles in a high-...

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

    Energy Technology Data Exchange (ETDEWEB)

    Farid, Hafiz Muhammad Tahir, E-mail: tahirfaridbzu@gmail.com [Department of Physics, Bahauddin Zakariya, University Multan, 60800 (Pakistan); Ahmad, Ishtiaq; Ali, Irshad [Department of Physics, Bahauddin Zakariya, University Multan, 60800 (Pakistan); Ramay, Shahid M. [College of Science, Physics and Astronomy Department, King Saud University, P.O. Box 2455, 11451 Riyadh (Saudi Arabia); Mahmood, Asif [Chemical Engineering Department, College of Engineering, King Saud University, Riyadh (Saudi Arabia); Murtaza, G. [Centre for Advanced Studies in Physics, GC University, Lahore 5400 (Pakistan)

    2017-07-15

    Highlights: • Magnesium based spinel ferrites were successfully synthesized by sol-gel method. • Dielectric constant shows the normal spinel ferrites behavior. • The dc conductivity are found to decrease with increasing temperature. • The samples with low conductivity have high values of activation energy. • The Impedance decreases with increasing frequency of applied field. - Abstract: Spinel ferrites with nominal composition MgPr{sub y}Fe{sub 2−y}O{sub 4} (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 MgFe{sub 2}O{sub 4} 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.

  1. High energy density layered-spinel hybrid cathodes for lithium ion rechargeable batteries

    Energy Technology Data Exchange (ETDEWEB)

    Basu, S., E-mail: sbasumajumder@yahoo.com [Department of Physics, Indian Institute of Technology Kharagpur, Kharagpur 721 302 (India); Dahiya, P.P.; Akhtar, Mainul [Materials Science Center, Indian Institute of Technology Kharagpur, Kharagpur 721 302 (India); Ray, S.K. [Department of Physics, Indian Institute of Technology Kharagpur, Kharagpur 721 302 (India); Chang, J.K. [Institute of Materials Science and Engineering, National Central University, Taiwan (China); Majumder, S.B. [Materials Science Center, Indian Institute of Technology Kharagpur, Kharagpur 721 302 (India)

    2016-11-15

    Highlights: • Structural integration of layered domains in spinel matrix of the composite particles. • Highest discharge capacity (275 mAh g{sup −1}) in composite with 30.0 mole% Li{sub 2}MnO{sub 3}. • Reasonably good rate capability of layered-spinel composite cathode. • Capacity fading with cycling is related to cubic to tetragonal structural phase transition. - Abstract: High energy density Li{sub 2}MnO{sub 3} (layered)–LiMn{sub 1.5}Ni{sub 0.5}O{sub 4} (spinel) composite cathodes have been synthesized using auto-combustion route. Rietveld refinements together with the analyses of high resolution transmission electron micrographs confirm the structural integration of Li{sub 2}MnO{sub 3} nano-domains into the LiMn{sub 1.5}Ni{sub 0.5}O{sub 4} matrix of the composite cathodes. The discharge capacity of the composite cathodes are due to the intercalation of Li{sup +} ion in the tetrahedral (8a) and octahedral (16c) sites of the spinel component and also the insertion of Li{sup +} in the freshly prepared MnO{sub 2} lattice, formed after Li{sub 2}O extraction from the Li{sub 2}MnO{sub 3} domains. The capacity fading of the composite cathodes are explained to be due to the layered to spinel transition of the Li{sub 2}MnO{sub 3} component and Li{sup +} insertion into the octahedral site of the spinel lattices which trigger cubic to tetragonal phase transition resulting volume expansion which eventually retard the Li{sup +} intercalation with cycling.

  2. Direct observation of cation distributions of ideal inverse spinel CoFe2O4 nanofibres and correlated magnetic properties

    KAUST Repository

    Zeng, Xue; Zhang, Junwei; Zhu, Shimeng; Deng, Xia; Ma, Hongbin; Zhang, Junli; Zhang, Qiang; Li, Peng; Xue, Desheng; Mellors, Nigel J; Zhang, Xixiang; Peng, Yong

    2017-01-01

    multiferroic heterostructures. Although we know that the distribution of cations (Fe3+ and Co2+) in a spinel structure governs its magnetic properties, their distribution in the so-called ideal inverse spinel structure of a ferrite, CoFe2O4, has not yet been

  3. Detrital and early chemical remanent magnetization in redbeds and their rock magnetic signature: Zicapa Formation, southern Mexico

    Science.gov (United States)

    Sierra-Rojas, Maria Isabel; Molina-Garza, Roberto Stanley

    2018-06-01

    Poles from continental redbeds are a large fraction of the world's palaeomagnetic database. Nonetheless, the time of acquisition and origin of the remanent magnetization of redbeds has been long debated. We report palaeomagnetic data, rock magnetic data and microscope observations for Lower Cretaceous redbeds in southern Mexico. These data allow us to discriminate between the hysteresis properties of remanent magnetizations of detrital and chemical origin, and to establish the early origin of a chemical remanence. Red sandstones of the Zicapa Formation contain a multicomponent remanence revealed by thermal demagnetization, and consisting of three stable components with partially overlapping laboratory unblocking temperatures of 600 °C, (low, intermediate and high temperature, respectively). They are interpreted as a viscous remanence residing in detrital magnetite, a chemical remanence residing in authigenic hematite and a depositional remanence residing in detrital hematite, respectively. The low-temperature component is nearly parallel to the recent dipole field. The tilt-corrected overall site means of the intermediate (chemical) and high temperature (depositional) components are indistinguishable (Dec = 282.0°, Inc = 12.4°, k = 13.33, α95 = 10.1°, N = 17, for the intermediate temperature; and Dec = 272.5°, Inc = 16.5°, k = 14.04, α95 = 11, N = 14, for the high temperature). Elongation/inclination analysis suggests that depositional and chemical components require applying an f = factor of approximately 0.4. Both of these components define a magnetic polarity zonation, but the polarity of the chemical and detrital components may or may not be the same. The chemical remanence coincides, more often than not, with the polarity of the depositional remanence of the overlying (younger) strata, suggesting a delay in remanence acquisition of tens to a few hundred ka for the chemical component. Pigmentary and detrital haematite were recognized with microscopic

  4. Detrital processing in streams exposed to acidic precipitation in the Central Appalachian Mountains

    International Nuclear Information System (INIS)

    Meegan, S.K.; Perry, S.A.; Perry, W.B.

    1996-01-01

    Continuing high rates of acidic deposition in the eastern United States may lead to long-term effects on stream communities, because sensitive catchments are continuing to lose anions and cations. A two-year study of the effects of pH and associated water chemistry variables on detrital processing in three streams with different bedrock geology in the Monongahela National Forest, West Virginia were investigated. Leaf pack processing rates and macroinvertebrate colonization and microbial biomass (ATP concentration) on the packs in the three stream were compared. It was found that macroinvertebrate and microbial communities differed both among streams that differed in their capacity to buffer the effects of acidic precipitation and among years in the same stream; these differences in biotic communities were not large enough to affect rates of leaf processing between the two years of the study, but they did significantly affect processing rates between acidic and circumneutral streams

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

    Science.gov (United States)

    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 LiMn2-y-zLiyMzO4 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.

  6. The influence of γ-irradiation on electrophysical properties of spinel-based oxide ceramics

    International Nuclear Information System (INIS)

    Kovalskiy, A.P.; Shpotyuk, O.I.; Hadzaman, I.V.; Mrooz, O.Ya.; Vakiv, M.M.

    2000-01-01

    The influence of 60 Co γ-irradiation with 1.25 MeV average energy and 1 MGy absorbed dose on electrophysical properties of Cu-, Ni-, Co- and Mn-based spinel ceramic materials in the Cu x Ni 1-x-y Co 2y Mn 2-y O 4 (0,1≤x≤0,8;0,1≤y≤0,9-x) system is investigated. The γ-induced increasing of the electrical resistance is observed for the investigated samples of various compositions. It is supposed that these changes are explained by cationic redistribution in the spinel sublattices of the ceramics

  7. Investigation of spinel-related and orthorhombic LiMNO2 cathodes for rechargeable lithium batteries

    CSIR Research Space (South Africa)

    Gummow, RJ

    1994-05-01

    Full Text Available ~ and with carbon at 600~ have been evaluated in rechargeable lithium cells. The cathodes which initially have a composition close to LiMnO2 contain structures related to the lithiated-spinel phase Li2\\[Mn2104 and/or orthorhombic Li... the cathode structure to yield an "over-discharged" state which is possible, for example, with a Lix\\[Mn2104 spinel cathode. 7 Lix\\[Mn2\\]O4 operates at approximately 4 V vs. lithium over the range 0 < x -< 1 and has a...

  8. Spinel dissolution via addition of glass forming chemicals. Results of preliminary experiments

    Energy Technology Data Exchange (ETDEWEB)

    Fox, K. M. [Savannah River Site (SRS), Aiken, SC (United States); Johnson, F. C. [Savannah River Site (SRS), Aiken, SC (United States)

    2015-11-01

    Increased loading of high level waste in glass can lead to crystallization within the glass. Some crystalline species, such as spinel, have no practical impact on the chemical durability of the glass, and therefore may be acceptable from both a processing and a product performance standpoint. In order to operate a melter with a controlled amount of crystallization, options must be developed for remediating an unacceptable accumulation of crystals. This report describes preliminary experiments designed to evaluate the ability to dissolve spinel crystals in simulated waste glass melts via the addition of glass forming chemicals (GFCs).

  9. Changes in biogenic and detrital fluxes across the last two glacial terminations at the Shatsky Rise

    Science.gov (United States)

    Bradtmiller, L. I.; Kinsley, C. W.; McGee, D.; Ford, H. L.; Perala-Dewey, J.; Zhang, Y.

    2017-12-01

    The Shatsky Rise is located within strong gradients in SST and biological productivity between the subtropical and subarctic Pacific gyres. The region is highly sensitive to changes in atmospheric and oceanic circulation on glacial-interglacial timescales, which affect the delivery of Fe-bearing dust and other major nutrients, respectively. Here we use a range of proxies in an attempt to determine the effects of changes in westerly winds and gyre boundaries on dust delivery and biological productivity. We present 230Th-normalized fluxes of opal, Corg, CaCO3, and detrital material at ODP Site 1208 over the last two glacial terminations, extending to 145ka. Opal, Corg, and carbonate are products of surface biological productivity, while most detrital material at this site arrives in the form of windborne East Asian dust. In addition, we calculate the concentration of authigenic U as an indicator of relative oxygenation of the sediment water interface. We observe elevated opal and dust fluxes during the last two glacial maxima, and a decrease in both components during deglaciations. Authigenic U shows distinct peaks at the onset of both terminations. The peak at the penultimate deglaciation is also associated with a large peak in opal flux, while the peak in authigenic U during the last termination does not appear to be associated with any large changes in biogenic fluxes. We compare our records with other data from the subtropical-subarctic transition zone, and suggest that our data are consistent with northward shift of the mean position of the westerly jet and subarctic front during deglaciations.

  10. 3-D Characterization of Detrital Zircon Grains and its Implications for Fluvial Transport, Mixing, and Preservation Bias

    Science.gov (United States)

    Markwitz, V.; Kirkland, C. L.; Mehnert, A.; Gessner, K.; Shaw, J.

    2017-12-01

    Detrital zircon studies can suffer from selective loss of provenance information due to U-Pb age discordance, metamictization, metamorphic overprinting and fluviatile transport processes. The relationship between isotopic composition and zircon grain shape, and how grain shape is modified during transport, is largely unknown. We combine X-ray tomography with U-Pb geochronology to quantify how fluvial transport affects 3-D zircon shape, detrital age signature, and grain density along the Murchison River, whose catchment comprises Eoarchean to Early Paleozoic source rocks in Western Australia. We acquired tomographic volumes and isotopic data from 373 detrital zircons to document changes in size, shape and density in transport direction, and explore how grain shape, age spectra and the proportion of discordant material vary along the channel. Results show that shape characteristics are sensitive to transport distance, stream gradient, proximity to source material, and whether the source consists of primary or recycled zircons. With increasing transport distance, grain lengths decrease more than their widths. Furthermore, the loss of metamict grains occurs at a near constant rate, resulting in a linear increase of mean calculated zircon density by ca. 0.03 g/cm3 per 100 km transport distance. 3-D grain shape is therefore strongly linked to detrital age signature, and mean grain density is a function of the absolute transport distance. 3-D shape characteristics provide valuable information on detrital zircon populations, including the interaction between source materials with fluvial transport processes, which significantly affects preservation bias and, by inference, the representativeness of the sampled data.

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

    Science.gov (United States)

    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.

  12. Recycling Spent Primary Cells for the Synthesis of Spinel ZnMn 2 O ...

    African Journals Online (AJOL)

    The mixture was then placed in a fireclay crucible and irradiated in a domestic microwave oven (Pioneer, Model PM-25 L, 2450 MHz, 1000 W) for 20 minutes and reaction products were separated and characterised. Spherical particles of spinel zinc manganese oxide (ZnMn2O4) were isolated after crushing the reduced ...

  13. The bulk modulus of cubic spinel selenides: an experimental and theoretical study

    DEFF Research Database (Denmark)

    Waskowska, A.; Gerward, Leif; Olsen, J.S.

    2009-01-01

    It is argued that mainly the selenium sublattice determines the overall compressibility of the cubic spinel selenides, AB2Se4, and that the bulk modulus for these compounds is about 100GPa. The hypothesis is supported by experiments using high-pressure X-ray diffraction and synchrotron radiation...

  14. Compositional variations of chromiferous spinel in Mg-rich rocks of ...

    Indian Academy of Sciences (India)

    tions typical of spinels found in mid-ocean ridge basalts. ... composition of the source region of the magmas ... The Deccan Traps, one of the largest continen- tal LIPs ... outcrops in the Seychelles Islands (Mahoney 1988; ...... Beane J E 1994 A role for lower continental crust in flood ... magmatic evolution; J. Asian Earth Sci.

  15. Kinetic model for quartz and spinel dissolution during melting of high-level-waste glass batch

    International Nuclear Information System (INIS)

    Pokorny, Richard; Rice, Jarrett A.; Crum, Jarrod V.; Schweiger, Michael J.; Hrma, Pavel

    2013-01-01

    The dissolution of quartz particles and the growth and dissolution of crystalline phases during the conversion of batch to glass potentially affects both the glass melting process and product quality. Crystals of spinel exiting the cold cap to molten glass below can be troublesome during the vitrification of iron-containing high-level wastes. To estimate the distribution of quartz and spinel fractions within the cold cap, we used kinetic models that relate fractions of these phases to temperature and heating rate. Fitting the model equations to data showed that the heating rate, apart from affecting quartz and spinel behavior directly, also affects them indirectly via concurrent processes, such as the formation and motion of bubbles. Because of these indirect effects, it was necessary to allow one kinetic parameter (the pre-exponential factor) to vary with the heating rate. The resulting kinetic equations are sufficiently simple for the detailed modeling of batch-to-glass conversion as it occurs in glass melters. The estimated fractions and sizes of quartz and spinel particles as they leave the cold cap, determined in this study, will provide the source terms needed for modeling the behavior of these solid particles within the flow of molten glass in the melter

  16. Spinel and orthopyroxene exsolved from clinopyroxene in the Haladala pluton in the middle Tianshan (Xinjiang, China)

    Science.gov (United States)

    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.

  17. Low dielectric loss in nano-Li-ferrite spinels prepared by sol–gel ...

    Indian Academy of Sciences (India)

    ... Refresher Courses · Symposia · Live Streaming. Home; Journals; Bulletin of Materials Science; Volume 39; Issue 1. Low dielectric loss in nano-Li-ferrite spinels prepared by sol–gel auto-combustion technique. Mamata Maisnam Nandeibam Nilima Maisnam Victory Sumitra Phanjoubam. Volume 39 Issue 1 February 2016 ...

  18. 6Li MAS NMR Study of Lithium Insertion into Hydrothermally Prepared Li-Ti-O Spinel

    Czech Academy of Sciences Publication Activity Database

    Krtil, Petr; Dědeček, Jiří; Kostlánová, Tereza; Brus, Jiří

    2004-01-01

    Roč. 7, č. 7 (2004), A163-A166 ISSN 1099-0062 R&D Projects: GA ČR GA203/03/0823 Institutional research plan: CEZ:AV0Z4040901 Keywords : lithium insertion * spinel * NMR Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.271, year: 2004

  19. Synthesis and characterization of inverse spinels, intercalation materials for Li-ion batteries

    NARCIS (Netherlands)

    Van Landschoot, N.

    2006-01-01

    Chapter 2 describes the solid-state synthesis of LiNiVO4 and LiCoVO4. The materials are prepared at 800C and are phase pure, as shown by X-ray diffraction and have the inverse spinel structure. Due to the solid-state synthesis the particle size is quite large and the particle size distribution is

  20. Spinel Li2CoTi3O8 nanometer obtained for application as pigment

    International Nuclear Information System (INIS)

    Costa de Camara, M. S.; Alves Pimentel, L.; Longo, E.; Nobrega Azevedo, L. da; Araujo Melo, D. M. de

    2016-01-01

    Pigments are used in ceramics, cosmetics, inks, and other applications widely materials. To this must be single and easily reproducible. Moreover, the pigments obtained in the nanoscale are more stable, reproducible and highlight color in small amounts compared with those obtained in micrometer scale. The mixed oxides with spinel structures AB 2 O 4 have important applications, including: pigments, refractories, catalytic and electronic ceramics. In this context, the aim of this work was the preparation of powder Li 2 CoTi 3 O 8 spinel phase with nanometer particle size of the polymeric precursor method (Pechini) and characterization by means of thermal analysis (TG/DTA) X-ray diffraction (XRD), refined by the Rietveld method, BET, transmission electron microscopy (TEM), Raman and colorimetric coordinates. The pigment was obtained by heat treatment of 400 degree centigrade to 1000 degree centigrade after pyrolysis at 300 degree centigrade/1 h for removing the organic material. Li 2 CoTi 3 O 8 desired spinel phase was obtained from 500 degree centigrade, and presenting stability nanometer to about 1.300 degree centigrade. Spinel green phase introduced at temperatures in the range of 400 degree centigrade and 500 degree centigrade, and 600 degree centigrade at temperatures between blue and 1000 degree centigrade. (Author)

  1. Synthesis of lithium-manganese-oxide spinels: A study by thermal analysis

    CSIR Research Space (South Africa)

    Thackeray, MM

    1994-12-01

    Full Text Available The synthesis of lithium-manganese-oxide spinels by reaction of Li2CO3 and MnCO3 in air and under nitrogen to T(max) = 600°C has been investigated by thermogravimetric analysis and differential scanning calorimetry. When the reaction is conducted...

  2. Spinel versus layered structures for lithium cobalt oxide synthesized at 400-degrees-c

    CSIR Research Space (South Africa)

    Gummow, RJ

    1993-03-01

    Full Text Available -type structure) give comparable fits to the data. This structural anomaly is discussed in terms of the refinements and electrochemical data obtained when lithium is extracted from LiCoO2 in non-aqueous cells at room temperature. A spinel-related model for LixCoO2...

  3. Synthesis and structural characterization of defect spinels in the Lithium-Manganese-Oxide system

    CSIR Research Space (South Africa)

    Thackeray, MM

    1993-10-01

    Full Text Available Lithium-manganese-oxides prepared at moderate temperatures are under investigation as insertion electrodes for rechargeable lithium batteries. The structures of two defect-spinel compounds synthesised by the reaction of MnCO3 and Li2CO3 at 400...

  4. Synthesis and structural characterization of defect spinels in the lithium-manganese-oxide system

    CSIR Research Space (South Africa)

    Thackeray, MM

    1993-10-01

    Full Text Available Lithium-manganese-oxides prepared at moderate temperatures are under investigation as insertion electrodes for rechargeable lithium batteries. The structures of two defect-spinel compounds synthesized by the reaction of MnCO3 and Li2CO3 at 400°C...

  5. Flotation Behaviors of Perovskite, Titanaugite, and Magnesium Aluminate Spinel Using Octyl Hydroxamic Acid as the Collector

    Directory of Open Access Journals (Sweden)

    Weiqing Wang

    2017-08-01

    Full Text Available The flotation behaviors of perovskite, titanaugite, and magnesium aluminate spinel (MA-spinel, using octyl hydroxamic acid (OHA as the collector, were investigated using microflotation experiments, zeta-potential measurements, Fourier transform infrared (FT-IR analyses, X-ray photoelectron spectroscopy (XPS analyses, and flotation experiments on artificially mixed minerals. The microflotation experiments show that the floatability of perovskite is clearly better than titanaugite and MA-spinel at around pH 5.5, while titanaugite possesses certain floatability at pH 6.0–6.5, and MA-spinel displays good floatability at pH > 8.0. The results of the FT-IR and XPS analyses show that OHA mainly interacts with Ti, resulting in perovskite flotation, and that the Al on titanaugite, as well as the Mg and Al on the MA-spinel surface, chemically react with OHA under acidic conditions. However, OHA mainly reacts with the Ti and Ca on the perovskite surface, Ca and Mg on the titanaugite surface, and Mg and Al on the MA-spinel surface under alkaline conditions. The results of the artificially mixed mineral flotation experiment show that the concentrate of TiO2 grade increased from 19.73% to 30.18% at pH 5.4, which indicates that a weakly acidic solution is the appropriate condition for the flotation separation of perovskite from titanaugite and MA-spinel. The results of the modified slag flotation experiments show that the TiO2 grade of concentrate increased from 18.13% to 23.88% at pH 5.4, through the open circuit test of “one roughing and one cleaning”. OHA displays selectivity toward perovskite in the modified slag flotation, but the consumption of H2SO4 is very high. The CaSO4 precipitate covered on the mineral surfaces results in poor TiO2 grade and recovery.

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

    Science.gov (United States)

    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.

  7. Spinel-rich lithologies in the lunar highland crust: Linking lunar samples, crystallization experiments and remote sensing

    Science.gov (United States)

    Gross, J.; Treiman, A. H.

    2012-12-01

    The discovery of areas rich in (Mg,Fe)-Al spinel on the rims and central peaks of lunar impact basins (by the M3 mapping spectrometer on Chandrayaan-1) has revived the old puzzle of the origin of lunar spinel. (Mg,Fe)-Al spinel is rare but widespread in lunar highlands rocks, and thus might be an important component of the lunar crust [1-3]. However, the origin of this spinel is not clear. Lunar (Mg,Fe)-Al spinel could have formed (1) during 'normal' basalt petrogenesis at high pressure; (2) during low-pressure crystallization of melts rich in olivine and plagioclase components, e.g. impact-melted lunar troctolite; or (3) formed at low pressure during assimilation of anorthosite into picritic magma; thus, lunar spinel-rich areas represent old (pre-impact) intrusions of magma. In the absence of spinel-rich samples from the Moon, however, these ideas have been highly speculative. Here we describe a rock fragment from lunar meteorite ALHA 81005 that we recently reported [4] that not only contains spinel, but is the first spinel-rich lunar sample described. This fragment contains ~30% (Mg,Fe)Al spinel and is so fine grained that it reasonably could represent a larger rock body. However, the fragment is so rich in spinel that it could not have formed by melting a peridotitic mantle or a basaltic lunar crust. The clast's small grain size and its apparent disequilibrium between spinel and pyroxene suggest fairly rapid crystallization at low pressure. It could have formed as a spinel cumulate from an impact melt of troctolitic composition; or from a picritic magma that assimilated crustal anorthosite on its margins. The latter mechanism is preferred because it explains the petrographic and chemical features of our clast, and is consistent with the regional setting of the Moscoviense spinel deposit [4]. To better understand the origin and formation history(s) of spinel-rich rocks, we also performed liquidus/crystallization experiments at low-pressure as analogues for impact

  8. The centralized control of elemental mercury emission from the flue gas by a magnetic rengenerable Fe-Ti-Mn spinel.

    Science.gov (United States)

    Liao, Yong; Xiong, Shangchao; Dang, Hao; Xiao, Xin; Yang, Shijian; Wong, Po Keung

    2015-12-15

    A magnetic Fe-Ti-Mn spinel was developed to adsorb gaseous Hg(0) in our previous study. However, it is currently extremely restricted in the control of Hg(0) emission from the flue gas for at least three reasons: sorbent recovery, sorbent regeneration and the interference of the chemical composition in the flue gas. Therefore, the effect of SO2 and H2O on the adsorption of gaseous Hg(0) on the Fe-Ti-Mn spinel and the regeneration of spent Fe-Ti-Mn spinel were investigated in this study. Meanwhile, the procedure of the centralized control of Hg(0) emission from the flue gas by the magnetic Fe-Ti-Mn spinel has been analyzed for industrial application. The spent Fe-Ti-Mn spinel can be regenerated by water washing followed by the thermal treatment at 450 °C with no obvious decrease of its ability for Hg(0) capture. Meanwhile, gaseous Hg(0) in the flue gas can be remarkably concentrated during the regeneration, facilitating its safe disposal. Initial pilot test demonstrated that gaseous Hg(0) in the real flue gas can be concentrated at least 100 times by the Fe-Ti-Mn spinel. Therefore, Fe-Ti-Mn spinel was a novel magnetic regenerable sorbent, which can be used for the centralized control of Hg(0) emission from the flue gas. Copyright © 2015 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    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.

  10. Trace-element and Nd-isotope systematics in detrital apatite of the Po river catchment: Implications for provenance discrimination and the lag-time approach to detrital thermochronology

    Science.gov (United States)

    Malusà, Marco G.; Wang, Jiangang; Garzanti, Eduardo; Liu, Zhi-Chao; Villa, Igor M.; Wittmann, Hella

    2017-10-01

    Detrital thermochronology is often employed to assess the evolutionary stage of an entire orogenic belt using the lag-time approach, i.e., the difference between the cooling and depositional ages of detrital mineral grains preserved in a stratigraphic succession. The impact of different eroding sources to the final sediment sink is controlled by several factors, including the short-term erosion rate and the mineral fertility of eroded bedrock. Here, we use apatite fertility data and cosmogenic-derived erosion rates in the Po river catchment (Alps-Apennines) to calculate the expected percentage of apatite grains supplied to the modern Po delta from the major Alpine and Apenninic eroding sources. We test these predictions by using a cutting-edge dataset of trace-element and Nd-isotope signatures on 871 apatite grains from 14 modern sand samples, and we use apatite fission-track data to validate our geochemical approach to provenance discrimination. We found that apatite grains shed from different sources are geochemically distinct. Apatites from the Lepontine dome in the Central Alps show relative HREE enrichment, lower concentrations in Ce and U, and higher 147Sm/144Nd ratios compared to apatites derived from the External Massifs. Derived provenance budgets point to a dominant apatite contribution to the Po delta from the high-fertility Lepontine dome, consistent with the range independently predicted from cosmonuclide and mineral-fertility data. Our results demonstrate that the single-mineral record in the final sediment sink can be largely determined by high-fertility source rocks exposed in rapidly eroding areas within the drainage. This implies that the detrital thermochronology record may reflect processes affecting relatively small parts of the orogenic system under consideration. A reliable approach to lag-time analysis would thus benefit from an independent provenance discrimination of dated mineral grains, which may allow to proficiently reconsider many

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

    Science.gov (United States)

    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 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 while Cameroon and Morocco spinels fall in the magmatic one. Consequently, the xenoliths sampled from a probably juvenile SCLM at the edge of the most important lithospheric roots (i.e. Cameroon and Morocco) apparently have spinels possibly fractionated in situ from percolating melts and do not represent a real spinel-peridotite facies. On the contrary mantle

  12. The White Nile as a source for Nile sediments: Assessment using U-Pb geochronology of detrital rutile and monazite

    Science.gov (United States)

    Be'eri-Shlevin, Yaron; Avigad, Dov; Gerdes, Axel

    2018-04-01

    Basement terranes exposed at the headwaters of the White Nile include Archean-Paleoproterozoic rocks of the Congo Craton, whose northern sectors were severely reworked during Neoproterozoic orogeny. New U-Pb analyses of detrital rutile and monazite from early Quaternary to Recent coastal quartz sands of Israel, at the northeast extension of the Nile sedimentary system, yield mostly late Neoproterozoic ages, with a dominant peak at ca. 600 Ma. While derivation from the reworked sectors of the Craton cannot be negated, the absence of pre-Neoproterozoic rutile and monazite indicates that the detrital contribution from the Congo cratonic nuclei into the main Nile was insignificant. The near absence of White Nile basement-derived heavy minerals from the Nile sands arriving at the Eastern Mediterranean may be explained by a number of factors such as relatively minor erosion of the Cratonic basement nuclei during the Quaternary, late connection of the White Nile to the main Nile system with a possibility that northern segments connected prior to more southerly ones, and a long-term effective sediment blockage mechanism at the mouth of White Nile. Likewise, our previous study demonstrated that Nile sands display a detrital zircon U-Pb-Hf pattern consistent with significant recycling of NE African Paleozoic sediments. It is thus plausible that any detrital contribution from White Nile basement rocks was thoroughly diluted by eroded Paleozoic sediments, or their recycled products, which were likely the greatest sand reservoir in the region. This study adds to previous studies showing the advantage of a multi mineral U-Pb geochronology strategy in constraining sediment provenance patterns.

  13. Late Permian rivers draining the uplifted Cape Fold Belt: magnetostratigraphy and detrital thermochronology of Karoo Basin sediments

    Science.gov (United States)

    Tohver, E.; Schmieder, M.; Arosio, R.; Lanci, L.; Jourdan, F.; Wilson, A.; Ratcliffe, K.; Payenberg, T.; Flint, S.

    2017-12-01

    The Cape Fold Belt and Karoo Basin of southern Africa formed during the Permian orogeny that affected the 13,000 km southern margin of the Gondwanan continent. In this report, we synthesize new and recent magnetostratigraphic and geochronologic data to establish a chronostratigraphic framework for Karoo Basin sedimentation for comparison with the thermal/exhumation history of the Cape Fold Belt. The source-sink model is evaluated using new data from detrital muscovite and zircon from 2 km composite section of fluvial sandstone and mudstones deposited at ca.275 - 260 Ma. Coherent age populations of detrital zircon grains indicate rapid incorporation of contemporary volcanic ashbeds into the sedimentary record. In contrast, cooling age distributions of detrital muscovite are typically ca. 5 - 10 Ma older than the age of deposition; similar lag times are observed from modern sediments in active mountain belts. Trace element geochemical signatures demonstrate a clear shift towards crustal recycling via headland erosion in the Beaufort Group relative to the underlying Ecca Group. These observations pinpoint the age of uplift for the Cape Fold Belt, which began to function as the major sediment source for the foreland Karoo Basin with the deposition of the uppermost Ecca Group and basal Beaufort Group.

  14. Detrital microbial community development and phosphorus dynamics in a stream ecosystem

    Energy Technology Data Exchange (ETDEWEB)

    Perkins, R.E.; Elwood, J.W.; Sayler, G.S.

    1986-06-01

    Detrital microbial community development and phosphorus dynamics in a lotic system were investigated in non-recirculating laboratory streams contains leaf detritus. Temporal patterns of microbial colonization, as determined by scanning electron microscopy, indicate leaf species dependency and that bacteria were the first colonizers followed by fungi. An extensive glycocalyx layer developed. Phosphorus incorporation rates of both the whole community and intracellular components were determined by time-course measurements of /sup 33/PO/sub 4/ or /sup 32/PO/sub 4/. Phosphorus turnover rates were determined by a sequential double-labeling procedure using /sup 33/PO/sub 4/ and /sup 32/PO/sub 4/, in which the microbiota were labeled with /sup 33/P until in isotopic equilibrium, then /sup 32/P was added. The turnover rate was determined by time-course measurements of the ratio /sup 32/P to /sup 33/P. Snail grazing resulted in an increase in phosphorus metabolism per unit microbial biomass; however, per unit area of leaf surface no increase was observed. Grazing also caused a two-fold reduction in microbial biomass. The results indicate that microbiota associated with decomposing leaves slowly recycle phosphorus, are slowly growing, and have a low metabolic activity. The spiraling length is shortened by microbiota on a short-term basis; however, it may increase on a long-term basis due to hydrological transport of detritus downstream.

  15. Detrital zircon ages in Buller and Takaka terranes, New Zealand : constraints on early Zealandia history

    International Nuclear Information System (INIS)

    Adams, C.J.; Mortimer, N.; Campbell, H.J.; Griffin, W.L.

    2015-01-01

    Detrital zircon ages are presented for 34 early Palaeozoic sandstones from Buller and Takaka terranes, New Zealand, and formerly adjacent parts of Australia-Antarctica. The Buller-Takaka datasets always have two major groups: Ordovician-late Neoproterozoic, 444-700 Ma (but mainly 540-700 Ma), termed 'Gondwana Assembly' (GA), and early Neoproterozoic-Mesoproterozoic, 700-1600 Ma (but mainly 900-1200 Ma), termed 'Rodinia Assembly' (RA). In both terranes, significant age components within these groups are strikingly similar and also have RA/GA ratios, 0.6-1.8. The Cambrian volcanic arc of the Takaka Terrane has contributed little to the zircon patterns. Proportions of Late Cambrian-Early Ordovician zircons, characteristic of granitoid sources in the Ross-Delamerian Orogen are low. The zircons are predominantly reworked with contemporary zircons only evident in a few Buller datasets. The zircon patterns suggest that two major sources (late Mesoproterozoic and late Neoproterozoic), enduring over 120 Ma, were widely distributed and it is postulated they form Precambrian basement beneath southern Zealandia. (author).

  16. Detrital microbial community development and phosphorus dynamics in a stream ecosystem

    International Nuclear Information System (INIS)

    Perkins, R.E.; Elwood, J.W.; Sayler, G.S.

    1986-06-01

    Detrital microbial community development and phosphorus dynamics in a lotic system were investigated in non-recirculating laboratory streams contains leaf detritus. Temporal patterns of microbial colonization, as determined by scanning electron microscopy, indicate leaf species dependency and that bacteria were the first colonizers followed by fungi. An extensive glycocalyx layer developed. Phosphorus incorporation rates of both the whole community and intracellular components were determined by time-course measurements of 33 PO 4 or 32 PO 4 . Phosphorus turnover rates were determined by a sequential double-labeling procedure using 33 PO 4 and 32 PO 4 , in which the microbiota were labeled with 33 P until in isotopic equilibrium, then 32 P was added. The turnover rate was determined by time-course measurements of the ratio 32 P to 33 P. Snail grazing resulted in an increase in phosphorus metabolism per unit microbial biomass; however, per unit area of leaf surface no increase was observed. Grazing also caused a two-fold reduction in microbial biomass. The results indicate that microbiota associated with decomposing leaves slowly recycle phosphorus, are slowly growing, and have a low metabolic activity. The spiraling length is shortened by microbiota on a short-term basis; however, it may increase on a long-term basis due to hydrological transport of detritus downstream

  17. Structural, electronic and magnetic properties of partially inverse spinel CoFe2O4: a first-principles study

    International Nuclear Information System (INIS)

    Hou, Y H; Liu, Z W; Yu, H Y; Zhong, X C; Qiu, W Q; Zeng, D C; Wen, L S; Zhao, Y J

    2010-01-01

    Partially inverse spinel CoFe 2 O 4 , which may be prepared through various heat treatments, differs remarkably from the ideal inverse spinel in many properties. The structure of partially inverse spinel CoFe 2 O 4 as well as its electronic and magnetic properties through a systemic theoretical calculation of (Co 1-x Fe x ) Tet (Co x Fe 2-x ) Oct O 4 (x = 0, 0.25, 0.5, 0.75 and 1.0) have been investigated by the generalized gradient approximation (GGA) + U approach. It is found that the Co and Fe ions prefer their high spin configurations with higher spin moments at octahedral sites in all the studied cases, in line with experimental observations. The Co ions at the octahedral sites favour being far away from each other in the partial inverse spinels, which also show half metallicity at certain inversion degrees.

  18. Ion-probe U–Pb dating of authigenic and detrital opal from Neogene-Quaternary alluvium

    Science.gov (United States)

    Neymark, Leonid; Paces, James B.

    2013-01-01

    Knowing depositional ages of alluvial fans is essential for many tectonic, paleoclimatic, and geomorphic studies in arid environments. The use of U–Pb dating on secondary silica to establish the age of Neogene-Quaternary clastic sediments was tested on samples of authigenic and detrital opal and chalcedony from depths of ∼25 to 53 m in boreholes at Midway Valley, Nevada. Dating of authigenic opal present as rinds on rock clasts and in calcite/silica cements establishes minimum ages of alluvium deposition; dating of detrital opal or chalcedony derived from the source volcanic rocks gives the maximum age of sediment deposition.Materials analyzed included 12 samples of authigenic opal, one sample of fracture-coating opal from bedrock, one sample of detrital opal, and two samples of detrital chalcedony. Uranium–lead isotope data were obtained by both thermal ionization mass spectrometry and ion-microprobe. Uranium concentrations ranged from tens to hundreds of μg/g. Relatively large U/Pb allowed calculation of 206Pb/238U ages that ranged from 1.64±0.36 (2σ) to 6.16±0.50 Ma for authigenic opal and from 8.34±0.28 to 11.2±1.3 Ma for detrital opal/chalcedony. Three samples with the most radiogenic Pb isotope compositions also allowed calculation of 207Pb/235U ages, which were concordant with 206Pb/238U ages from the same samples.These results indicate that basin development at Midway Valley was initiated between about 8 and 6 Ma, and that the basin was filled at long-term average deposition rates of less than 1 cm/ka. Because alluvium in Midway Valley was derived from adjacent highlands at Yucca Mountain, the low rates of deposition determined in this study may imply a slow rate of erosion of Yucca Mountain. Volcanic strata underlying the basin are offset by a number of buried faults to a greater degree than the relatively smooth-sloping bedrock/alluvium contact. These geologic relations indicate that movement on most faults ceased prior to erosional

  19. The first find of spinel peridotite in the Southern Kazakhstan: Structure, composition, and parameters of high-pressure metamorphism

    Science.gov (United States)

    Pilitsyna, A. V.; Tretyakov, A. A.; Alifirova, T. A.; Degtyarev, K. E.; Kovalchuk, E. V.

    2017-09-01

    Spinel peridotite, metamorphosed in high-pressure conditions, was first described within the Western part of the Central Asian Orogenic Belt. The spinel peridotite has the characteristics of Mg-Cr ultramafites indicating the mantle origin of its protolith. The preliminary estimation of the metamorphism peak for the model system MgO-Al2O3—SiO2-Cr2O3 (MASCr) is 10-19 kbar at 680-800°C.

  20. Observation and manipulation of magnetic domains in sol gel derived thin films of spinel ferrites

    Science.gov (United States)

    Datar, Ashwini A.; Mathe, Vikas L.

    2017-12-01

    Thin films of spinel ferrites, namely zinc substituted nickel, cobalt ferrite, and manganese substituted cobalt ferrite, were synthesized using sol-gel derived spin-coating techniques. The films were characterized using x-ray diffraction, field emission scanning electron microscopy, Fourier transform infrared spectroscopy and Raman spectroscopy techniques for the analysis of structural, morphological and vibrational band transition properties, which confirm the spinel phase formation of the films. The magnetic force microscopy (MFM) technique was used to observe the magnetic domain structure present in the synthesized films. Further, the films were subjected to an external DC magnetic field of 2 kG to orient the magnetic domains and analyzed using an ex situ MFM technique.

  1. Mg-spinel lithology: A new rock type on the lunar farside

    Science.gov (United States)

    Pieters, C.M.; Besse, S.; Boardman, J.; Buratti, B.; Cheek, L.; Clark, R.N.; Combe, J.-P.; Dhingra, D.; Goswami, J.N.; Green, R.O.; Head, J.W.; Isaacson, P.; Klima, R.; Kramer, G.; Lundeen, S.; Malaret, E.; McCord, T.; Mustard, J.; Nettles, J.; Petro, N.; Runyon, C.; Staid, M.; Sunshine, J.; Taylor, L.A.; Thaisen, K.; Tompkins, S.; Whitten, J.

    2011-01-01

    High-resolution compositional data from Moon Mineralogy Mapper (M 3) for the Moscoviense region on the lunar farside reveal three unusual, but distinctive, rock types along the inner basin ring. These are designated "OOS" since they are dominated by high concentrations of orthopyroxene, olivine, and Mg-rich spinel, respectively. The OOS occur as small areas, each a few kilometers in size, that are widely separated within the highly feldspathic setting of the basin rim. Although the abundance of plagioclase is not well constrained within the OOS, the mafic mineral content is exceptionally high, and two of the rock types could approach pyroxenite and harzburgite in composition. The third is a new rock type identified on the Moon that is dominated by Mg-rich spinel with no other mafic minerals detectable (lunar crust; they may thus be near contemporaneous with crustal products from the cooling magma ocean. Copyright ?? 2011 by the American Geophysical Union.

  2. The influence of {gamma}-irradiation on electrophysical properties of spinel-based oxide ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Kovalskiy, A.P.; Shpotyuk, O.I. E-mail: karat@ipm.lviv.ua; Hadzaman, I.V.; Mrooz, O.Ya.; Vakiv, M.M

    2000-05-02

    The influence of {sup 60}Co {gamma}-irradiation with 1.25 MeV average energy and 1 MGy absorbed dose on electrophysical properties of Cu-, Ni-, Co- and Mn-based spinel ceramic materials in the Cu{sub x}Ni{sub 1-x-y}Co{sub 2y}Mn{sub 2-y}O{sub 4} (0,1{<=}x{<=}0,8;0,1{<=}y{<=}0,9-x) system is investigated. The {gamma}-induced increasing of the electrical resistance is observed for the investigated samples of various compositions. It is supposed that these changes are explained by cationic redistribution in the spinel sublattices of the ceramics.

  3. Coincident site lattice-matched InGaN on (111) spinel substrates

    International Nuclear Information System (INIS)

    Norman, A. G.; Dippo, P. C.; Moutinho, H. R.; Simon, J.; Ptak, A. J.

    2012-01-01

    Coincident site lattice-matched wurtzite (0001) In 0.31 Ga 0.69 N, emitting in the important green wavelength region, is demonstrated by molecular beam epitaxy on a cubic (111) MgAl 2 O 4 spinel substrate. The coincident site lattice matching condition involves a 30 deg. rotation between the lattice of the InGaN epitaxial layer and the lattice of the spinel. This work describes an alternative approach towards realizing more compositionally homogenous InGaN films with low dislocation density emitting in the ''green gap'' of low efficiency currently observed for semiconductor light emitting diodes (LEDs). This approach could lead to higher efficiency green LEDs presently of great interest for solid-state lighting applications.

  4. Coincident site lattice-matched InGaN on (111) spinel substrates

    Energy Technology Data Exchange (ETDEWEB)

    Norman, A. G.; Dippo, P. C.; Moutinho, H. R.; Simon, J.; Ptak, A. J. [National Renewable Energy Laboratory, Golden, Colorado 80401 (United States)

    2012-04-09

    Coincident site lattice-matched wurtzite (0001) In{sub 0.31}Ga{sub 0.69}N, emitting in the important green wavelength region, is demonstrated by molecular beam epitaxy on a cubic (111) MgAl{sub 2}O{sub 4} spinel substrate. The coincident site lattice matching condition involves a 30 deg. rotation between the lattice of the InGaN epitaxial layer and the lattice of the spinel. This work describes an alternative approach towards realizing more compositionally homogenous InGaN films with low dislocation density emitting in the ''green gap'' of low efficiency currently observed for semiconductor light emitting diodes (LEDs). This approach could lead to higher efficiency green LEDs presently of great interest for solid-state lighting applications.

  5. High-pressure phase of the cubic spinel NiMn2O4

    DEFF Research Database (Denmark)

    Åsbrink, S.; Waskowska, A.; Olsen, J. Staun

    1998-01-01

    experimental uncertainty, there is no volume change at the transition. The cia ratio of the tetragonal spinel is almost independent of pressure and equal to 0.91. The phase transition is attributed to the Jahn-Teller-type distortion and the ionic configurationcan be assumed as (Mn3+)(tetr)[Ni2+Mn3+](oct......It has been observed that the fee spinel NiMn2O4 transforms to a tetragonal structure at about 12 GPa. The tetragonal phase does not revert to the cubic phase upon decompression and its unit-cell constants at ambient pressure are a(0)=8.65(8) and c(0)=7.88(15) Angstrom (distorted fee). Within thr......). The bulk modulus of the cubic phase is 206(4) GPa....

  6. Direct observation of cation distributions of ideal inverse spinel CoFe2O4 nanofibres and correlated magnetic properties

    KAUST Repository

    Zeng, Xue

    2017-04-25

    Low-dimensional spinel ferrites have recently attracted increasing attention because their tunable magnetic properties make them attractive candidates as spin-filtering tunnel barriers in spintronic devices and as magnetic components in artificial multiferroic heterostructures. Although we know that the distribution of cations (Fe3+ and Co2+) in a spinel structure governs its magnetic properties, their distribution in the so-called ideal inverse spinel structure of a ferrite, CoFe2O4, has not yet been imaged with sub-ångstrom resolution. In this work, we fill this gap in evidence by reporting a direct observation of the distribution of cations in an ideal inverse spinel structure of CoFe2O4 nanofibres using aberration-corrected transmission electron microscopy (TEM). The ordering of Co2+ and Fe3+ at the octahedral sites imaged along either [001], [011] or [-112] orientation was identified as 1 : 1, in accordance with the ideal inverse spinel structure. The saturation magnetisation calculated based on the crystal structure as determined from the TEM image is in good agreement with that measured experimentally on the spinel CoFe2O4 nanofibres, further confirming results from TEM.

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

    Science.gov (United States)

    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 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.

  8. Subsolidus Evolution of the Magnetite-Spinel-UlvöSpinel Solid Solutions in the Kovdor Phoscorite-Carbonatite Complex, NW Russia

    Directory of Open Access Journals (Sweden)

    Gregory Yu. Ivanyuk

    2017-11-01

    Full Text Available The Kovdor phoscorite-carbonatite ore-pipe rocks form a natural series, where apatite and magnetite first gradually increase due to the presence of earlier crystallizing forsterite in the pipe marginal zone and then decrease as a result of carbonate development in the axial zone. In all lithologies, magnetite grains contain (oxyexsolution inclusions of comparatively earlier ilmenite group minerals and/or later spinel, and their relationship reflects the concentric zonation of the pipe. The temperature and oxygen fugacity of titanomagnetite oxy-exsolution decreases in the natural rock sequence from about 500 °C to about 300 °C and from NNO + 1 to NNO − 3 (NNO is Ni-NiO oxygen fugacity buffer, with a secondary positive maximum for vein calcite carbonatite. Exsolution spinel forms spherical grains, octahedral crystals, six-beam and eight-beam skeletal crystals co-oriented with host magnetite. The ilmenite group minerals occur as lamellae oriented along {111} and {100} planes of oxy-exsolved magnetite. The kinetics of inclusion growth depends mainly on the diffusivity of cations in magnetite: their comparatively low diffusivities in phoscorite and carbonatites of the ore-pipe internal part cause size-independent growth of exsolution inclusions; while higher diffusivities of cations in surrounding rocks, marginal forsterite-rich phoscorite and vein calcite carbonatite result in size-dependent growth of inclusions.

  9. Re4As6S3, a thio-spinel-related cluster system

    DEFF Research Database (Denmark)

    Besnard, Celine; Svensson, Christer; Ståhl, Kenny

    2003-01-01

    . The rhenium atoms form tetrahedral clusters linked via tetrahedral arsenic clusters to produce an NaCl-type arrangement. The oxidation state of rhenium is IV and the number of electrons shared by the rhenium atoms in the cluster is 12. The structure is based on an ordered defect thio-spinel A((1-x))B(2)X(4......) where the B-type atoms form tetrahedral clusters....

  10. Tailoring the magnetic properties and magnetorheological behavior of spinel nanocrystalline cobalt ferrite by varying annealing temperature

    Czech Academy of Sciences Publication Activity Database

    Sedlacik, M.; Pavlinek, V.; Peer, Petra; Filip, Petr

    2014-01-01

    Roč. 18, č. 43 (2014), s. 6919-6924 ISSN 1477-9226 R&D Projects: GA ČR GA202/09/1626 Grant - others:GA MŠk(CZ) ED2.1.00/03.0111 Institutional support: RVO:67985874 Keywords : spinel nanocrystalline cobalt ferrite * nanoparticles * magnetorheological effect Subject RIV: BK - Fluid Dynamics Impact factor: 4.197, year: 2014

  11. Synthesis of high-surface-area spinel-type MgAl2O4 nanoparticles ...

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 40; Issue 1. Synthesis of high-surface-area spinel-type MgAl 2 O 4 nanoparticles by [Al(sal) 2 (H 2 O) 2 ] 2 [Mg(dipic) 2 ] and [Mg(H 2 O) 6 ][Al(ox) 2 (H 2 O) 2 ] 2 ·5H 2 O: influence of inorganic precursor type. Volume 40 Issue 1 February 2017 pp 45-53 ...

  12. Morphology evolution in spinel manganite films deposited from an aqueous solution

    International Nuclear Information System (INIS)

    Ko, Song Won; Li, Jing; Trolier-McKinstry, Susan

    2012-01-01

    Spinel manganite films were deposited by the spin spray technique at low deposition temperatures ( 1000, agglomeration of small particles was dominant, which suggests that homogeneous nucleation is dominant during deposition. Heterogeneous nucleation was critical to obtain dense films. - Highlights: ► Film microstructure depends on supersaturation. ► Heterogeneous nucleation induces dense and continuous films. ► The spin spray technique enables use of a variety of substrates.

  13. Irradiation effects and behaviour of fission products in zirconia and spinel

    International Nuclear Information System (INIS)

    Gentils, A.

    2003-10-01

    Crystalline oxides, such as zirconia (ZrO 2 ) and spinel (MgAl 2 O 4 ), are promising inert matrices for the transmutation of plutonium and minor actinides. This work deals with the study of the physico-chemical properties of these matrices, more specifically their behaviour under irradiation and their capacity to retain fission products. Irradiations at low energy and incorporation of stable analogs of fission products (Cs, I, Xe) into yttria-stabilized zirconia and magnesium-aluminate spinel single crystals were performed by using the ion implanter IRMA (CSNSM-Orsay). Irradiations at high energy were made on several heavy ion accelerators (GANIL-Caen, ISL-Berlin, HIL-Warsaw). The damage induced by irradiation and the release of fission products were monitored by in situ Rutherford Backscattering Spectrometry experiments. Transmission electron microscopy was also used in order to determine the nature of the damage induced by irradiation. The results show that irradiation of ZrO 2 and MgAl 2 O 4 with heavy ions (about hundred keV and about hundred MeV) induces a huge structural damage in crystalline matrices. Total disorder (amorphization) is however never reached in zirconia, contrary to what is observed in the case of spinel. The results also emphasize the essential role played by the concentration of implanted species on their retention capacity. A dramatic release of fission products was observed when the concentration exceeds a threshold of a few atomic percent. Irradiation of implanted samples with medium-energy noble-gas ions leads to an enhancement of the fission product release. The exfoliation of spinel crystals implanted at high concentration of Cs ions is observed after a thermal treatment at high temperature. (author)

  14. Chemical synthesis of nickel ferrite spinel designed as an insulating bilayer coating on ferromagnetic particles

    Czech Academy of Sciences Publication Activity Database

    Strečková, M.; Hadraba, Hynek; Bureš, R.; Fáberová, M.; Roupcová, Pavla; Kuběna, Ivo; Medvecký, L.; Girman, V.; Kollár, P.; Füzer, J.; Čižmár, E.

    2015-01-01

    Roč. 270, MAY (2015), s. 66-76 ISSN 0257-8972 R&D Projects: GA ČR(CZ) GA14-25246S; GA MŠk(CZ) ED1.1.00/02.0068 Institutional support: RVO:68081723 Keywords : soft magnetic composite * NiFe2O4 spinel ferrite * coating * precipitation method * focused ion beam Subject RIV: JG - Metallurgy Impact factor: 2.139, year: 2015

  15. Plasma sprayed manganeseecobalt spinel coatings: Process sensitivity on phase, electrical and protective performance

    Czech Academy of Sciences Publication Activity Database

    Han Jung, S.; Pala, Zdeněk; Sampath, S.

    2016-01-01

    Roč. 304, February (2016), s. 234-243 ISSN 0378-7753 R&D Projects: GA ČR GB14-36566G Institutional support: RVO:61389021 Keywords : Interconnect protection * Cr-poisoning * Manganese cobalt spinel * Electrical conductivity * Plasma spray Subject RIV: JE - Non-nuclear Energetics, Energy Consumption ; Use Impact factor: 6.395, year: 2016 http://www.sciencedirect.com/science/article/pii/S0378775315305383

  16. Synthesis of ultrasmall Li-Mn spinel oxides exhibiting unusual ion exchange, electrochemical, and catalytic properties

    Science.gov (United States)

    Miyamoto, Yumi; Kuroda, Yoshiyuki; Uematsu, Tsubasa; Oshikawa, Hiroyuki; Shibata, Naoya; Ikuhara, Yuichi; Suzuki, Kosuke; Hibino, Mitsuhiro; Yamaguchi, Kazuya; Mizuno, Noritaka

    2015-10-01

    The efficient surface reaction and rapid ion diffusion of nanocrystalline metal oxides have prompted considerable research interest for the development of high functional materials. Herein, we present a novel low-temperature method to synthesize ultrasmall nanocrystalline spinel oxides by controlling the hydration of coexisting metal cations in an organic solvent. This method selectively led to Li-Mn spinel oxides by tuning the hydration of Li+ ions under mild reaction conditions (i.e., low temperature and short reaction time). These particles exhibited an ultrasmall crystallite size of 2.3 nm and a large specific surface area of 371 ± 15 m2 g-1. They exhibited unique properties such as unusual topotactic Li+/H+ ion exchange, high-rate discharge ability, and high catalytic performance for several aerobic oxidation reactions, by creating surface phenomena throughout the particles. These properties differed significantly from those of Li-Mn spinel oxides obtained by conventional solid-state methods.

  17. Synthesis of ultrasmall Li–Mn spinel oxides exhibiting unusual ion exchange, electrochemical, and catalytic properties

    Science.gov (United States)

    Miyamoto, Yumi; Kuroda, Yoshiyuki; Uematsu, Tsubasa; Oshikawa, Hiroyuki; Shibata, Naoya; Ikuhara, Yuichi; Suzuki, Kosuke; Hibino, Mitsuhiro; Yamaguchi, Kazuya; Mizuno, Noritaka

    2015-01-01

    The efficient surface reaction and rapid ion diffusion of nanocrystalline metal oxides have prompted considerable research interest for the development of high functional materials. Herein, we present a novel low-temperature method to synthesize ultrasmall nanocrystalline spinel oxides by controlling the hydration of coexisting metal cations in an organic solvent. This method selectively led to Li–Mn spinel oxides by tuning the hydration of Li+ ions under mild reaction conditions (i.e., low temperature and short reaction time). These particles exhibited an ultrasmall crystallite size of 2.3 nm and a large specific surface area of 371 ± 15 m2 g−1. They exhibited unique properties such as unusual topotactic Li+/H+ ion exchange, high-rate discharge ability, and high catalytic performance for several aerobic oxidation reactions, by creating surface phenomena throughout the particles. These properties differed significantly from those of Li–Mn spinel oxides obtained by conventional solid-state methods. PMID:26456216

  18. RHEED oscillations in spinel ferrite epitaxial films grown by conventional planar magnetron sputtering

    Science.gov (United States)

    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.

  19. Spinel formation for stabilizing simulated nickel-laden sludge with aluminum-rich ceramic precursors.

    Science.gov (United States)

    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.

  20. Lattice vibrations of materials for lithium rechargeable batteries II. Lithium extraction-insertion in spinel structures

    International Nuclear Information System (INIS)

    Julien, C.M.; Camacho-Lopez, M.A.

    2004-01-01

    Lithiated spinel manganese oxides with various amounts of lithium have been prepared through solid-state reaction and electrochemical intercalation and deintercalation. Local structure of the samples are studied using Raman scattering and Fourier transform infrared spectroscopy. We report vibrational spectra of lithiated manganese oxides Li x Mn 2 O 4 as a function of lithium concentration in the range 0.1≤x≤2.0. Raman and Fourier transform infrared (FTIR) spectral results indicated multiple-phase reactions when the lithium content is modified in the spinel lattice. Lattice dynamics of lithiated spinel manganese oxides have been interpreted using either a classical factor-group analysis or a local environment model. The structural modifications have been studied on the basis of vibrations of LiO 4 tetrahedral and MnO 6 octahedral units when Li/Mn≤0.5, and LiO 4 , LiO 6 , and MnO 6 structural units when Li/Mn>0.5

  1. Cations in Octahedral Sites: A Descriptor for Oxygen Electrocatalysis on Transition-Metal Spinels

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Chao; Feng, Zhenxing; Scherer, Günther G.; Barber, James; Shao-Horn, Yang; Xu, Zhichuan J. (Nanyang); (ICL); (Oregon State U.); (TUM-CREATE); (MIT)

    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, 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.

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

    International Nuclear Information System (INIS)

    Feng, Zhenxing; Chen, Xiao; Fister, Timothy T.; Bedzyk, Michael J.; Fenter, Paul

    2016-01-01

    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, while 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.

  3. The role of praseodymium substituted ions on electrical and magnetic properties of Mg spinel ferrites

    Energy Technology Data Exchange (ETDEWEB)

    Farid, Muhammad Tahir, E-mail: tahirfaridbzu@gmail.com; Ahmad, Ishtiaq; Kanwal, Muddassara; Murtaza, Ghulam; Ali, Irshad; Khan, Sajjad Ahmad

    2017-04-15

    Spinel ferrites with composition MgPr{sub y}Fe{sub 2−y}O{sub 4} (y=0.0, 0.025, 0.05, 0.075, 0.10) were successfully synthesized using sol-gel auto-combustion technique. The structural prisoperties of a prepared sintered powder were characterized with the help of X-ray Diffraction (XRD) and then also by using Scanning electron microscopy (SEM). Electrical measurements demonstrate that resistivity and activation energy increases with the Praseodymium substitution while dc resistivity decreases with the rise of temperature showing the semiconductor nature of the synthesized ferrites. Remanence and the saturation magnetization (M{sub s}) decrease while coercivity (H{sub c}) also increases with the increase in praseodymium contents. Anisotropic constant is observed to exhibit similar behavior as H{sub C}. The above mentioned parameters suggest that the synthesized samples are favorable for microwave absorbing purposes. - Highlights: • Magnesium based spinel ferrites were successfully synthesized by sol-gel method. • The spinel phase has been observed in all samples. • The dc resistivity are found to increase with increasing Pr content • The samples with high resistivity have high values of activation energy. • The Ms Decreases with increasing Pr contents while Hc increases.

  4. RHEED oscillations in spinel ferrite epitaxial films grown by conventional planar magnetron sputtering

    Directory of Open Access Journals (Sweden)

    T. Ojima

    2018-04-01

    Full Text Available Real-time in situ reflection high energy electron diffraction (RHEED observations of Fe3O4, γ-Fe2O3, and (Co,Fe3O4 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.

  5. SHRIMP U-Pb dating of detrital zircons in metamorphic rocks from northern Kyushu, western Japan

    International Nuclear Information System (INIS)

    Tsutsumi, Yukiyasu; Yokoyama, Kazumi; Terada, Kentaro; Sano, Yuji

    2003-01-01

    Radiometric ages of detrital zircons in psammitic schists from the Nagasaki, Kurume, Konoha and Kiyama areas, northern Kyushu, were obtained from 238 U/ 206 Pb ratio and isotopic compositions of Pb using a Sensitive High Resolution Ion Microprobe (SHRIMP II). Zircons from the Nagasaki, Kurume and Konoha areas show bimodal age distribution with peaks at ca. 1900 Ma and 250 Ma. It is suggested from this study that the older zircons were derived from Proterozoic landmass and the Korean Peninsula. Zircons from the Kiyama metamorphic rock show a different pattern with ages concentrated at 380-590 Ma. Such zircons are rare in rock samples from the Nagasaki, Kurume and Konoha areas, indicating that Kiyama rocks and a different origin than those from the other three areas. The youngest zircons from the Kiyama, Nagasaki, Kurume and Konoha areas show ages of 382±23 Ma, 238±13 Ma, 249±13 Ma, and 175±4 Ma, respectively, These data mark the upper age limit of their deposition. Since a continuous igneous activity occurred during the period from 300 to 170 Ma in Far East Asia, and the metamorphic age has been close to the zircon age of each area, these youngest ages for the Nagasaki, Kurume and Konoha areas are considered nearly contemporary to the depositional ages. An evaluation of the nature of metamorphism and available ages suggest the possibility that the Nagasaki metamorphic rocks as well as the schist from the Kurume area belong to the Suo zone of the Sangun belt, whereas the metamorphic rocks in the Konoha area may belong to the Ryoke belt or Suo zone of the Sangun belt. (author)

  6. Detrital phosphorus as a proxy of flooding events in the Changjiang River Basin

    Energy Technology Data Exchange (ETDEWEB)

    Meng, Jia [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Qingdao 266100 (China); College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100 (China); Yao, Peng, E-mail: yaopeng@mail.ouc.edu.cn [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Qingdao 266100 (China); Qingdao Collaborative Innovation Center of Marine Science and Technology, Qingdao 266100 (China); Institute of Marine Organic Geochemistry, Ocean University of China, Qingdao 266100 (China); Bianchi, Thomas S. [Department of Geological Sciences, University of Florida, Gainesville, FL 32611-2120 (United States); Li, Dong; Zhao, Bin; Xu, Bochao [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Qingdao 266100 (China); College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100 (China); Yu, Zhigang [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Qingdao 266100 (China); Institute of Marine Organic Geochemistry, Ocean University of China, Qingdao 266100 (China)

    2015-06-01

    In this study, sediment grain size (MGS), specific surface area (SSA), total organic carbon (TOC) contents, C/N molar ratios, stable carbon isotope, and P species in a sediment core, collected from the East China Sea (ECS) inner-shelf were measured to explore the applicability of detrital phosphorus (De-P) as a potential indicator of past flooding events in the Changjiang River Basin (CRB). In particular, we examined the linkages between the evolution of floods with regional climate changes and anthropogenic activities in the CRB. Peaks of De-P concentrations in sediments corresponded well with the worst flooding events of the CRB over the past two centuries (e.g., 1850s, 1860s, 1900s, 1920s, 1950s, 1980s, and 2000s). Moreover, De-P also corresponded well with the extreme hypoxic events in 1981 and 1998 in the Changjiang Estuary as indicated by Mo/Al ratios, indicating potential linkages between De-P as a flooding proxy to flood-induced hypoxia events in this region. In addition, a robust relationship was found among De-P, the floods in 1950s, 1980s, and 2000s of the CRB, the intensive El Niño-Southern Oscillation (ENSO), the abnormally weak East Asian Summer Monsoon (EASM) and the warm phase of Pacific Decadal Oscillation (PDO), suggesting that De-P also provided insights to linkages between regional climate change and flooding events in this region. - Highlights: • De-P was used to track past floods in the Changjiang River Basin (CRB). • De-P may serve as a proxy for flood-induced hypoxia events in the Changjiang Estuary. • De-P may be a proxy for examining linkages between floods and climatic drivers.

  7. Detrital phosphorus as a proxy of flooding events in the Changjiang River Basin

    International Nuclear Information System (INIS)

    Meng, Jia; Yao, Peng; Bianchi, Thomas S.; Li, Dong; Zhao, Bin; Xu, Bochao; Yu, Zhigang

    2015-01-01

    In this study, sediment grain size (MGS), specific surface area (SSA), total organic carbon (TOC) contents, C/N molar ratios, stable carbon isotope, and P species in a sediment core, collected from the East China Sea (ECS) inner-shelf were measured to explore the applicability of detrital phosphorus (De-P) as a potential indicator of past flooding events in the Changjiang River Basin (CRB). In particular, we examined the linkages between the evolution of floods with regional climate changes and anthropogenic activities in the CRB. Peaks of De-P concentrations in sediments corresponded well with the worst flooding events of the CRB over the past two centuries (e.g., 1850s, 1860s, 1900s, 1920s, 1950s, 1980s, and 2000s). Moreover, De-P also corresponded well with the extreme hypoxic events in 1981 and 1998 in the Changjiang Estuary as indicated by Mo/Al ratios, indicating potential linkages between De-P as a flooding proxy to flood-induced hypoxia events in this region. In addition, a robust relationship was found among De-P, the floods in 1950s, 1980s, and 2000s of the CRB, the intensive El Niño-Southern Oscillation (ENSO), the abnormally weak East Asian Summer Monsoon (EASM) and the warm phase of Pacific Decadal Oscillation (PDO), suggesting that De-P also provided insights to linkages between regional climate change and flooding events in this region. - Highlights: • De-P was used to track past floods in the Changjiang River Basin (CRB). • De-P may serve as a proxy for flood-induced hypoxia events in the Changjiang Estuary. • De-P may be a proxy for examining linkages between floods and climatic drivers

  8. Incorporating detrital conditioning in outdoor microcosms dosed with JP-8 jet fuel

    International Nuclear Information System (INIS)

    Matthews, R.A.; Markiewicz, A.; Harter, V.; Landis, W.G.

    1995-01-01

    The authors have developed an outdoor microcosm system that incorporates detrital conditioning to test the hypothesis that microbiota play a critical role in altering the community response to hydrocarbon toxicants. The microcosms were constructed using 568 L tanks, arranged in 6 units of 4 tanks, with each unit equidistant from a central conditions tank (CT). During pre-treatment, the microcosms and CT were filled with nutrient-amended well water, artificial sediment, leaf packs containing dried maple leaves, elodea fragment, and unglazed tiles for periphyton growth. Water circulation was maintained at the rate of 24 exchanges per day. After four weeks, invertebrates from local ponds were added to the CT. Leafpacks were added to the CT and microcosms every two weeks; eight week old packs were discarded after returning invertebrates to the CT. On a weekly basis, 25% of the sediments, leaf packs, tiles, and elodea from each microcosms were transferred to another microcosm; the CT walls and tiles were scraped; an the water quality was monitored. Circulation was discontinued one week prior to dosing. On 4/12/96, the microcosms were dosed to contain 0--0.25 microg/L of JP-8 jet fuel. Within two weeks the GC/MS hydrocarbon concentrations were very low in the water column of the highest treatment group. There has been little acute toxicity, despite selecting doses that caused severe, acute toxicity in laboratory microcosm studies. The presence of a complex, detritus-based microbial community appears to mitigate the influences of the toxicant on the microcosms

  9. Detrital shadows: estuarine food web connectivity depends on fluvial influence and consumer feeding mode.

    Science.gov (United States)

    Howe, Emily; Simenstad, Charles A; Ogston, Andrea

    2017-10-01

    We measured the influence of landscape setting on estuarine food web connectivity in five macrotidal Pacific Northwest estuaries across a gradient of freshwater influence. We used stable isotopes (δ 13 C, δ 15 N, δ 34 S) in combination with a Bayesian mixing model to trace primary producer contributions to suspension- and deposit-feeding bivalve consumers (Mytilus trossulus and Macoma nasuta) transplanted into three estuarine vegetation zones: emergent marsh, mudflat, and eelgrass. Eelgrass includes both Japanese eelgrass (Zostera japonica) and native eelgrass (Zostera marina). Fluvial discharge and consumer feeding mode strongly influenced the strength and spatial scale of observed food web linkages, while season played a secondary role. Mussels displayed strong cross-ecosystem connectivity in all estuaries, with decreasing marine influence in the more fluvial estuaries. Mussel diets indicated homogenization of detrital sources within the water column of each estuary. In contrast, the diets of benthic deposit-feeding clams indicated stronger compartmentalization in food web connectivity, especially in the largest river delta where clam diets were trophically disconnected from marsh sources of detritus. This suggests detritus deposition is patchy across space, and less homogenous than the suspended detritus pool. In addition to fluvial setting, other estuary-specific environmental drivers, such as marsh area or particle transport speed, influenced the degree of food web linkages across space and time, often accounting for unexpected patterns in food web connectivity. Transformations of the estuarine landscape that alter river hydrology or availability of detritus sources can thus potentially disrupt natural food web connectivity at the landscape scale, especially for sedentary organisms, which cannot track their food sources through space. © 2017 by the Ecological Society of America.

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

    Science.gov (United States)

    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

  11. Thermodynamic Modelling of Fe-Cr-Ni-Spinel Formation at the Light-Water Reactor Conditions

    International Nuclear Information System (INIS)

    Kurepin, V. A.; Kulik, D. A.; Hitpold, A.; Nicolet, M.

    2002-03-01

    In the light water reactors (LWR), the neutron activation and transport of corrosion products is of concern in the context of minimizing the radiation doses received by the personnel during maintenance works. A practically useful model for transport and deposition of the stainless steel corrosion products in LWR can only be based on an improved understanding of chemical processes, in particular, on the attainment of equilibrium in this hydrothermal system, which can be described by means of a thermodynamic solid-solution -aqueous-solution (SSAS) model. In this contribution, a new thermodynamic model for a Fe-Cr-Ni multi-component spinel solid solutions was developed that considers thermodynamic consequences of cation interactions in both spinel sub-Iattices. The obtained standard thermodynamic properties of two ferrite and two chromite end-members and their mixing parameters at 90 bar pressure and 290 *c temperature predict a large miscibility gap between (Fe,Ni) chromite and (Fe,Ni) ferrite phases. Together with the SUPCRT92-98 thermo- dynamic database for aqueous species, the 'spinel' thermodynamic dataset was applied to modeling oxidation of austenitic stainless steel in hydrothermal water at 290*C and 90 bar using the Gibbs energy minimization (GEM) algorithm, implemented in the GEMS-PSI code. Firstly, the equilibrium compositions of steel oxidation products were modelIed as function of oxygen fugacity .fO 2 by incremental additions of O 2 in H 2 O-free system Cr-Fe- Ni-O. Secondly, oxidation of corrosion products in the Fe-Cr-Ni-O-H aquatic system was modelIed at different initial solid/water ratios. It is demonstrated that in the transition region from hydrogen regime to oxygen regime, the most significant changes in composition of two spinel-oxide phases (chromite and ferrite) and hematite must take place. Under more reduced conditions, the Fe-rich ferrite (magnetite) and Ni-poor chromite phases co-exist at equilibrium with a metal Ni phase, maintaining

  12. Effects of synthetic parameters on structure and electrochemical performance of spinel lithium manganese oxide by citric acid-assisted sol-gel method

    International Nuclear Information System (INIS)

    Yi Tingfeng; Dai Changsong; Gao Kun; Hu Xinguo

    2006-01-01

    The spinel lithium manganese oxide cathode materials were prepared by citric acid-assisted sol-gel method at 623-1073 K in air. The effects of pH value, raw material, synthesis temperature and time on structure and electrochemical performance of spinel lithium manganese oxide are investigated by X-ray diffraction (XRD), scanning electronic microscope (SEM) and cyclic voltammetry (CV). XRD data results strongly suggest that the synthesis temperature is the dominating factors of the formation of spinel phase, and spinel lithium manganese oxide powder with various crystallites size can be obtained by controlling the sintering time. CV shows that spinel lithium manganese oxide powder formed about 973 K presents the best electrochemical performance with well separated two peaks and the highest peak current. Charge-discharge test indicates that spinel lithium manganese oxide powders calcined at higher temperatures have high discharge capacity and capacity loss, and sintered at lower temperatures has low discharge capacity and high capacity retention

  13. Effects of synthetic parameters on structure and electrochemical performance of spinel lithium manganese oxide by citric acid-assisted sol-gel method

    Energy Technology Data Exchange (ETDEWEB)

    Yi Tingfeng [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China)]. E-mail: tfyihit@hit.edu.cn; Dai Changsong [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China); Gao Kun [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China); Hu Xinguo [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China)

    2006-11-30

    The spinel lithium manganese oxide cathode materials were prepared by citric acid-assisted sol-gel method at 623-1073 K in air. The effects of pH value, raw material, synthesis temperature and time on structure and electrochemical performance of spinel lithium manganese oxide are investigated by X-ray diffraction (XRD), scanning electronic microscope (SEM) and cyclic voltammetry (CV). XRD data results strongly suggest that the synthesis temperature is the dominating factors of the formation of spinel phase, and spinel lithium manganese oxide powder with various crystallites size can be obtained by controlling the sintering time. CV shows that spinel lithium manganese oxide powder formed about 973 K presents the best electrochemical performance with well separated two peaks and the highest peak current. Charge-discharge test indicates that spinel lithium manganese oxide powders calcined at higher temperatures have high discharge capacity and capacity loss, and sintered at lower temperatures has low discharge capacity and high capacity retention.

  14. Modification of Alumina and Spinel Inclusions by Calcium in Liquid Steel

    Science.gov (United States)

    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

  15. Detrital zircon provenance of the Hartselle Sandstone Unit, Southeastern USA: Insights into sediment source, paleogeography, and setting

    Science.gov (United States)

    Harthy, M. A.; Gifford, J.

    2017-12-01

    The Hartselle sandstone is an excellent example of an Oil sand, a resource rich in bitumen. The unit is a light-colored thick-bedded to massive quartzose sandstone, that is widespread across an area from Georgia in the east to Mississippi in the west, and south from Alabama to Kentucky as a northern border. Formation thickness ranges from 0 to more than 150 feet. The unit has been stratigraphically dated to the Middle-Upper Mississippian age. One hypothesis suggests that the sandstone unit formed from the geological remains of barrier islands located in the ocean between Gondwana and Laurentia. The Hartselle is thought to have formed by the movement waves and currents along the shoreline, which carried sand and concentrated it into a set of northwest to southeast trending barrier islands. Transgression-regression events shifted the islands back and forth in relation to the position of the shoreline, leading to the large areal extent of the unit. However, the current data are not enough to explain the geographical position of the Hartselle sandstone unit as it is not running parallel to the ancient shoreline. Another mystery is the source of the sand, some believing the source was from the south (Gondwana) and others that erosion was from the north (Laurentia). Detrital zircon provenance analysis will address the uncertainty in sediment source. We will compare zircon U-Pb age spectra to possible Laurentian and Gondwanan source areas to discriminate between these possibilities. In addition, the age of the youngest detrital zircon population will provide additional constraints on the maximum age of deposition for the unit. These detrital ages will also help us to understand the tectonic setting at the time of Hartselle deposition. Lastly, we aim to explain the widespread nature of the unit and the processes involved in the formation of the Hartselle sandstone. When taken together, these interpretations will illuminate the age, depositional and tectonic setting of a

  16. Exploring Lithium-Cobalt-Nickel Oxide Spinel Electrodes for ≥3.5 V Li-Ion Cells

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Eungje; Blauwkamp, Joel; Castro, Fernando C.; Wu, Jinsong; Dravid, Vinayak P.; Yan, Pengfei; Wang, Chongmin; Kim, Soo; Wolverton, Christopher; Benedek, Roy; Dogan, Fulya; Park, Joong Sun; Croy, Jason R.; Thackeray, Michael M.

    2016-10-19

    Recent reports have indicated that a manganese oxide spinel component, when embedded in a relatively small concentration in layered xLi2MnO3(1-x)LiMO2 (M=Ni, Mn, Co) electrode systems, can act as a stabilizer that increases their capacity, rate capability, cycle life, and first-cycle efficiency. These findings prompted us to explore the possibility of exploiting lithiated cobalt oxide spinel stabilizers by taking advantage of (1) the low mobility of cobalt ions relative to manganese and nickel ions in close-packed oxides and (2) their higher potential (~3.6 V vs. Li0) relative to manganese oxide spinels (~2.9 V vs. Li0) for the spinel-to-lithiated spinel electrochemical reaction. In particular, we have revisited the structural and electrochemical properties of lithiated spinels in the LiCo1-xNixO2 (0x0.2) system, first reported almost 25 years ago, by means of high-resolution (synchrotron) X-ray diffraction, transmission electron microscopy, nuclear magnetic resonance spectroscopy, electrochemical cell tests, and theoretical calculations. The results provide a deeper understanding of the complexity of intergrown layered/lithiated spinel LiCo1-xNixO2 structures, when prepared in air between 400 and 800 C, and the impact of structural variations on their electrochemical behavior. These structures, when used in low concentration, offer the possibility of improving the cycling stability, energy, and power of high energy (≥3.5 V) lithium-ion cells.

  17. Effect of Feed Melting, Temperature History and Minor Component Addition on Spinel Crystallization in High-Level Waste Glass

    International Nuclear Information System (INIS)

    Izak, Pavel; Hrma, Pavel R.; Arey, Bruce W.; Plaisted, Trevor J.

    2001-01-01

    This study was undertaken to help design mathematical models for high-level waste (HLW) glass melter that simulate spinel behavior in molten glass. Spinel, (Fe,Ni,Mn) (Fe,Cr)2O4, is the primary solid phase that precipitates from HLW glasses containing Fe and Ni in sufficient concentrations. Spinel crystallization affects the anticipated cost and risk of HLW vitrification. To study melting reactions, we used simulated HLW feed, prepared with co-precipitated Fe, Ni, Cr, and Mn hydroxides. Feed samples were heated up at a temperature-increase rate (4C/min) close to that which the feed experiences in the HLW glass melter. The decomposition, melting, and dissolution of feed components (such as nitrates, carbonates, and silica) and the formation of intermediate crystalline phases (spinel, sodalite (Na8(AlSiO4)6(NO2)2), and Zr-containing minerals) were characterized using evolved gas analysis, volume-expansion measurement, optical microscope, scanning electron microscope, thermogravimetric analysis, differential scanning calorimetry, and X-ray diffraction. Nitrates and quartz, the major feed components, converted to a glass-forming melt by 880C. A chromium-free spinel formed in the nitrate melt starting from 520C and Sodalite, a transient product of corundum dissolution, appeared above 600C and eventually dissolved in glass. To investigate the effects of temperature history and minor components (Ru,Ag, and Cu) on the dissolution and growth of spinel crystals, samples were heated up to temperatures above liquidus temperature (TL), then subjected to different temperature histories, and analyzed. The results show that spinel mass fraction, crystals composition, and crystal size depend on the chemical and physical makeup of the feed and temperature history

  18. Extracting information on the spatial variability in erosion rate stored in detrital cooling age distributions in river sands

    Science.gov (United States)

    Braun, Jean; Gemignani, Lorenzo; van der Beek, Peter

    2018-03-01

    One of the main purposes of detrital thermochronology is to provide constraints on the regional-scale exhumation rate and its spatial variability in actively eroding mountain ranges. Procedures that use cooling age distributions coupled with hypsometry and thermal models have been developed in order to extract quantitative estimates of erosion rate and its spatial distribution, assuming steady state between tectonic uplift and erosion. This hypothesis precludes the use of these procedures to assess the likely transient response of mountain belts to changes in tectonic or climatic forcing. Other methods are based on an a priori knowledge of the in situ distribution of ages to interpret the detrital age distributions. In this paper, we describe a simple method that, using the observed detrital mineral age distributions collected along a river, allows us to extract information about the relative distribution of erosion rates in an eroding catchment without relying on a steady-state assumption, the value of thermal parameters or an a priori knowledge of in situ age distributions. The model is based on a relatively low number of parameters describing lithological variability among the various sub-catchments and their sizes and only uses the raw ages. The method we propose is tested against synthetic age distributions to demonstrate its accuracy and the optimum conditions for it use. In order to illustrate the method, we invert age distributions collected along the main trunk of the Tsangpo-Siang-Brahmaputra river system in the eastern Himalaya. From the inversion of the cooling age distributions we predict present-day erosion rates of the catchments along the Tsangpo-Siang-Brahmaputra river system, as well as some of its tributaries. We show that detrital age distributions contain dual information about present-day erosion rate, i.e., from the predicted distribution of surface ages within each catchment and from the relative contribution of any given catchment to the

  19. Extracting information on the spatial variability in erosion rate stored in detrital cooling age distributions in river sands

    Directory of Open Access Journals (Sweden)

    J. Braun

    2018-03-01

    Full Text Available One of the main purposes of detrital thermochronology is to provide constraints on the regional-scale exhumation rate and its spatial variability in actively eroding mountain ranges. Procedures that use cooling age distributions coupled with hypsometry and thermal models have been developed in order to extract quantitative estimates of erosion rate and its spatial distribution, assuming steady state between tectonic uplift and erosion. This hypothesis precludes the use of these procedures to assess the likely transient response of mountain belts to changes in tectonic or climatic forcing. Other methods are based on an a priori knowledge of the in situ distribution of ages to interpret the detrital age distributions. In this paper, we describe a simple method that, using the observed detrital mineral age distributions collected along a river, allows us to extract information about the relative distribution of erosion rates in an eroding catchment without relying on a steady-state assumption, the value of thermal parameters or an a priori knowledge of in situ age distributions. The model is based on a relatively low number of parameters describing lithological variability among the various sub-catchments and their sizes and only uses the raw ages. The method we propose is tested against synthetic age distributions to demonstrate its accuracy and the optimum conditions for it use. In order to illustrate the method, we invert age distributions collected along the main trunk of the Tsangpo–Siang–Brahmaputra river system in the eastern Himalaya. From the inversion of the cooling age distributions we predict present-day erosion rates of the catchments along the Tsangpo–Siang–Brahmaputra river system, as well as some of its tributaries. We show that detrital age distributions contain dual information about present-day erosion rate, i.e., from the predicted distribution of surface ages within each catchment and from the relative contribution of

  20. The Origin of the Chinese Central Tianshan Block in the Southern Central Asian Orogenic Belt: Evidence from Detrital Zircon Study

    Science.gov (United States)

    Huang, Z.; Long, X.; Yuan, C.

    2016-12-01

    The Chinese Central Tianshan Block (CTB) is one of the oldest continental fragments in the southern Central Asian Orogenic Belt (CAOB). Although it is vital for understanding the evolution of the CAOB, its origin has been poorly studied. The CTB was previously suggested to have been originated from the North China, the South China, the Tarim cratons or the East European Craton (Baltica). A total of 165 concordant U-Pb and Hf isotopic analyses of detrital zircon are obtained from three meta-sediments in the CTB, including one meta-sandstone from Xingxingxia formation and one meta-sandstone as well as one quartzite from Kawabulake formation. Detrital zircon grains from the Xingxingxia and Kawabulake formations are dominated by respective youngest age populations at 1002 Ma and 930-960 Ma, providing constraints on the maximum depositional ages for these two formations. Zircon grains from the meta-sediments have very similar age distributions, with two dominant peaks at 0.93-1.0 Ga and 1.0-1.6 Ga and a minor peak at 2.3-2.7 Ga. They have similar Hf isotopic signatures, suggesting that the meta-sediments in the CTB share similar sedimentary provenance. The early Neoproterozoic detrital zircon grains are mainly local-derived, whereas the Paleo-Mesoproterozoic grains are both autochthonous and allochthonous. The occurrence of these Mesoproterozoic and Neoproterozoic zircon grains are coincident with the Nuna breakup and the Rodinia assembly. This suggests that the CTB might experience the tectonic switching of the Nuna to the Rodinia. The distinct Meso-Neoproterozoic age patterns and Hf isotopic compositions of these detrital grains from the CTB and the surrounding blocks indicate that the CTB was not located close to the North China, the South China or the Tarim cratons in Precambrian. Our new data suggest that the CTB was most likely once a part of the East European Craton before the Neoproterozoic. This study was supported by National Basic Research Program of China

  1. The lower Mesozoic record of detrital zircon U-Pb geochronology of Sonora, Mexico, and its paleogeographic implications

    OpenAIRE

    González-León, Carlos M.; Valencia, Víctor A.; Lawton, Timothy F.; Amato, Jeffrey M.; Gehrels, George E.; Leggett, William J.; Montijo-Contreras, Óscar; Fernández, Miguel A.

    2009-01-01

    Detrital zircon U-Pb geochronology from each of the formations of the Triassic-Lower Jurassic Barranca and El Antimonio groups of central and northwestern Sonora and from the Lower Jurassic Basomari and Middle Jurassic Lily formations of northern Sonora indicate they contain distinctive zircon populations. A Proterozoic population has peak ages near 1.8, 1.7, 1.6, 1.4, and 1.1 Ga. A population of Permo-Triassic grains with important peak ages near 269, 254, 245, 234 and 227 Ma. A third popula...

  2. Detrital thermochronology of Rhine, Elbe and Meuse river sediment (Central Europe): implications for provenance, erosion and mineral fertility

    Science.gov (United States)

    Glotzbach, C.; Busschers, F. S.; Winsemann, J.

    2018-03-01

    Here we present detrital apatite fission track (AFT), zircon fission track (ZFT) and a few apatite (U-Th)/He (AHe) data of Middle Pleistocene to modern Rhine, Meuse and Elbe river sediments in order to resolve processes that control detrital age distributions (provenance, erosion and mineral fertility). We used a modelling approach to compare observed with theoretically predicted age distributions from an interpolated in situ AFT and ZFT age map. In situ cooling ages do show large differences in the Rhine drainage basin, facilitating the differentiation between different source regions. Inconsistencies between observed and theoretical age distributions of the Meuse and Elbe samples can be explained by mixing and reworking of sediments with different provenances (Meuse Middle Pleistocene terrace sediment) and a yet unexplored source region with old AFT ages (Elbe samples). Overall, the results show that detrital thermochronology is capable of identifying the provenance of Middle Pleistocene to modern sediments. The AFT age distributions of Rhine sediments are dominated ( 70%) by AFT ages representing the Alps. A possible explanation is higher erosion rates in the Alps as compared to areas outside the Alps. A Late Pleistocene sample from the Upper Rhine Graben contains apatite grains from the Molasse and Hegau volcanics, which we explain with a shift of the headwaters of the Rhine to the north as a result of intense Middle Pleistocene Riss glaciation. Contrary to the observed dominance of Alpine-derived AFT ages in Rhine sediments, the relative contribution of zircon ages with sources in the Alps is lower and significantly decreases downstream, suggesting a major source of zircons outside the Alps. This can be explained by increased zircon fertility of sediments derived from the Rhenish massif. Therefore, we conclude that erosion and mineral fertility are the main processes controlling detrital AFT and ZFT age distributions of the sampled river sediment. In case of

  3. Investigating the Early Carbon Cycle Using Carbonaceous Inclusions and Dissolved Carbon in Detrital Zircon

    Science.gov (United States)

    Bell, E. A.; Boehnke, P.; Harrison, M.; Mao, W. L.

    2015-12-01

    Because the terrestrial rock record extends only to ~4 Ga and older materials thus far identified are limited to detrital zircons, information about volatile abundances and cycles on early Earth is limited. Carbon, for instance, plays an important role not only in the modern biosphere but also in deep recycling of materials between the crust and mantle. We are investigating the record of carbon abundance and origin in Hadean zircons from Jack Hills (W. Australia) using two main approaches. First, carbon may partition into the zircon structure at trace levels during crystallization from a magma, and better understanding of this partitioning behavior will allow for zircon's use as a monitor of magmatic carbon contents. We have measured carbon abundances in zircon from a variety of igneous rocks (gabbro; I-, A-, and S-type granitoids) via SIMS and found that although abundances are typically low (average raw 12C/30Si ~ 1x10-6), S-type granite zircons can reach a factor of 1000 over this background. Around 10% of Hadean zircons investigated show similar enrichments, consistent with other evidence for the derivation of many Jack Hills zircons from S-type granitoids and with the establishment of modern-level carbon abundances in the crust by ca. 4.2 Ga. Diamond and graphite inclusions reported in the Jack Hills zircons by previous studies proved to be contamination by polishing debris, leaving the true abundance of these materials in the population uncertain. On a second front, we have identified and investigated primary carbonaceous inclusions in these zircons. From a population of over 10,000 Jack Hills zircons, we identified one concordant 4.10±0.01 Ga zircon that contains primary graphite inclusions (so interpreted due to their enclosure in a crack-free zircon host as shown by transmission X-ray microscopy and their crystal habit). Their δ13CPDB of -24±5‰ is consistent with a biogenic origin and, in the absence of a likely inorganic mechanism to produce such a

  4. A series of spinel phase cathode materials prepared by a simple hydrothermal process for rechargeable lithium batteries

    International Nuclear Information System (INIS)

    Liang Yanyu; Bao Shujuan; Li Hulin

    2006-01-01

    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. - Graphical abstract: It is a SEM image of the spinel LiMn 2 O 4 , which was prepared by this novel hydrothermal procedure. It illustrates that reasonable-crystallized spinel oxide has occurred through the special hydrothermal process and the average particle size declined to about 1 μm. This homogeneous grain size distribution provides an important morphological basis for the reversibility and accessibility of lithium ion insertion/extraction reactions

  5. Sodium storage capability of spinel Li4Mn5O12

    International Nuclear Information System (INIS)

    Zhang, Jiaolong; Wang, Wenhui; Li, Yingshun; Yu, Denis Y.W.

    2015-01-01

    Highlights: • Electrochemical behavior of spinel Li 4 Mn 5 O 12 is examined in Na-ion battery. • A capacity of 120.7 mAh g −1 is obtained during the first sodiation process. • Na storage performance is found to be strongly dependent on particle size. • Ion-exchange between Li ions and Na ions occurs in Li 4 Mn 5 O 12 structure upon cycling. • Loss of crystallinity with cycling, leading to capacity fading. - Abstract: Spinel Li 4 Mn 5 O 12 , a well-known 3 V Li-ion battery (LIB) material with excellent cycling stability and good rate capability, is examined as Na-ion battery (NIB) cathode for the first time. Electrochemical studies clearly show that Na ions can be reversibly inserted into and extracted from the three-dimensional spinel structure. However, unlike in LIB, the available capacity in NIB is strongly dependent on the particle size and current rate due to the sluggish Na-ion transport in solid phase. Cycle performance of Li 4 Mn 5 O 12 in NIB is also inferior to that in LIB. Ex-situ X-ray diffraction study indicates a gradual loss of crystallinity with cycling, and that the crystal lattice undergoes an irreversible expansion during the initial 20 cycles. Inductively coupled plasma spectroscopy shows a decrease of Li/Mn ratio in Li 4 Mn 5 O 12 with cycling. The results suggest that Li ions are removed from the material during the charging process. The charge-discharge mechanism is also discussed in the paper.

  6. On the Utility of Spinel Oxide Hosts for Magnesium-Ion Batteries.

    Science.gov (United States)

    Knight, James C; Therese, Soosairaj; Manthiram, Arumugam

    2015-10-21

    There is immense interest to develop Mg-ion batteries, but finding suitable cathode materials has been a challenge. The spinel structure has many advantages for ion insertion and has been successfully used in Li-ion batteries. We present here findings on the attempts to extract Mg from MgMn2O4-based spinels with acid (H2SO4) and with NO2BF4. The acid treatment was able to fully remove all Mg from MgMn2O4 by following a mechanism involving the disproportionation of Mn(3+), and the extraction rate decreased with increasing cation disorder. Samples with additional Mg(2+) ions in the octahedral sites (e.g., Mg1.1Mn1.9O4 and Mg1.5Mn1.5O4) also exhibit complete or near complete demagnesiation due to an additional mechanism involving ion exchange of Mg(2+) by H(+), but no Mg could be extracted from MgMnAlO4 due to the disruption of Mn-Mn interaction/contact across shared octahedral edges. In contrast, no Mg could be extracted with the oxidizing agent NO2BF4 from MgMn2O4 or Mg1.5Mn1.5O4 as the electrostatic repulsion between the divalent Mg(2+) ions prevents Mg(2+) diffusion through the 16c octahedral sites, unlike Li(+) diffusion, suggesting that spinels may not serve as potential hosts for Mg-ion batteries. The ability to extract Mg with acid in contrast to that with NO2BF4 is attributed to Mn dissolution from the lattice and the consequent reduction in electrostatic repulsion. The findings could provide insights toward the design of Mg hosts for Mg-ion batteries.

  7. Long term in vivo imaging with Cr{sup 3+} doped spinel nanoparticles exhibiting persistent luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Viana, B., E-mail: bruno.viana@chimie-paristech.fr [PSL Research University, Chimie ParisTech−CNRS, Institut de Recherche de Chimie Paris, 75005 Paris (France); Chimie-ParisTech, Paris cedex F-75231 (France); Sharma, S.K.; Gourier, D. [PSL Research University, Chimie ParisTech−CNRS, Institut de Recherche de Chimie Paris, 75005 Paris (France); Chimie-ParisTech, Paris cedex F-75231 (France); Maldiney, T.; Teston, E.; Scherman, D. [Unité de Technologies Chimiques et Biologiques pour la Santé (UTCBS), CNRS UMR 8258, INSERM U 1022, Paris cedex F-75270 (France); Université Paris Descartes, Sorbonne Paris Cité, Faculté des Sciences Pharmaceutiques et Biologiques, Paris cedex F-75270 (France); Chimie-ParisTech, Paris cedex F-75231 (France); Richard, C., E-mail: cyrille.richard@parisdescartes.fr [Unité de Technologies Chimiques et Biologiques pour la Santé (UTCBS), CNRS UMR 8258, INSERM U 1022, Paris cedex F-75270 (France); Université Paris Descartes, Sorbonne Paris Cité, Faculté des Sciences Pharmaceutiques et Biologiques, Paris cedex F-75270 (France); Chimie-ParisTech, Paris cedex F-75231 (France)

    2016-02-15

    Persistent luminescence is a singular property of some materials which are able to store the excitation or light irradiation energy at intrinsic traps or defects before slowly emitting lower energy photons within several hours. When such compounds are prepared as nanoparticles (NPs), when functionalization is realized to get colloidal materials well dispersed in aqueous medium, such nanoprobes open the use of the persistent luminescence for bioimaging applications. Recently, the numbers of in vivo applications increased with new modalities and new expectations. In this review, we focused our attention on the ZnGa{sub 2}O{sub 4}:Cr (ZGO:Cr) nanoparticles. When ZnGa{sub 2}O{sub 4} (ZGO), a normal spinel is doped with Cr{sup 3+} ions, a high brightness persistent luminescence material with an emission spectrum perfectly matching the transparency window of living tissues is obtained. It allows in vivo mouse imaging with an excellent target-to-background ratio. One interesting characteristic of ZGO:Cr lies in the fact that its persistent luminescence can be excited with orange/red light, well below its band gap energy and in the transparency window of living tissues. This important property allows multiple re-excitations to perform long term bioimaging. Antisite defects of the direct spinel structure are assumed to provide shallow traps which store the excitation light. Charge release by room temperature thermal excitation and recombination center, here trivalent chromium, are responsible for the persistent luminescence. Following a primary excitation (UV or visible), one also observed that trapped charges can be released under 977 nm light stimulation for several spinel gallate materials, therefore increasing the modalities and the materials envisioned for in vivo excitation of these NPs. - Highlights: • Review of the persistent luminescence for bio-imaging. • Long term bioimaging by in vivo excitation and photostimulation. • Challenges and main advances in the

  8. Crustal growth history of the Korean Peninsula:Constraints from detrital zircon ages in modern river sediments

    Institute of Scientific and Technical Information of China (English)

    Taejin Choi; Yong Il Lee; Yuji Orihashi

    2016-01-01

    U-Pb analyses were carried out on detrital zircon grains from major river-mouth sediments draining South Korea to infer provenance characteristics and the crustal growth history of the southern Korean Peninsula, using a laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS). The Korean Peninsula is located in the East Asian continental margin and mainly comprises three Precambrian massifs and two metamorphic belts in between them. We obtained 515 concordant to slightly discordant zircon ages ranging from ca. 3566 to ca. 48 Ma. Regardless of river-mouth location, predominance of Mesozoic (249e79 Ma) and Paleoproterozoic (2491e1691 Ma) ages with subordinate Archean ages in-dicates that the zircon ages reflect present exposures of plutonic/metamorphic rocks in the drainage basins of the South Korean rivers and the crustal growth of the southern Korean Peninsula was focused in these two periods. Comparison of detrital zircon-age data between the North and South Korean river sediments reveals that the Paleoproterozoic zircon age distributions of both regions are nearly identical, while the NeoproterozoicePaleozoic ages exist and the Mesozoic ages are dominant in southern Korean Peninsula. This result suggests that Precambrian terrains in Korea record the similar pre-Mesozoic magmatic history and that the influence of Mesozoic magmatism was mainly focused in South Korea.

  9. Triassic North American paleodrainage networks and sediment dispersal of the Chinle Formation: A quantitative approach utilizing detrital zircons

    Science.gov (United States)

    Blum, M. D.; Umbarger, K.

    2017-12-01

    The Triassic Chinle Formation is a fluvial succession deposited in a backarc setting across the present-day Colorado Plateau of the southwestern United States. Existing studies have proposed various mechanisms responsible for the unique stratigraphic architecture and depositional sequences of the Chinle. However, these studies lack necessary age control to correlate stratigraphic patterns with contemporaneous mechanisms. This study will collect new samples for detrital zircon analysis, as well as upgrade existing samples (to n=300) from Dickinson and Gehrels (2008), to improve the resolution of Triassic sediment provenance from source-to-sink. The improved dataset allows appraisal of the multiple provenance terranes that contributed to the Chinle depositional system to delineate and reconstruct paleodrainage patterns. The additional samples will be collected systematically from the base of the Chinle, and vertically throughout the section to capture a regional story of how the continental scale drainage reorganized through time. U-Pb ages of detrital zircons will be utilized to provide quantitative fingerprinting information to constrain interpretations for the origin and transport history of the Chinle fluvial succession in time and space.

  10. Breeding Westland petrels as providers of detrital carbon and nitrogen for soil arthropods : a stable isotope study

    International Nuclear Information System (INIS)

    Hawke, D.J.; Clark, J.M.; Vallance, J.R.

    2013-01-01

    Seabirds deposit large quantities of marine detritus on land, but little is known of the soil arthropods processing this material. Burrow-nesting seabirds concentrate their activities within their burrows, so we tested the hypothesis that burrow arthropod fauna is more marine-like in its isotopic enrichment ( 13 C/ 12 C, 15 N/ 14 N); expressed as δ 13 C and δ 15 N) than the arthropods on the adjacent forest floor. Results from a Westland petrel (Procellaria westlandica) colony on the South Island of New Zealand did not support the hypothesis. Instead, δ 15 N was universally marine (13-22 per mil). While δ 13 C separated into two clusters, the distribution was not according to arthropod provenance. Most taxa had a terrestrial δ 13 C; only two taxa (a leiodid beetle and the mesostigmatic mite Ayersacarus woodi) incorporated marine C. The leiodid beetle occurs both in burrows and on the forest floor; beetles from both habitats had a marine δ 13 C. Ayersacarus woodi is found only in burrows. We conclude that, in this system, marine and terrestrial detrital C is processed separately, and that marine detrital C enters the terrestrial ecosystem through a very few arthropod taxa. (author). 33 refs., 1 fig.

  11. Frequent Prescribed Burning as a Long-term Practice in Longleaf Pine Forests Does Not Affect Detrital Chemical Composition.

    Science.gov (United States)

    Coates, T Adam; Chow, Alex T; Hagan, Donald L; Wang, G Geoff; Bridges, William C; Dozier, James H

    2017-09-01

    The O horizon, or detrital layer, of forest soils is linked to long-term forest productivity and health. Fuel reduction techniques, such as prescribed fire, can alter the thickness and composition of this essential ecosystem component. Developing an understanding of the changes in the chemical composition of forest detritus due to prescribed fire is essential for forest managers and stakeholders seeking sustainable, resilient, and productive ecosystems. In this study, we evaluated fuel quantity, fuel structure, and detrital chemical composition in longleaf pine ( Miller) forests that have been frequently burned for the last 40 yr at the Tom Yawkey Wildlife Center in Georgetown, SC. Our results suggest that frequent prescribed fire reduces forest fuel quantity ( burned detritus. Our burning activities varied in the short term, consisting of annual dormant, annual growing, and biennial dormant season burns. Seasonal distinctions were present for fuel quantity and vertical fuel structure, but these differences were not noted for the benzene/phenol ratio. These results are significant as more managers consider burning existing longleaf stands while determining effective management practices for longleaf stands yet to be established. Managers of such stands can be confident that frequent, low-intensity, low-severity prescribed burns in longleaf pine forests do little to affect the long-term chemical composition of forest detritus. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

  12. Nanoparticles of spinel and perovskite ferromagnets and prospects for their application in medicine

    Energy Technology Data Exchange (ETDEWEB)

    Belous, A. G., E-mail: belous@ionc.kar.net, E-mail: solopan@ukr.net, E-mail: yelenicho@ukr.net; Solopan, S. O., E-mail: belous@ionc.kar.net, E-mail: solopan@ukr.net, E-mail: yelenicho@ukr.net; Yelenich, O. V., E-mail: belous@ionc.kar.net, E-mail: solopan@ukr.net, E-mail: yelenicho@ukr.net [Institute of General and Inorganic Chemistry, prospekt Palladina 32-34, 03142 Kyiv (Ukraine); Tovstolytkin, A. I., E-mail: atov@imag.kiev.ua [Institute of Magnetism, bulvar Vernadskoho 36-b, 03142 Kyiv (Ukraine); Kolodiazhnyi, T. V., E-mail: kolodiazhnyi.taras@nims.go.jp [National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); Osinsky, S. P., E-mail: osion@onconet.kiev.ua, E-mail: bybnovskayal@ukr.net; Bubnovskaya, L. N., E-mail: osion@onconet.kiev.ua, E-mail: bybnovskayal@ukr.net [R.E. Kavetsky Institute of Experimental Pathology, Oncology and Radiobiology, vul. Vasylkivska 45, 03022 Kyiv (Ukraine)

    2014-11-05

    In this work, nanoparticles of La{sub 0.75}Sr{sub 0.25}MnO{sub 3} compounds with perovskite structure and AFe{sub 2}O{sub 4} (A = Mn, Fe, Co, Ni, Zn) with spinel structure have been synthesized by precipitation from diethylene glycol and microemulsion using Triton X-100 surfactant. Comparative X-ray diffraction and magnetic studies of the synthesized nanoparticles have been carried out. Magnetic fluids prepared from synthesized nanopowders have been characterized by calorimetric measurements of specific loss power (SLP)

  13. Solid-liquid phase equilibria of Fe-Cr-Al alloys and spinels

    Science.gov (United States)

    McMurray, J. W.; Hu, R.; Ushakov, S. V.; Shin, D.; Pint, B. A.; Terrani, K. A.; Navrotsky, A.

    2017-08-01

    Ferritic FeCrAl alloys are candidate accident tolerant cladding materials. There is a paucity of data concerning the melting behavior for FeCrAl and its oxides. Analysis tools have therefore had to utilize assumptions for simulations using FeCrAl cladding. The focus of this study is to examine in some detail the solid-liquid phase equilibria of FeCrAl alloys and spinels with the aim of improving the accuracy of severe accident scenario computational studies.

  14. Sepentinized Peridotite Spinel Composition: Northern Central Indian Ridge at 6°39

    Science.gov (United States)

    Ray, D.; Banerjee, R.; Iyer, S. D.; Balaram, V.; Speakman, J.

    2005-12-01

    Exposures of serpentinized peridotites on the seafloor at slow-spreading ridges have been interpreted either as accretion of ridge segments in a magma-starved condition along the non-transform setting or as preferential outcrops at ridge offsets in transform fault setting. Here we present the mineral chemistry and geochemistry of serpentinites and serpentinized spinel peridotites recovered from an off axis region (corner high) at south of Vityaz transform fault (6°39'S), Northern Central Indian Ridge. Our purpose is to use mineral chemical data of serpentine and spinel to investigate the effect of low temperature alteration processes and degree of partial melting. Serpentine composition shows presence of high Mg-rich lizardite and chrysotile pseudomorphs and these rocks mostly preserve `mesh rim', `window' and `hourglass' textures, representing extensive hydration during low temperature hydrothermal alteration. In thin section, serpentine veins (mainly lensoidal, pinch and swell or anastomosing) are common, sometime crosscutting the `mesh rim' textures to attest to the intensity of serpentinization process. In one sample, a 1.9 cm-thick feldspathic vein crosscut the serpentinite as a porphyroblast and this indicates discontinuity in magmatic crust caused due to less magma input at off-axis region facilitate the intrusion of short-living feeder dykes of highly fractionated late magmatic liquids within the peridotite. In addition, in hand specimen, presence of smaller-scale striations analogous to slickenlines on serpentinite surfaces suggests low-angle faulting, which could have enhanced pervasive serpentinization during their subsequent emplacement. Individual serpentine grain displays very low Ca content (0.01 wt%) suggesting possible absence of any secondary Ca-rich phases also verified by very low Sr content (connotation. Limited data on composition of individual spinel porphyroclast exhibits substantial variation in their Mg# (mole [Mg/ Mg+Fe2]) and Cr# (mole

  15. Multifunctional thick-film structures based on spinel ceramics for environment sensors

    International Nuclear Information System (INIS)

    Vakiv, M; Hadzaman, I; Klym, H; Shpotyuk, O; Brunner, M

    2011-01-01

    Temperature sensitive thick films based on spinel-type NiMn 2 O 4 -CuMn 2 O 4 -MnCo 2 O 4 manganites with p- and p + -types of electrical conductivity and their multilayer p + -p structures were studied. These thick-film elements possess good electrophysical characteristics before and after long-term ageing test at 170 deg. C. It is shown that degradation processes connected with diffusion of metallic Ag into film grain boundaries occur in one-layer p-and p + -conductive films. Some part of the p + -p structures were of high stability, the relative electrical drift being no more than 1 %.

  16. In-situ synchrotron PXRD study of spinel LiMn2O4 nanocrystal formation

    DEFF Research Database (Denmark)

    Birgisson, Steinar; Jensen, Kirsten Marie Ørnsbjerg; Christiansen, Troels Lindahl

    Many solvothermal reactions have a great potential for environmentally friendly and easily scalable way for producing nanocrystalline materials on an industrial scale. Here we study hydrothermal formation of spinel LiMn2O4 which is a well-known cathode material for Li-ion batteries. The LiMn2O4...... nanoparticles are formed by reducing KMnO4 in an aqueous solution containing Li-ions. The reducing agent is an alcohol (here ethanol) and the reaction takes place under high pressure and temperature. The LiMn2O4 nanocrystals are unstable towards further reduction to Mn3O4 nanocrystals. Possible reaction route...

  17. Synthesis of {gamma}-aluminium oxynitride spinel using thermal plasma technique

    Energy Technology Data Exchange (ETDEWEB)

    Panda, Pravuram; Singh, S. K.; Sinha, S. P. [School of Applied Science (Physics), KIIT University, Bhubaneswar 751024 (India); Advanced Materials Technology Department, IMMT (CSIR), Bhubaneswar 751013 (India); School of Applied Science (Physics), KIIT University, Bhubaneswar 751024 (India)

    2012-07-23

    The synthesis technique of {gamma}-AlON in NH{sub 3} plasma using extended arc thermal plasma reactor have been reported. Dense cubic AlON spinel was synthesized in liquid state by fusion of mixture of Al{sub 2}O{sub 3} and AlN powder under thermal plasma. The density of the fused AlON was found to be 3.64 g/cc which is 98.11% of theoretical value. The formation of AlON was confirmed from XRD and Raman studies. Well faceted structure of plasma fused AlON was observed in FE-SEM micrograph.

  18. Fabrication of MgAl2O4 spinel/niobium laminar composites by plasma spraying

    International Nuclear Information System (INIS)

    Boncoeur, M.; Lochet, N.; Miomandre, F.; Schnedecker, G.

    1994-01-01

    The feasibility of plasma spray manufacturing of laminar ceramic matrix composites made of alternate thin layers of a ceramic oxide and a metal is demonstrated with a composite made of 7 layers, each 0.2 mm thick, of MgAl 2 O 4 spinel and niobium. Microstructure and mechanical characteristics have been studied with both as-sprayed and heat-treated under vacuum at 1400 C conditions. It is shown that the as-sprayed composite is brittle but becomes pseudo-plastic after heat treatment. These laminar composites are very attractive for the manufacturing of large surface, few millimeter thick components. (from authors). 4 figs., 4 refs

  19. Spinel ferrite nanocrystals embedded inside ZnO: magnetic, electronic andmagneto-transport properties

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Shengqiang; Potzger, K.; Xu, Qingyu; Kuepper, K.; Talut, G.; Marko, D.; Mucklich, A.; Helm, M.; Fassbender, J.; Arenholz, E.; Schmidt, H.

    2009-08-21

    In this paper we show that spinel ferrite nanocrystals (NiFe{sub 2}O{sub 4}, and CoFe{sub 2}O{sub 4}) can be texturally embedded inside a ZnO matrix by ion implantation and post-annealing. The two kinds of ferrites show different magnetic properties, e.g. coercivity and magnetization. Anomalous Hall effect and positive magnetoresistance have been observed. Our study suggests a ferrimagnet/semiconductor hybrid system for potential applications in magneto-electronics. This hybrid system can be tuned by selecting different transition metal ions (from Mn to Zn) to obtain various magnetic and electronic properties.

  20. Effects of γ-irradiation upon the optical behavior of spinel

    International Nuclear Information System (INIS)

    White, G.S.; Lee, K.H.; Crawford, J.H.Jr.

    1977-01-01

    The effect of 137 Cs gamma irradiation (0.67 MeV photons) upon the optical absorption and thermoluminescence of spinel (MgAl 2 O 4 ) is studied. Exposure to gamma radiation provides electrons which are captured at Fesup(3+) in octahedral sites, thereby producing Fesup(2+) and destroying the 4.8 and 6.4 eV absorption bands. Isochronal annealing curves of the 3.1 and 4.8 eV peaks are given. A reciprocal relationship between the recovery of the 4.8 eV band and the thermoluminescence immediately after irradiation and after sitting over night has been measured

  1. Hydration of refractory cements, with spinel phase generated in-situ

    International Nuclear Information System (INIS)

    Lavat, A.E; Grasselli, M.C; Giuliodori Lovecchio, E

    2008-01-01

    High alumina refractory materials with additions of synthetic spinel (MgAl 2 O 4 ) have good thermo mechanical and attack from slag properties, which are useful in many technological applications. The spinel phase generated in-situ, MA, has proven to be a suitable and economic alternative to the use of sintered or electrocast spinels. Prior studies have established synthesis conditions for refractory cements with the spinel phase generated in-situ (CCAMA) starting with alumina mixtures and Buenos Aires dolomites. The binding properties of the aluminous cements depend on the hydrated calcium aluminates that form in the setting and hardening stages of the pastes. To avoid breaks, the refractory material must undergo programmed heating before reaching the serviceable temperature. It should also include the present phases and the transformations that occur at different temperatures. In this context knowledge about the green mineral composition and its response to an increase in temperature is especially important. This work presents studies to define the composition of CCAMA cement mortars at different hydration ages, and to estimate phase proportions and behavior during dehydration. DRX and FTIR techniques are applied in order to follow the structural changes that take place during the hydration process. The evolution of the dehydration is also studied, mostly using FTIR. The mortars were prepared with a water/cement ration of 0.5, recommended for this kind of work. The hydration was carried out at room temperature and samples were analyzed at the following ages: 15 min.; 1 h.; 1, 3, 7, 14, 28, 60 and 90 days. With the results the evolution of the phases as a function of the age of the hydration were studied. The main hydrate that was formed was CAH 10 , with a significantly increased proportion during the first 14 days of hydration. Its carbonation was also observed by the presence of calcium carboaluminates and the formation of gibbsite. The MA phase is also

  2. A series of spinel phase cathode materials prepared by a simple hydrothermal process for rechargeable lithium batteries

    Science.gov (United States)

    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.

  3. Mechanical characterization of magnesium aluminate MgO·nAl2O3 spinel single crystals irradiated with Cu- ions

    International Nuclear Information System (INIS)

    Ohmura, Takahito; Lee, Chi-Gyu; Kishimoto, Naoki

    2003-01-01

    Ion-irradiation response of spinel single crystals was investigated using a nanoindentation technique. Specimens of stoichiometric (n=1) and non-stoichiometric (n=2.4) single crystals of MgO n(Al 2 O 3 ) spinel were irradiated with 60 keV Cu - ion at room temperature. Dose rate ranged from 1 to 100 μA/cm 2 , and a total dose was kept constant at 3x10 16 ions/cm 2 . Both plastic hardness and elastic modulus of all the irradiated specimens were softened. Radiation-induced swelling simultaneously occurred. Rutherford back scattering spectroscopy detected disordering of spinel crystalline structure. Accordingly, the radiation-induced softening and swelling are ascribed to accumulation of point defects associated with the disordering. In comparison between the stoichiometric and the non-stoichiometric specimens, the radiation-induced softening is suppressed in the non-stoichiometric composition. (author)

  4. Structure of spinel at high temperature using in-situ XANES study at the Al and Mg K-edge

    Energy Technology Data Exchange (ETDEWEB)

    Ligny, D de [Universite Claude Bernard Lyon 1, LPCML, 69622 Villeurbanne (France); Neuville, D R [Physique des Mineraux et Magmas, Geochimie-Cosmochimie, CNRS-IPGP, 4 place Jussieu, 75005 Paris (France); Flank, A-M; Lagarde, P, E-mail: deligny@pcml.univ-lyon1.f [Synchrotron SOLEIL, L' Orme des Merisiers, Saint Aubin, 91192 France (France)

    2009-11-15

    We present structural information obtained on spinel at high temperature (298-2400 K) using in situ XANES at the Mg and Al K-edge. Spinel, {sup [4]}(Al{sub x},Mg{sub 1-x}){sup [6]}(Al{sub 2-x},Mg{sub x})O{sub 4}, with increasing temperature, show a substitution of Mg by Al and Al by Mg in their respective sites. This substitution corresponds to an inversion of the Mg and Al sites. Furthermore, both experiments at the Al and Mg K-edges are in good agreement with XANES calculation made using FDMNES code.

  5. Electrochemical and spectroscopic characterization of lithium titanate spinel Li{sub 4}Ti{sub 5}O{sub 12}

    Energy Technology Data Exchange (ETDEWEB)

    Schneider, Holger; Maire, Pascal [Paul Scherrer Institut, Electrochemistry Laboratory, Section Electrochemical Energy Storage, CH-5232 Villigen PSI (Switzerland); Novak, Petr, E-mail: petr.novak@psi.ch [Paul Scherrer Institut, Electrochemistry Laboratory, Section Electrochemical Energy Storage, CH-5232 Villigen PSI (Switzerland)

    2011-10-30

    Herein we describe electrochemical and spectroscopic properties of lithium titanate spinel as well as an easy method based on colorimetry to determine the lithium content of electrodes containing lithium titanate spinel as active material. Raman microspectrometry measurements have been performed to follow lithium insertion into and extraction from the active material, respectively. The Raman signals display a pronounced fading of intensity already at low levels of lithium intercalation and disappear at a SOC higher than {approx}10%. However, the colorimetric method can be used up to a SOC of 50%.

  6. Influence of Mn-Co Spinel Coating on Oxidation Behavior of Ferritic SS Alloys for SOFC Interconnect Applications

    DEFF Research Database (Denmark)

    Venkatachalam, Vinothini; Molin, Sebastian; Kiebach, Wolff-Ragnar

    2014-01-01

    Chromia forming ferritic stainless steels (SS) are being considered for intermediate temperature solid oxide fuel cell interconnect applications. However, protective coatings are in general needed to avoid chromium volatilization and poisoning of cathodes from chromium species. Mn-Co spinel is one...... of the promising candidates to prevent chromium outward diffusion, improve oxidation resistance and ensure high electrical conductivity over the lifetime of interconnects. In the present study, uniform and well adherent Mn-Co spinel coatings were produced on Crofer 22APU using electrophoretic deposition (EPD...

  7. Simple synthetic route to manganese-containing nanowires with the spinel crystal structure

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Lei; Zhang, Yan; Hudak, Bethany M.; Wallace, Damon K.; Kim, Doo Young; Guiton, Beth S.

    2016-08-15

    This report describes a new route to synthesize single-crystalline manganese-containing spinel nanowires (NWs) by a two-step hydrothermal and solid-state synthesis. Interestingly, a nanowire or nanorod morphology is maintained during conversion from MnO{sub 2}/MnOOH to CuMn{sub 2}O{sub 4}/Mg{sub 2}MnO{sub 4}, despite the massive structural rearrangement this must involve. Linear sweep voltammetry (LSV) curves of the products give preliminary demonstration that CuMn{sub 2}O{sub 4} NWs are catalytically active towards the oxygen evolution reaction (OER) in alkaline solution, exhibiting five times the magnitude of current density found with pure carbon black. - Highlights: • Synthesis of single-crystalline manganese-containing spinel nanowires. • Binary oxide nanowire converted to ternary oxide wire through solid state reaction. • Approach to structure conversion with shape retention could be generally applicable. • Copper and Manganese display multiple oxidation states with potential for catalysis. • CuMn{sub 2}O{sub 4} nanowires show promise as catalysts for the oxygen evolution reaction.

  8. Observation of large low-field magnetoresistance in spinel cobaltite: A new half-metal

    KAUST Repository

    Li, Peng

    2015-12-10

    Low-field magnetoresistance is an effective and energy-saving way to use half-metallic materials in magnetic reading heads and magnetic random access memory. Common spin-polarized materials with low field magnetoresistance effect are perovskite-type manganese, cobalt, and molybdenum oxides. In this study, we report a new type of spinel cobaltite materials, self-assembled nanocrystalline NiCo2O4, which shows large low field magnetoresistance as large as –19.1% at 0.5 T and –50% at 9 T (2 K). The large low field magnetoresistance is attributed to the fast magnetization rotation of the core nanocrystals. The surface spin-glass is responsible for the observed weak saturation of magnetoresistance under high fields. Our calculation demonstrates that the half-metallicity of NiCo2O4 comes from the hopping eg electrons within the tetrahedral Co-atoms and the octahedral Ni-atoms. The discovery of large low-field magnetoresistance in simple spinel oxide NiCo2O4, a non-perovskite oxide, leads to an extended family of low-field magnetoresistance materials. (© 2016 WILEY-VCH Verlag GmbH &Co. KGaA, Weinheim)

  9. Experimental and ab initio investigations on textured Li–Mn–O spinel thin film cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, J., E-mail: Julian.Fischer@kit.edu [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials (IAM), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Music, D. [RWTH Aachen University, Materials Chemistry, Kopernikusstrasse 10, 52074 Aachen (Germany); Bergfeldt, T.; Ziebert, C.; Ulrich, S.; Seifert, H.J. [Karlsruhe Institute of Technology (KIT), Institute for Applied Materials (IAM), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany)

    2014-12-01

    This paper describes the tailored preparation of nearly identical lithium–manganese–oxide thin film cathodes with different global grain orientations. The thin films were synthesized by rf magnetron sputtering from a LiMn{sub 2}O{sub 4}-target in a pure argon plasma. Under appropriate processing conditions, thin films with a cubic spinel structure and a nearly similar density and surface topography but different grain orientation, i.e. (111)- and (440)-textured films, were achieved. The chemical composition was determined by inductively coupled plasma optical emission spectroscopy and carrier gas hot extraction. The constitution- and microstructure were evaluated by X-ray diffraction and Raman spectroscopy. The surface morphology and roughness were investigated by scanning electron and atomic force microscopy. The differently textured films represent an ideal model system for studying potential effects of grain orientation on the lithium ion diffusion and electrochemical behavior in LiMn{sub 2}O{sub 4}-based thin films. They are nearly identical in their chemical composition, atomic bonding behavior, surface-roughness, morphology and thickness. Our initial ab initio molecular dynamics data indicate that Li ion transport is faster in (111)-textured structure than in (440)-textured one. - Highlights: • Thin film model system of differently textured cubic Li–Mn–O spinels. • Investigation of the Li–Mn–O thin film mass density by X-ray reflectivity. • Ab initio molecular dynamics simulation on Li ion diffusion in LiMn{sub 2}O{sub 4}.

  10. Ferromagnetic-phase transition in the spinel-type CuCr2Te4

    International Nuclear Information System (INIS)

    Suzuyama, Takeshi; Awaka, Junji; Yamamoto, Hiroki; Ebisu, Shuji; Ito, Masakazu; Suzuki, Takashi; Nakama, Takao; Yagasaki, Katsuma; Nagata, Shoichi

    2006-01-01

    Ferromagnetic-phase transition in spinel-type CuCr 2 Te 4 has been clearly observed. CuCr 2 Te 4 is a telluride-spinel with the lattice constant a=11.134A, which has been synthesized successfully. The heat capacity exhibits a sharp peak due to the ferromagnetic-phase transition with the Curie temperature T C =326K. This value of T C corresponds exactly to that of the negative peak of dM/dT in low field of 1.0Oe. The magnetic susceptibility shows the Curie-Weiss behavior between 380 and 650K with the effective magnetic moment μ eff =4.14μ B /Cr-ion and the Weiss constant θ=+357K. The low temperature magnetization indicates the spin-wave excitations, where the existence of first term of Bloch T 3/2 law and the next T 5/2 term are verified experimentally. This spin-wave excitation is detected up to approximately 250K which is a fairly high temperature

  11. Crystal field and site deformation in spinels and pentavalent uranium compounds

    International Nuclear Information System (INIS)

    Drifford, M.; Soulie, E.

    1976-01-01

    Magnesium aluminates with different alumina contents have the spinel structure. The optical absorption spectra of doped spinel compounds (Cr 3+ , Ni 2+ , Co 2+ ) or E.S.R. spectra (Cr 3+ , Mn 2+ ) are used for the investigation of the position of the doping materials and the deformation of the crystal sites, and give information on the structural disorders. The local structural information given by the doping materials are compared with the mean structure parameters obtained from X-ray diffraction. The optical absorption spectrum and the principal components of the g tensor for UF 6 Cs and the thermal variation in the magnetic susceptibility for UF 8 Cs 3 and UF 8 (NH 4 ) are used for determining the parameters of the electron Hamiltonian for the f 1 configuration. A rather significant covalent aspect is evidenced for UF 6 Cs, in the framework of the model of Eisenstein and Pryce, this property being weaker for the other two complex compounds. The three parameters giving the crystal field at a deformed cubic site with Dsub(3d) symmetry in the Newman superposition model are noticeably weaker for the 8-coordination than for the 6-coordination. As for UF 8 Cs 3 and UF 8 (NH 4 ) 3 a calculation predicts an electronic levels with a very low excitation, at about 110 and 70cm -1 respectively [fr

  12. Dislocation loops in spinel crystals irradiated successively with deep and shallow ion implants

    International Nuclear Information System (INIS)

    Ai, R.X.; Cooper, E.A.; Sickafus, K.E.; Nastasi, M.; Bordes, N.; Ewing, R.C.

    1993-01-01

    This study examines the influence of microstructural defects on irradiation damage accumulation in the oxide spinel. Single crystals of the compound MgAl 2 O 4 with surface normal [111] were irradiated under cryogenic temperature (100K) either with 50 keV Ne ions (fluence 5.0 x 10 12 /cm 2 ), 400 keV Ne ions (fluence 6.7 x 10 13 /cm 2 ) or successively with 400 keV Ne ions followed by 50 keV Ne ions. The projected range of 50 keV Ne ions in spinel is ∼50 mn (''shallow'') while the projected range of 400 keV Ne ions is ∼500 mn (''deep''). Transmission electron microscopy (TEM) was used to examine dislocation loops/defect clusters formed by the implantation process. Measurements of the dislocation loop size were made using weak-beam imaging technique on cross-sectional TEM ion-implanted specimens. Defect clusters were observed in both deep and shallow implanted specimens, while dislocation loops were observed in the shallow implanted sample that was previously irradiated by 400 keV Ne ions. Cluster size was seen to increase for shallow implants in crystals irradiated with a deep implant (size ∼8.5 nm) as compared to crystals treated only to a shallow implant (size ∼3.1 nm)

  13. Observation of large low-field magnetoresistance in spinel cobaltite: A new half-metal

    KAUST Repository

    Li, Peng; Xia, Chuan; Zheng, Dongxing; Wang, Ping; Jin, Chao; Bai, Haili

    2015-01-01

    Low-field magnetoresistance is an effective and energy-saving way to use half-metallic materials in magnetic reading heads and magnetic random access memory. Common spin-polarized materials with low field magnetoresistance effect are perovskite-type manganese, cobalt, and molybdenum oxides. In this study, we report a new type of spinel cobaltite materials, self-assembled nanocrystalline NiCo2O4, which shows large low field magnetoresistance as large as –19.1% at 0.5 T and –50% at 9 T (2 K). The large low field magnetoresistance is attributed to the fast magnetization rotation of the core nanocrystals. The surface spin-glass is responsible for the observed weak saturation of magnetoresistance under high fields. Our calculation demonstrates that the half-metallicity of NiCo2O4 comes from the hopping eg electrons within the tetrahedral Co-atoms and the octahedral Ni-atoms. The discovery of large low-field magnetoresistance in simple spinel oxide NiCo2O4, a non-perovskite oxide, leads to an extended family of low-field magnetoresistance materials. (© 2016 WILEY-VCH Verlag GmbH &Co. KGaA, Weinheim)

  14. Experimental and ab initio investigations on textured Li–Mn–O spinel thin film cathodes

    International Nuclear Information System (INIS)

    Fischer, J.; Music, D.; Bergfeldt, T.; Ziebert, C.; Ulrich, S.; Seifert, H.J.

    2014-01-01

    This paper describes the tailored preparation of nearly identical lithium–manganese–oxide thin film cathodes with different global grain orientations. The thin films were synthesized by rf magnetron sputtering from a LiMn 2 O 4 -target in a pure argon plasma. Under appropriate processing conditions, thin films with a cubic spinel structure and a nearly similar density and surface topography but different grain orientation, i.e. (111)- and (440)-textured films, were achieved. The chemical composition was determined by inductively coupled plasma optical emission spectroscopy and carrier gas hot extraction. The constitution- and microstructure were evaluated by X-ray diffraction and Raman spectroscopy. The surface morphology and roughness were investigated by scanning electron and atomic force microscopy. The differently textured films represent an ideal model system for studying potential effects of grain orientation on the lithium ion diffusion and electrochemical behavior in LiMn 2 O 4 -based thin films. They are nearly identical in their chemical composition, atomic bonding behavior, surface-roughness, morphology and thickness. Our initial ab initio molecular dynamics data indicate that Li ion transport is faster in (111)-textured structure than in (440)-textured one. - Highlights: • Thin film model system of differently textured cubic Li–Mn–O spinels. • Investigation of the Li–Mn–O thin film mass density by X-ray reflectivity. • Ab initio molecular dynamics simulation on Li ion diffusion in LiMn 2 O 4

  15. Synthesis, Characterization, and Sensor Applications of Spinel ZnCo2O4 Nanoparticles

    Directory of Open Access Journals (Sweden)

    Juan Pablo Morán-Lázaro

    2016-12-01

    Full Text Available Spinel ZnCo2O4 nanoparticles were synthesized by means of the microwave-assisted colloidal method. A solution containing ethanol, Co-nitrate, Zn-nitrate, and dodecylamine was stirred for 24 h and evaporated by a microwave oven. The resulting solid material was dried at 200 °C and subsequently calcined at 500 °C for 5 h. The samples were characterized by scanning electron microscopy (SEM, transmission electron microscopy (TEM, X-ray diffraction (XRD, and Raman spectroscopy, confirming the formation of spinel ZnCo2O4 nanoparticles with average sizes between 49 and 75 nm. It was found that the average particle size decreased when the dodecylamine concentration increased. Pellets containing ZnCo2O4 nanoparticles were fabricated and tested as sensors in carbon monoxide (CO and propane (C3H8 gases at different concentrations and temperatures. Sensor performance tests revealed an extremely high response to 300 ppm of CO at an operating temperature of 200 °C.

  16. P-type zinc oxide spinels: application to transparent conductors and spintronics

    International Nuclear Information System (INIS)

    Stoica, Maria; S Lo, Cynthia

    2014-01-01

    We report on the electronic and optical properties of two theoretically predicted stable spinel compounds of the form ZnB 2 O 4 , where B = Ni or Cu; neither compound has been previously synthesized, so we compare them to the previously studied p-type ZnCo 2 O 4 spinel. These new materials exhibit spin polarization, which is useful for spintronics applications, and broad conductivity maxima near the valence band edge that indicate good p-type dopability. We show that 3d electrons on the octahedrally coordinated Zn atom fall deep within the valence band and do not contribute significantly to the electronic structure near the band edge of the material, while the O 2p and tetrahedrally coordinated B 3d electrons hybridize broadly in the shallow valence states, resulting in increasing curvature (i.e., decreased electron effective mass) of valence bands near the band edge. In particular, ZnCu 2 O 4 exhibits high electrical conductivities in the p-doping region near the valence band edge that, at σ=2×10 4  S cm −1 , are twice the maximum found for ZnCo 2 O 4 , a previously synthesized compound in this class of materials. This material also exhibits ferromagnetism in all of its most stable structures, which makes it a good candidate for further study as a dilute magnetic semiconductor. (paper)

  17. Single-crystalline MgAl2O4 spinel nanotubes using a reactive and removable MgO nanowire template

    International Nuclear Information System (INIS)

    Fan Hongjin; Knez, Mato; Scholz, Roland; Nielsch, Kornelius; Pippel, Eckhard; Hesse, Dietrich; Goesele, Ulrich; Zacharias, Margit

    2006-01-01

    Using MgO nanowires as a reactive template, we fabricated for the first time single-crystal MgAl 2 O 4 spinel nanotubes through an interfacial solid-state reaction of MgO-Al 2 O 3 core-shell nanowires. Single-crystal MgO nanowires are coated with a conformal thin layer of amorphous Al 2 O 3 via atomic layer deposition. Subsequent annealing at 700 deg. C activates the interfacial reaction between MgO and Al 2 O 3 , transforming the alumina shell into a spinel shell. Finally, after etching away the remaining MgO core in ammonia sulfuric solution, MgAl 2 O 4 spinel nanotubes are obtained. As a transition from conventional planar spinel layers via thin-film interface reactions, our result might open a window for the fabrication of a wide variety of MgO-based spinel one-dimensional nanostructures

  18. Thermodynamic Modelling of Fe-Cr-Ni-Spinel Formation at the Light-Water Reactor Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Kurepin, V.A.; Kulik, D.A.; Hitpold, A.; Nicolet, M

    2002-03-01

    In the light water reactors (LWR), the neutron activation and transport of corrosion products is of concern in the context of minimizing the radiation doses received by the personnel during maintenance works. A practically useful model for transport and deposition of the stainless steel corrosion products in LWR can only be based on an improved understanding of chemical processes, in particular, on the attainment of equilibrium in this hydrothermal system, which can be described by means of a thermodynamic solid-solution -aqueous-solution (SSAS) model. In this contribution, a new thermodynamic model for a Fe-Cr-Ni multi-component spinel solid solutions was developed that considers thermodynamic consequences of cation interactions in both spinel sub-Iattices. The obtained standard thermodynamic properties of two ferrite and two chromite end-members and their mixing parameters at 90 bar pressure and 290 *c temperature predict a large miscibility gap between (Fe,Ni) chromite and (Fe,Ni) ferrite phases. Together with the SUPCRT92-98 thermo- dynamic database for aqueous species, the 'spinel' thermodynamic dataset was applied to modeling oxidation of austenitic stainless steel in hydrothermal water at 290*C and 90 bar using the Gibbs energy minimization (GEM) algorithm, implemented in the GEMS-PSI code. Firstly, the equilibrium compositions of steel oxidation products were modelIed as function of oxygen fugacity .fO{sub 2} by incremental additions of O{sub 2} in H{sub 2}O-free system Cr-Fe- Ni-O. Secondly, oxidation of corrosion products in the Fe-Cr-Ni-O-H aquatic system was modelIed at different initial solid/water ratios. It is demonstrated that in the transition region from hydrogen regime to oxygen regime, the most significant changes in composition of two spinel-oxide phases (chromite and ferrite) and hematite must take place. Under more reduced conditions, the Fe-rich ferrite (magnetite) and Ni-poor chromite phases co-exist at equilibrium with a metal Ni

  19. U-Pb SHRIMP ages of detrital zircons from Hiriyur formation in Chitradurga Greenstone belt and its implication to the Neoarchean evolution of Dharwar craton, South India

    International Nuclear Information System (INIS)

    Nasheeth, A.; Okudaira, T.; Horie, K.; Hokada, T.; Satish Kumar, M.

    2016-01-01

    We report newly obtained U-Pb SHRIMP ages of detrital zircons from metagreywackes in the Hiriyur Formation (Chitradurga Group, Dharwar Supergroup) from the central eastern part of the Chitradurga greenstone belt. U-Pb analyses yield three major Neoarchean age populations ranging from 2.70 - 2.54 Ga with some minor age population of Mesoarchean. The maximum age of deposition is constrained by the youngest detrital zircon population at 2546 Ma. This is the first report of the occurrence of supracrustal rocks less than 2.58 Ga in the central part of Chitradurga greenstone belt. Close evaluation of detrital ages with the published ages of surrounding igneous rocks suggest that the youngest detrital zircons might be derived from rocks of the Eastern Dharwar craton and the inferred docking of the western and eastern Dharwar cratons happened prior to the deposition of the Hiriyur Formation. The Chitradurga shear zone, dividing the Dharwar craton into western and eastern blocks, probably developed after the deposition. Furthermore, the lower intercept is interpreted as evidence for the Pan-African overprints in the study area. (author)

  20. Detrital zircon without detritus: a result of 496-Ma-old fluid-rock interaction during the gold-lode formation of Passagem, Minas Gerais, Brazil

    Science.gov (United States)

    Cabral, Alexandre Raphael; Zeh, Armin

    2015-01-01

    Zircon and xenotime occur in tourmaline-rich hydrothermal pockets in the auriferous lode of Passagem de Mariana, a world-class gold deposit. Zircon grains show pristine oscillatory zoning, but many of them are altered, exhibiting porous domains filled with graphite. Uranium-Pb dating of zircon, using in-situ laser ablation-inductively coupled plasma-mass spectrometry, yields ages between 3.2 and 2.65 Ga, which match those for detrital zircon of the footwall quartzite of the > 2.65-Ga-old Moeda Formation. Discordant analyses point to zircon-age resetting during the Brasiliano orogeny at ca. 500 Ma. This interpretation is supported by U-Pb dating of euhedral xenotime immediately adjacent to altered zircon within the same tourmaline pocket. The xenotime grains give a Concordia age of 496.3 ± 2.0 Ma, which is identical to that determined for monazite of a quartz-hematite vein-type deposit (i.e., jacutinga lode) in the region (Itabira), another important mineralisation style of gold. The occurrence of relatively abundant inherited detrital zircon, but absence of rock fragments in the tourmaline pocket investigated here, implies that detrital material was completely replaced by tourmaline. The graphite overprint on the altered detrital zircon attests to a reducing fluid, which was likely formed by fluid-rock interaction with carbonaceous phyllite of the Batatal Formation, the host rock of the Passagem lode.

  1. Significance of detrital zircons in upper Devonian ocean-basin strata of the Sonora allochthon and Lower Permian synorogenic strata of the Mina Mexico foredeep, central Sonora, Mexico

    Science.gov (United States)

    Poole, F.G.; Gehrels, G.E.; Stewart, John H.

    2008-01-01

    U-Pb isotopic dating of detrital zircons from a conglomeratic barite sandstone in the Sonora allochthon and a calciclastic sandstone in the Mina Mexico foredeep of the Minas de Barita area reveals two main age groups in the Upper Devonian part of the Los Pozos Formation, 1.73-1.65 Ga and 1.44-1.42 Ga; and three main age groups in the Lower Permian part of the Mina Mexico Formation, 1.93-1.91 Ga, 1.45-1.42 Ga, and 1.1-1.0 Ga. Small numbers of zircons with ages of 2.72-2.65 Ga, 1.30-1.24 Ga, ca. 2.46 Ga, ca. 1.83 Ga, and ca. 0.53 Ga are also present in the Los Pozos sandstone. Detrital zircons ranging in age from 1.73 to 1.65 Ga are considered to have been derived from the Yavapai, Mojave, and Mazatzal Provinces and their transition zones of the southwestern United States and northwestern Mexico. The 1.45-1.30 Ga detrital zircons were probably derived from scattered granite bodies within the Mojave and Mazatzal basement rocks in the southwestern United States and northwestern Mexico, and possibly from the Southern and Eastern Granite-Rhyolite Provinces of the southern United States. The 1.24-1.0 Ga detrital zircons are believed to have been derived from the Grenville (Llano) Province to the east and northeast or from Grenvilleage intrusions or anatectites to the north. Several detrital zircon ages ranging from 2.72 to 1.91 Ga were probably derived originally from the Archean Wyoming Province and Early Paleoproterozoic rocks of the Lake Superior region. These older detrital zircons most likely have been recycled one or more times into the Paleozoic sandstones of central Sonora. The 0.53 Ga zircon is believed to have been derived from a Lower Cambrian granitoid or meta-morphic rock northeast of central Sonora, possibly in New Mexico and Colorado, or Oklahoma. Detrital zircon geochronology suggests that most of the detritus in both samples was derived from Laurentia to the north, whereas some detritus in the Permian synorogenic foredeep sequence was derived from the

  2. Faulting and erosion in the Argentine Precordillera during changes in subduction regime: Reconciling bedrock cooling and detrital records

    Science.gov (United States)

    Fosdick, Julie C.; Carrapa, Barbara; Ortíz, Gustavo

    2015-12-01

    The Argentine Precordillera is an archetypal retroarc fold-and-thrust belt that records tectonics associated with changing subduction regimes. The interactions between exhumation and faulting in the Precordillera were investigated using apatite and zircon (U-Th-Sm)/He and apatite fission track thermochronometry from the Precordillera and adjacent geologic domains. Inverse modeling of thermal histories constrains eastward in-sequence rock cooling associated with deformation and erosion from 18 to 2 Ma across the Central Precordillera tracking thrusting during this time. The youngest AHe ages (5-2 Ma) and highest erosion rates are located in the eastern and western extremities of the Precordillera and indicate that recent denudation is concentrated at its structural boundaries. Moreover, synchronous rapid Pliocene cooling of the Frontal Cordillera, Eastern Precordillera, and Sierra del Valle Fértil was coeval with initiation of basement-involved faulting in the foreland. Detrital zircon U-Pb geochronology from the ca. 16-8.1 Ma Bermejo foreland basin strata suggests fluvial connectivity westward beyond the Frontal Cordillera to the Main Cordillera and Coast Range followed by an important shift in sediment provenance at ca. 10 Ma. At this time, we suggest that a substantial decrease in Permo-Triassic igneous sources in the Frontal Cordillera and concurrent increase in recycled zircons signatures of Paleozoic strata are best explained by uplift and erosion of the Precordillera during widening of the thrust-belt. Bedrock thermochronology and modeling indicate a 2-6 Myr lag time between faulting-related cooling in the hinterland and the detrital record of deformation in the foreland basin, suggesting that for tectonically active semi-arid settings, bedrock cooling may be more sensitive to onset of faulting. We suggest that high erosion rates in the Frontal Cordillera and Eastern Precordillera are associated with increased interplate coupling during shallowing of the

  3. Compositional controls on spinel clouding and garnet formation in plagioclase of olivine metagabbros, Adirondack Mountains, New York

    Science.gov (United States)

    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.

  4. High-pressure behaviour of selenium-based spinels and related structures - an experimental and theoretical study

    International Nuclear Information System (INIS)

    Waskowska, A; Gerward, L; Olsen, J Staun; Feliz, M; Llusar, R; Gracia, L; Marques, M; Recio, J M

    2004-01-01

    The high-pressure structural behaviour of the cubic spinel CdCr 2 Se 4 (space group Fd3barm) and tetragonal CdGa 2 Se 4 (I4bar) has been investigated experimentally and theoretically in order to understand the large difference in compressibility between the two selenides. The experimental values of the bulk modulus for these compounds are 101(2) and 48(2) GPa, respectively. These values compare well with 92 and 44 GPa obtained from first-principles calculations based on the density functional theory formalism. The observed difference in compressibility between the cubic and tetragonal structures can be understood in terms of polyhedral analysis. In a hypothetical cubic spinel structure Fd3barm), the calculated bulk modulus for CdGa 2 Se 4 is 85 GPa. This value together with the experimental and theoretical results for CdCr 2 Se 4 suggest that the selenium-based cubic spinels should have a bulk modulus about 100 GPa, which is half the value found for the oxide spinels

  5. Ferrimagnetism and spin excitation in a Ni–Mn partially inverted spinel prepared using a modified polymeric precursor method

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Rafael A. [Programa de Pos-Graduação em Ciência e Tecnologia de Materiais (POSMAT), Universidade Estadual Paulista, Faculdade de Ciências, Caixa Postal 473, 17033-360 Bauru, São Paulo (Brazil); Institut des Sciences Chimiques de Rennes – UMR 6226, Université de Rennes 1, F-35042 Rennes (France); Tedesco, Julio C.G.; Birk, Jonas O. [The Niels Bohr Institute, University of Copenhagen, DK-2100 Copenhagen (Denmark); Kalceff, Walter, E-mail: wkalceff@uts.edu.au [School of Physics and Advanced Materials, University of Technology Sydney (UTS), P.O. Box 123, Broadway, NSW 2007 (Australia); Yokaichiya, Fabiano [Laboratório Nacional de Luz Síncrotron (LNLS), Caixa Postal 6192, CEP 13083-970 Campinas, São Paulo (Brazil); Comissao Nacional de Energia Nuclear (CNEN), Instituto de Pesquisas Energeticas e Nucleares (IPEN), Reactor Multiproposito Brasileiro - RMB, Avenida Lineo Prestes 2242, Bloco A, Cidade Universitaria Armando Salles de Oliveira, Sao Paulo (Brazil); Rasmussen, Nina [The Niels Bohr Institute, University of Copenhagen, DK-2100 Copenhagen (Denmark); Peña, Octavio [Institut des Sciences Chimiques de Rennes – UMR 6226, Université de Rennes 1, F-35042 Rennes (France); Henry, Paul F. [European Spallation Source ESS AB, Box 176, 22100 Lund (Sweden); Simeoni, Giovanna G. [Heinz Maier-Leibnitz Zentrum (MLZ) and Physics Department, Technische Universität München, Lichtenbergstr. 1, 85748 Garching (Germany); Bordallo, Heloisa N. [The Niels Bohr Institute, University of Copenhagen, DK-2100 Copenhagen (Denmark); European Spallation Source ESS AB, Box 176, 22100 Lund (Sweden); and others

    2014-07-01

    We demonstrate that a Ni–Mn oxide partially inverted spinel (Ni{sub 1−ν}Mn{sub ν})[Ni{sub ν}Mn{sub 2−ν}]O{sub 4} having inversion degree ν ≈ 0.8 and produced by a modified polymeric precursor method exhibits behaviour previously reported only in monophased samples. The structure of the specimen was determined using Rietveld analysis of X-ray and neutron powder diffraction data, showing that at room temperature the material crystallizes in the Fd3{sup ¯}m space group with a lattice constant a = 8.392 Å. Combining magnetization measurements with neutron powder diffraction, we show that the magnetic structure of this spinel is associated with the interplay between the ferromagnetic and antiferromagnetic lattices which coexist due to the cations' presence on both tetrahedral and octahedral sites. Our analysis of the neutron diffraction data confirms the postulated magnetic structure involving a star-like moment arrangement, arising from competition for the B (octahedral) spinel sites by the Ni and Mn cations. Finally, we show that strong magnetic fluctuations are observed in the inelastic neutron scattering data. - Highlights: • Ni–Mn oxide partially-inverted spinel made by modified polymeric precursor method. • Magnetic measurements showed a ferrimagnetic and a parasitic magnetic transition. • NPD revealed a magnetic structure consistent with a star-like moment arrangement. • INS measurements indicated four distinct temperature-dependent magnetic regimes.

  6. EPR, mu-Raman and Crystallographic properties of spinel type ZnCr{sub 2}O{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Vargas-Hernandez, C; Almanza, O; Jurado, J F, E-mail: cvargash@unal.edu.c [Universidad Nacional de Colombia, Manizales-Colombia Laboratorio de Propiedades Opticas de Materiales-POM (Colombia)

    2009-05-01

    Structural, vibrational and electron paramagnetic resonance (EPR) analysis for compound ZnCr{sub 2}O{sub 4} are shown in this work. These types of materials are used in technological applications as humidity sensors and piezoelectric devices. The compound was obtained by mean of solid state reaction technique from binary precursors ZnO and Cr{sub 2}O{sub 3}. After three thermal treatments the sample structure was monitoring using X ray diffraction (XRD), the spinel cubic phase has been indexed within O{sup 7}{sub h}(Fd3m) spatial group. It is observed normal spinel phase. Micro-Raman analysis revealed bands for normal vibration modes of Zn and Cr atoms in tetrahedral and octahedral environments formed by oxygen atoms at approximately 400 and 900 cm{sup -1}, respectively. Bands around 941 cm{sup -1} are associated possibly to vacancies in the tetrahedral and octahedral sites due to interaction between Zn and Cr ions. EPR signal from 150 to 300 K isothermals indicates a transition between inverse spinel to normal spinel type in a central field around 3350 G. A signal at approximately 3400 G corresponding to the C'r{sup +3} in tetrahedral sites is observed near the central field.

  7. Magnetic ordering in the spinel compound Li[Mn2?xLix]O4(x = 0,0.04)

    NARCIS (Netherlands)

    Gaddy, J.; Lamsal, J.; Petrovic, M.; Montfrooij, W.; Schmets, A.; Vojta, T.

    2009-01-01

    The two B-site ions Mn3+ and Mn4+ in the stoichiometric spinel structure LiMn2O4 form a complex, columnar ordered pattern below the charge-ordering transition at room temperature. On further cooling to below 66 K, the system develops long-range antiferromagnetic order. In contrast, whereas

  8. Multiple Nebular Gas Reservoirs Recorded by Oxygen Isotope Variation in a Spinel-Rich CAI in CO3 MIL 090019

    Science.gov (United States)

    Simon, J. I.; Simon, S. B.; Nguyen, A. N.; Ross, D. K.; Messenger, S.

    2017-07-01

    We conducted NanoSIMS ion imaging studies of a primitive spinel-rich CAI from the MIL 090019 CO3 chondrite. It records radial O-isotopic heterogeneity among multiple occurrences of the same mineral, reflecting distinct nebular O-isotopic reservoirs.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  13. Tensile strain effect in ferroelectric perovskite oxide thin films on spinel magnesium aluminum oxide substrate

    Science.gov (United States)

    Zhou, Xiaolan

    Ferroelectrics are used in FeRAM (Ferroelectric random-access memory). Currently (Pb,Zr)TiO3 is the most common ferroelectric material. To get lead-free and high performance ferroelectric material, we investigated perovskite ferroelectric oxides (Ba,Sr)TiO3 and BiFeO3 films with strain. Compressive strain has been investigated intensively, but the effects of tensile strain on the perovskite films have yet to be explored. We have deposited (Ba,Sr)TiO3, BiFeO3 and related films by pulsed laser deposition (PLD) and analyzed the films by X-ray diffractometry (XRD), atomic force microscopy (AFM), etc. To obtain inherently fully strained films, the selection of the appropriate substrates is crucial. MgAl2O4 matches best with good quality and size, yet the spinel structure has an intrinsic incompatibility to that of perovskite. We introduced a rock-salt structure material (Ni 1-xAlxO1+delta) as a buffer layer to mediate the structural mismatch for (Ba,Sr)TiO3 films. With buffer layer Ni1-xAlxO1+delta, we show that the BST films have high quality crystallization and are coherently epitaxial. AFM images show that the films have smoother surfaces when including the buffer layer, indicating an inherent compatibility between BST-NAO and NAO-MAO. In-plane Ferroelectricity measurement shows double hysteresis loops, indicating an antiferroelectric-like behavior: pinned ferroelectric domains with antiparallel alignments of polarization. The Curie temperatures of the coherent fully strained BST films are also measured. It is higher than 900°C, at least 800°C higher than that of bulk. The improved Curie temperature makes the use of BST as FeRAM feasible. We found that the special behaviors of ferroelectricity including hysteresis loop and Curie temperature are due to inherent fully tensile strain. This might be a clue of physics inside ferroelectric stain engineering. An out-of-plane ferroelectricity measurement would provide a full whole story of the tensile strain. However, a

  14. Crystal growth and magnetic properties of spinel (Co,Mn)3O4

    Science.gov (United States)

    Kang, Sun Hee; Kim, Ill Won; Jeong, Yoon Hee; Koo, Tae Yeong

    2012-04-01

    Single crystals of cubic and tetragonal spinel Co3-xMnxO4 (x=1.0 and 1.5) were successfully grown using a solvent evaporation method with PbF2 flux. Single crystals in octahedral shape with a size of about 4 mm on edge were obtained from 100 cm3 Pt crucibles. Ferrimagnetic transitions were detected at 170 K and 160 K from the measurements of temperature dependent magnetization and specific heat of Co2MnO4 and Co1.5Mn1.5O4, respectively. Low temperature field-dependent magnetization curves give a strong indication of the non-collinear spin structure, offering an insulating Co3-xMnxO4 system as a possible candidate for examining the multiferroicity.

  15. Orbital physics in sulfur spinels: ordered, liquid and glassy ground states

    International Nuclear Information System (INIS)

    Buettgen, N; Hemberger, J; Fritsch, V; Krimmel, A; Muecksch, M; Nidda, H-A Krug von; Lunkenheimer, P; Fichtl, R; Tsurkan, V; Loidl, A

    2004-01-01

    Measurements of magnetization M(T, H), heat capacity C(T), NMR lineshift K(T) and linewidth Δ(T), neutron scattering S(Q, ω, T) and broadband dielectric spectroscopy ε(ω, T) provide experimental evidence of the different orbital ground states in the cubic sulfur spinels under investigation. In all compounds, the tetrahedrally coordinated Jahn-Teller ions Fe 2+ are characterized by a degeneracy of the orbital degrees of freedom. Particularly, we found a long-range orbital ordering in polycrystalline (PC) FeCr 2 S 4 , and a glassy freezing of the orbital degrees of freedom in FeCr 2 S 4 (single crystals) (SCs). In contrast, FeSc 2 S 4 belongs to the rare class of spin-orbital liquids, where quantum fluctuations accompanying the glassy freezing of the orbitals suppress long-range magnetic order

  16. Multifunctional thick-film structures based on spinel ceramics for environment sensors

    Energy Technology Data Exchange (ETDEWEB)

    Vakiv, M; Hadzaman, I; Klym, H; Shpotyuk, O [Institute of Materials of SRC ' Carat' , 202 Stryjska str., Lviv, 79031 (Ukraine); Brunner, M, E-mail: shpotyuk@novas.lviv.ua, E-mail: klymha@yahoo.com [Fachhochschule Koeln/University of Applied Sciences, 2 Betzdorfer str., Koeln, 50679 (Germany)

    2011-04-01

    Temperature sensitive thick films based on spinel-type NiMn{sub 2}O{sub 4}-CuMn{sub 2}O{sub 4}-MnCo{sub 2}O{sub 4} manganites with p- and p{sup +}-types of electrical conductivity and their multilayer p{sup +}-p structures were studied. These thick-film elements possess good electrophysical characteristics before and after long-term ageing test at 170 deg. C. It is shown that degradation processes connected with diffusion of metallic Ag into film grain boundaries occur in one-layer p-and p{sup +}-conductive films. Some part of the p{sup +}-p structures were of high stability, the relative electrical drift being no more than 1 %.

  17. Investigations into the effect of spinel oxide composition on rate of carbon deposition

    International Nuclear Information System (INIS)

    Allen, G.C.; Jutson, J.A.

    1987-11-01

    The deposition of carbon on fuel cladding and other steels results in a reduction in heat transfer efficiency. Methane and carbon monoxide are added to the gaseous coolant in the Advanced Gas Cooled Reactor (AGR) to reduce the radiolytic oxidation of the graphite moderator and this is known to increase the rate of carbon deposition. However, the composition of oxides formed on steel surfaces within the reactor may also influence deposition. In this investigation carefully characterised spinel type oxides of varying composition have been subjected to γ radiation under conditions of temperature, pressure and atmosphere similar to those experienced in the reactor. The rate of carbon deposition has been studied using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Analysis (EDX). (U.K.)

  18. Formation of a Spinel Coating on AZ31 Magnesium Alloy by Plasma Electrolytic Oxidation

    Science.gov (United States)

    Sieber, Maximilian; Simchen, Frank; Scharf, Ingolf; Lampke, Thomas

    2016-03-01

    Plasma electrolytic oxidation (PEO) is a common means for the surface modification of light metals. However, PEO of magnesium substrates in dilute electrolytes generally leads to the formation of coatings consisting of unfavorable MgO magnesium oxide. By incorporation of electrolyte components, the phase constitution of the oxide coatings can be modified. Coatings consisting exclusively of MgAl2O4 magnesium-aluminum spinel are produced by PEO in an electrolyte containing hydroxide, aluminate, and phosphate anions. The hardness of the coatings is 3.5 GPa on Martens scale on average. Compared to the bare substrate, the coatings reduce the corrosion current density in dilute sodium chloride solution by approx. one order of magnitude and slightly shift the corrosion potential toward more noble values.

  19. In-situ synchrotron PXRD study of spinel LiMn2O4 formation

    DEFF Research Database (Denmark)

    Birgisson, Steinar; Jensen, Kirsten Marie Ørnsbjerg; Christiansen, Troels Lindahl

    structural properties for the reaction being studied. Normally the reactions are started by heating and a constant temperature is kept throughout the experiment. In this study the hydrothermal reaction previously shown to produce spinel LiMn2O4 nanoparticles is studied in-situ to learn more about the phase......O4, depending on the initial concentration if Li-ions. An impurity phase, identified as Mn3O4, is also detected in different concentrations depending on reaction time and temperature. We have developed an experimental technique for in-situ measurements of solvothermal reactions under sub...... in the in-situ measurements it gives a unique opportunity to study reaction kinetics and thermodynamic quantities of the reactions. A temperature study of the reaction has been conducted to see how the formation rate and particle growth is affected by temperature while the precursor concentration is kept...

  20. Spontaneous electric polarization in the B-site magnetic spinel GeCu2O4

    Science.gov (United States)

    Yanda, Premakumar; Ghara, Somnath; Sundaresan, A.

    2018-04-01

    We report the observation of a spontaneous electric polarization at the antiferromagnetic ordering temperature (TN ∼ 33 K) of Cu2+ ions in the B-site magnetic spinel GeCu2O4, synthesized at high pressure and high temperature. This compound is known to crystallize in a tetragonal structure (space group I41/amd) due to Jahn-Teller distortion of Cu2+ ions and exhibit a collinear up-up-down-down (↑↑↓↓) antiferromagnetic spin configuration below TN. We found a clear dielectric anomaly at TN, where an electric polarization appears in the absence of applied magnetic field. The electric polarization is suppressed by applied magnetic fields, which demonstrates that the compound GeCu2O4 is a type-II multiferroic.

  1. Anomalous magnetoresistance in the spinel superconductor LiTi2O4.

    Science.gov (United States)

    Jin, K; He, G; Zhang, X; Maruyama, S; Yasui, S; Suchoski, R; Shin, J; Jiang, Y; Yu, H S; Yuan, J; Shan, L; Kusmartsev, F V; Greene, R L; Takeuchi, I

    2015-05-20

    LiTi2O4 is a unique compound in that it is the only known spinel oxide superconductor. The lack of high quality single crystals has thus far prevented systematic investigations of its transport properties. Here we report a careful study of transport and tunnelling spectroscopy in epitaxial LiTi2O4 thin films. An unusual magnetoresistance is observed which changes from nearly isotropic negative to prominently anisotropic positive as the temperature is decreased. We present evidence that shows that the negative magnetoresistance likely stems from the suppression of local spin fluctuations or spin-orbit scattering centres. The positive magnetoresistance suggests the presence of an orbital-related state, also supported by the fact that the superconducting energy gap decreases as a quadratic function of magnetic field. These observations indicate that the spin-orbital fluctuations play an important role in LiTi2O4 in a manner similar to high-temperature superconductors.

  2. Optical and dielectric properties of neutron irradiated MgAl2O4 spinels

    International Nuclear Information System (INIS)

    Ibarra, A.

    1996-01-01

    The radiation effects on the optical and electrical properties of stoichiometric MgAl 2 O 4 spinel specimens irradiated in FFTF-MOTA at temperatures between 385 and 750 C to fluence ranging from 5.3 to 24.9 x 10 26 n m -2 (E>0.1 McV) are measured. In the optical properties a strong absorption in the ultraviolet range is observed together with a small band around 20 000 cm -1 (510 nm). Two strong luminescence emissions are also observed around 700 nm, with excitation spectra in the ultraviolet region. In the electrical properties a strong decrease of conductivity is observed in the temperature range from 0 to 500 C. Other techniques (like dielectric spectroscopy and EPR) have been used. (orig.)

  3. Spinel-Bearing, Al-Rich Chrondrules in the Unequilibrated Ordinary Chondrite NWA7402

    Science.gov (United States)

    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.

  4. Creep of Polycrystalline Magnesium Aluminate Spinel Studied by an SPS Apparatus.

    Science.gov (United States)

    Ratzker, Barak; Sokol, Maxim; Kalabukhov, Sergey; Frage, Nachum

    2016-06-20

    A spark plasma sintering (SPS) apparatus was used for the first time as an analytical testing tool for studying creep in ceramics at elevated temperatures. Compression creep experiments on a fine-grained (250 nm) polycrystalline magnesium aluminate spinel were successfully performed in the 1100-1200 °C temperature range, under an applied stress of 120-200 MPa. It was found that the stress exponent and activation energy depended on temperature and applied stress, respectively. The deformed samples were characterized by high resolution scanning electron microscope (HRSEM) and high resolution transmission electron microscope (HRTEM). The results indicate that the creep mechanism was related to grain boundary sliding, accommodated by dislocation slip and climb. The experimental results, extrapolated to higher temperatures and lower stresses, were in good agreement with data reported in the literature.

  5. Activity of Aniline Methylation over Fe-Cu-Cr Ternary Spinel Systems

    Directory of Open Access Journals (Sweden)

    Reni George

    2014-03-01

    Full Text Available A series of spinels having thegeneral formula CuCr2-xFexO4 with x=0.25,0.75, 1.25, 1.75 were prepared by co-precipitation method. The catalysts werecharacterized by various physico-chemical methods like XRD, BET, UV-DRS, SEM,EDX, TPD etc. The reaction of aniline with methanol was studied in a fixed-bedreactor system as a potential source for the production of various methylanilines. It was observed that systems possessing low ‘x’ values are highlyselective and active for N-monoalkylation of aniline leading toN-methylaniline. Reaction parameters were properly varied to optimize thereaction conditions for obtaining N-methylaniline selectively and in betteryield. Among the systems CuCr1.75Fe0.25O4 isremarkable due to its very high activity and excellent stability. Under theoptimized conditions N-methylaniline selectivity exceeded 91%. CuCr1.25Fe0.75O4gives better conversion than CuCr1.75Fe0.25O4in CuCr2-xFexO4 series. The Lewis acid sitesof the catalysts are mainly responsible for the good catalytic performance. © 2014 BCREC UNDIP. All rights reservedSubmitted: 18th July 2013; Revised: 5th November 2013; Accepted: 1st December 2013[How to Cite: George, R., George, K., Sugunan, S. (2014. Activity of Aniline Methylation over Fe-Cu-Cr Ternary Spinel Systems. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (1: 39-44. (doi:10.9767/bcrec.9.1.5169.39-44][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.1.5169.39-44] 

  6. Microseismic Monitoring of the Olivine → Spinel Transition in Fayalite Under Non-Hydrostatic Stress

    Science.gov (United States)

    Officer, T.; Secco, R. A.

    2016-12-01

    In subduction zones, deep earthquakes are thought to be associated with faulting that arises from phase transformations. In order to test the viability of this mechanism experimentally, it is necessary to make microseismic measurements while the mineral under investigation is subjected to the pressure and temperature (P,T) environment at depth. A system has been developed capable of making in situ acoustic emission (AE) measurements on samples under P,T conditions representative of the upper mantle and transition zone. Experiments are performed in a 3000-ton multi-anvil press using an 18/11 octahedral cell with 6 piezoelectric transducers mounted on the rear side of the anvils. AE signals are collected at a sampling rate of 40 MHz using a triggered system and a data buffer for continuous recording so full waveforms of AE events are captured. The use of multiple transducers distributed in a microseismic array allows for events to be located within the sample through automatic arrival time picking and least squares inversion techniques. The multi-anvil apparatus constitutes an inherently noisy environment both acoustically and electrically, therefore methods of noise reduction were developed and will be discussed. This technique has been used to measure acoustic signals generated from the fracturing of quartz beads during high pressure deformation and to investigate the possibility that the phase transformation from olivine to spinel, known to occur in subduction zones, is associated with deep-focus earthquakes (300 - 690 km depth). The analog material fayalite (Fe2SiO4), the iron end member of olivine, has been examined. Information about its synthesis and sintering will be discussed as well as results of AE experiments on samples experiencing deviatoric stress under high pressure (P = 4-9 GPa) and high temperature (T = 773-1273 K) conditions in the spinel stability field.

  7. High Performance Flexible Pseudocapacitor based on Nano-architectured Spinel Nickel Cobaltite Anchored Multiwall Carbon Nanotubes

    International Nuclear Information System (INIS)

    Shakir, Imran

    2014-01-01

    Highlights: • Two-step fabrication method for nano-architectured spinel nickel cobaltite (NiCo 2 O 4 ) anchored MWCNTs composite. • High performance flexible energy-storage devices. • The NiCo 2 O 4 anchored MWCNTs Exhibits 2032 Fg −1 capacitance which is 1.62 times greater than pristine NiCo 2 O 4 at 1 Ag −1 . - Abstract: We demonstrate a facile two-step fabrication method for nano-architectured spinel nickel cobaltite (NiCo 2 O 4 ) anchored multiwall carbon nanotubes (MWCNTs) based electrodes for high performance flexible energy-storage devices. As electrode materials for flexible supercapacitors, the NiCo 2 O 4 anchored MWCNTs exhibits a high specific capacitance of 2032 Fg −1 , which is nearly 1.62 times greater than pristine NiCo 2 O 4 nanoflakes at 1 Ag −1 . The synthesized NiCo 2 O 4 anchored MWCNTs composite shows excellent rate performance (83.96% capacity retention at 30 Ag −1 ) and stability with coulombic efficiency over 96% after 5,000 cycles when being fully charged/discharged at 1 Ag −1 . Furthermore, NiCo 2 O 4 anchored MWCNTs achieve a maximum energy density of 48.32 Whkg −1 at a power density of 480 Wkg −1 which is 60% higher than pristine NiCo 2 O 4 electrode and significantly outperformed electrode materials based on NiCo 2 O 4 which are currently used in the state-of-the-art supercapacitors throughout the literature. This superior rate performance and high-capacity value offered by NiCo 2 O 4 anchored MWCNTs is mainly due to enhanced electronic and ionic conductivity, which provides a short diffusion path for ions and an easy access of electrolyte flow to nickel cobaltite redox centers besides the high conductivity of MWCNTs

  8. Phase relations and Gibbs energies of spinel phases and solid solutions in the system Mg-Rh-O

    Energy Technology Data Exchange (ETDEWEB)

    Jacob, K.T., E-mail: katob@materials.iisc.ernet.in [Department of Materials Engineering, Indian Institute of Science, Bangalore 560 012 (India); Prusty, Debadutta [Department of Materials Engineering, Indian Institute of Science, Bangalore 560 012 (India); Kale, G.M. [Institute for Materials Research, University of Leeds, Leeds, LS2 9JT (United Kingdom)

    2012-02-05

    Highlights: Black-Right-Pointing-Pointer Refinement of phase diagram for the system Mg-Rh-O and thermodynamic data for spinel compounds MgRh{sub 2}O{sub 4} and Mg{sub 2}RhO{sub 4} is presented. Black-Right-Pointing-Pointer A solid-state electrochemical cell is used for thermodynamic measurement. Black-Right-Pointing-Pointer An advanced design of the solid-state electrochemical cell incorporating buffer electrodes is deployed to minimize polarization of working electrode. Black-Right-Pointing-Pointer Regular solution model for the spinel solid solution MgRh{sub 2}O{sub 4} - Mg{sub 2}RhO{sub 4} based on ideal mixing of cations on the octahedral site is proposed. Black-Right-Pointing-Pointer Factors responsible for stabilization of tetravalent rhodium in spinel compounds are identified. - Abstract: Pure stoichiometric MgRh{sub 2}O{sub 4} could not be prepared by solid state reaction from an equimolar mixture of MgO and Rh{sub 2}O{sub 3} in air. The spinel phase formed always contained excess of Mg and traces of Rh or Rh{sub 2}O{sub 3}. The spinel phase can be considered as a solid solution of Mg{sub 2}RhO{sub 4} in MgRh{sub 2}O{sub 4}. The compositions of the spinel solid solution in equilibrium with different phases in the ternary system Mg-Rh-O were determined by electron probe microanalysis. The oxygen potential established by the equilibrium between Rh + MgO + Mg{sub 1+x}Rh{sub 2-x}O{sub 4} was measured as a function of temperature using a solid-state cell incorporating yttria-stabilized zirconia as an electrolyte and pure oxygen at 0.1 MPa as the reference electrode. To avoid polarization of the working electrode during the measurements, an improved design of the cell with a buffer electrode was used. The standard Gibbs energies of formation of MgRh{sub 2}O{sub 4} and Mg{sub 2}RhO{sub 4} were deduced from the measured electromotive force (e.m.f.) by invoking a model for the spinel solid solution. The parameters of the model were optimized using the measured

  9. Detrital zircon U-Pb geochronology of Cambrian to Triassic miogeoclinal and eugeoclinal strata of Sonora, Mexico

    Science.gov (United States)

    Gehrels, G.E.; Stewart, John H.

    1998-01-01

    One hundred and eighty two individual detrital zircon grains from Cambrian through Permian miogeoclinal strata, Ordovician eugeoclinal rocks, and Triassic post-orogenic sediments in northwestern Sonora have been analyzed. During Cambrian, Devonian, Permian, and Triassic time, most zircons accumulating along this part of the Cordilleran margin were shed from 1.40-1.45 and 1.62-1.78 Ga igneous rocks that are widespread in the southwestern United States and northwestern Mexico. Zircons with ages of approximately 1.11 Ga are common in Cambrian strata and were apparently shed from granite bodies near the sample site. The sources of 225-280 Ma zircons in our Triassic sample are more problematic, as few igneous rocks of these ages are recognized in northwestern Mexico. Such sources may be present but unrecognized, or the grains could have been derived from igneous rocks of the appropriate ages to the northwest in the Mojave Desert region, to the east in Chihuahua and Coahuila, or to the south in accreted(?) arc-type terranes. Because the zircon grains in our Cambrian and Devonian to Triassic samples could have accumulated in proximity to basement rocks near their present position or in the Death Valley region of southern California, our data do not support or refute the existence of the Mojave-Sonora megashear. Ordovician strata of both miogeoclinal and eugeoclinal affinity are dominated by >1.77 Ga detrital zircons, which are considerably older than most basement rocks in the region. Zircon grains in the miogeoclinal sample were apparently derived from the Peace River arch area of northwestern Canada and transported southward by longshore currents. The eugeoclinal grains may also have come from the Peace River arch region, with southward transport by either sedimentary or tectonic processes, or they may have been shed from off-shelf slivers of continents (perhaps Antarctica?) removed from the Cordilleran margin during Neoproterozoic rifting. It is also possible that the

  10. Interlayer growth kinetics of a binary solid-solution based on the thermodynamic extremal principle: Application to the formation of spinel at periclase-corundum contacts

    Czech Academy of Sciences Publication Activity Database

    Abart, R.; Svoboda, Jiří; Jeřábek, P.; Povoden-Karadeniz, E.; Habler, G.

    2016-01-01

    Roč. 316, č. 4 (2016), s. 309-328 ISSN 0002-9599 Institutional support: RVO:68081723 Keywords : reactive dffusion * interface migration * thermodynamic modeling * spinel Subject RIV: BJ - Thermodynamics Impact factor: 4.099, year: 2016

  11. Zn{sub x-1}Cu{sub x}Mn{sub 2}O{sub 4} spinels; synthesis, structural characterization and electrical evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Mendez M, F.; Lima, E.; Bosch, P.; Pfeiffer, H. [UNAM, Instituto de Investigaciones en Materiales, Circuito Exterior, Ciudad Universitaria, 04510 Mexico D. F. (Mexico); Gonzalez, F., E-mail: pfeiffer@iim.unam.m [Universidad Autonoma Metropolitana, Unidad Iztapalapa, Av. San Rafael Atlixco No. 186, Col. Vicentina, 09340 Mexico D. F. (Mexico)

    2010-07-01

    This work presents the structural characterization and electrical evaluation of Zn{sub x-1}Cu{sub x}Mn{sub 2}O{sub 4} spinels, which are materials presented as secondary phases into the vari stor ceramic systems. Samples were analyzed by X-ray diffraction, solid-state nuclear magnetic resonance, infrared spectroscopy, scanning electron microscopy and impedance spectroscopy. Although, the addition of copper to the ZnMn{sub 2}O{sub 4} spinel did not produce morphological changes, the structure and electrical behaviors changed considerably. Structurally, copper addition induced the formation of partial inverse spinels, and its addition increases significantly the electrical conductivity. Therefore, the formation of Zn{sub x-1}Cu{sub x}Mn{sub 2}O{sub 4} spinels, as secondary phases into the vari stor materials, may compromise significantly the vari stor efficiency. (Author)

  12. Sr and Ar isotope studies of detrital smectites from the Atlantic Ocean (D.S.D.P., Legs 43, 48 and 50)

    International Nuclear Information System (INIS)

    Clauer, N.; Lucas, J.

    1984-01-01

    Mineralogical, morphological and isotopic (Rb-Sr and K-Ar) determinations were made on some detrital smectites of Palaeocene and Cenomanian ages from D.S.D.P. drillings in the Atlantic Ocean. These minerals are not inert in their depositional environment; authigenic laths grow on detrital sheets with sharp borders. This authigenesis could occur slightly after deposition in a closed system, for some of these smectites. It has been tentatively quantified by the Rb-Sr and K-Ar isotopic methods, which seem also well suited to evaluate the chemical extent of this authigenesis. At least, no preferential loss of 40 Ar vs. 87 Sr could be detected in the minerals, even in those which are smaller than 0.2 μm. (Auth.)

  13. Contribution to the study of deep coastal detritic bottoms: the algal communities of the continental shelf off the Balearic Islands, Western Mediterranean

    Directory of Open Access Journals (Sweden)

    S. JOHER

    2015-09-01

    Full Text Available Three main algal-dominated coastal detritic communities from the continental shelf off Mallorca and Menorca (Balearic Islands, Western Mediterranean are described herein: maërl beds dominated by Spongites fruticulosus and forests of Laminaria rodriguezii located in the Menorca channel, and Peyssonnelia inamoena beds found along the Southern coast of Menorca. There seems to be a gradient of disturbance from the highly disturbed Peyssonnelia beds to the almost undisturbed L. rodriguezii forests. Whether this gradient is the result of current and past anthropogenic pressure (e.g. trawling intensity or is driven by natural environmental factors needs further assessment. Finally, the location of the target communities by means of ROV dives combined with the use of a Box-Corer dredge and beam trawl proved to be a good methodology in the study of the composition and structure of these deep water detritic communities.

  14. A new parameterization for surface ocean light attenuation in Earth System Models: assessing the impact of light absorption by colored detrital material

    OpenAIRE

    G. E. Kim; M.-A. Pradal; A. Gnanadesikan

    2015-01-01

    Light limitation can affect the distribution of biota and nutrients in the ocean. Light absorption by colored detrital material (CDM) was included in a fully coupled Earth System Model using a new parameterization for shortwave attenuation. Two model runs were conducted, with and without light attenuation by CDM. In a global average sense, greater light limitation associated with CDM increased surface chlorophyll, biomass and nutrients together. These changes can be attribut...

  15. Elucidating tectonic events and processes from variably tectonized conglomerate clast detrital geochronology: examples from the Hongliuhe Formation in the southern Central Asian Orogenic Belt, NW China

    Science.gov (United States)

    Cleven, Nathan; Lin, Shoufa; Davis, Donald; Xiao, Wenjiao; Guilmette, Carl

    2017-04-01

    This work expands upon detrital zircon geochronology with a sampling and analysis strategy dating granitoid conglomerate clasts that exhibit differing degrees of internal ductile deformation. As deformation textures within clastic material reflect the variation and history of tectonization in the source region of a deposit, we outline a dating methodology that can provide details of the provenance's tectonomagmatic history from deformation-relative age distributions. The method involves bulk samples of solely granitoid clasts, as they are representative of the magmatic framework within the provenance. The clasts are classified and sorted into three subsets: undeformed, slightly deformed, and deformed. LA-ICPMS U-Pb geochronology is performed on zircon separates of each subset. Our case study, involving the Permian Hongliuhe Formation in the southern Central Asian Orogenic Belt, analyzes each of the three clast subsets, as well as sandstone detrital samples, at three stratigraphic levels to yield a profile of the unroofed provenance. The age spectra of the clast samples exhibit different, wider distributions than sandstone samples, considered an effect of proximity to the respective provenance. Comparisons of clast data to sandstone data, as well as comparisons between stratigraphic levels, yield indications of key tectonic processes, in addition to the typical characteristics provided by detrital geochronology. The clast data indicates a minimal lag time, implying rapid exhumation rates, whereas sandstone data alone would indicate a 90 m.y. lag time. Early Paleozoic arc building episodes appear as Ordovician peaks in sandstone data, and Silurian-Devonian peaks in clast data, indicating a younging of magmatism towards the proximal provenance. A magmatic hiatus starts in the Devonian, correlating with the latest age of deformed clasts, interpreted as timing of collisional tectonics. Provenance interpretation using the correlations seen between the clast and sandstone

  16. Synthesis and magnetic properties of CoFe2O4 spinel ferrite nanoparticles doped with lanthanide ions

    International Nuclear Information System (INIS)

    Kahn, Myrtil L.; Zhang, Z. John

    2001-01-01

    Lanthanide ions have been doped into cobalt spinel ferrites using an oil-in-water micellar method to form CoLn 0.12 Fe 1.88 O 4 nanoparticles with Ln=Ce, Sm, Eu, Gd, Dy, or Er. Doping with lanthanide ions (Ln III ) modulates the magnetic properties of cobalt spinel ferrite nanoparticles. In particular cases of Gd 3+ or Dy 3+ ions, a dramatic increase in the blocking temperature and coercivity is observed. Indeed, the introduction of only 4% of Gd 3+ ions increases the blocking temperature ∼100 K and the coercivity 60%. Initial studies on the magnetic properties of these doped nanoparticles clearly demonstrate that the relationship between the modulation of magnetic properties and the nature of doped Ln III ions is interesting but very complex. [copyright] 2001 American Institute of Physics

  17. Synthesis and electrochemical characteristics of spinel LiMn2O4 via a precipitation spray-drying process

    International Nuclear Information System (INIS)

    Wu, H.M.; Tu, J.P.; Yuan, Y.F.; Li, Y.; Zhao, X.B.; Cao, G.S.

    2005-01-01

    Spinel LiMn 2 O 4 has been successfully synthesized using a precipitation spray-drying process. After the precursor was annealed at 750 deg. C for 10 h, the synthesized material was well-crystallized spinel particle, and exhibited uniform particle size distribution. From cyclic voltammetry results, there is an anomalous redox peaks (3.75/3.26 V). In the charge/discharge potential (versus Li) ranging from 3.2 to 4.5 V, it delivered a high initial discharge capacity of 123 mAh/g at a discharge rate of 60 μA/cm 2 (1/4 C rate). At a high discharge rate of 2.4 mA/cm 2 (10 C rate), the obtainable reversible capacity was 79 mAh/g. The simple procedure of precipitation spray-drying process is time and energy saving, and thus is promising for commercial application

  18. FC and ZFC magnetic properties of ferro-spinels (MFe2O4) prepared by solution-combustion method

    Science.gov (United States)

    Aravind, G.; Kumar, R. Vijaya; Nathaniyal, V.; Rambabu, T.; Ravinder, D.

    2017-07-01

    Magnetic ferro-spinels MFe2O4 (M= Co and Ni) prepared by citrate-gel solution combustion method using metal nitrates with low sintering temperature (500°C). From the XRD and TEM studies confirm that a nano crystalline nature of the prepared samples. Field Cooled (FC) and Zero Field Cooled (ZFC) magnetic studies of the prepared ferro-spinels are measured by using vibrating sample magnetometer (VSM). The resultant magnetization of the prepared samples as a function of an applied magnetic field 10 T was measured at two different temperatures 5 K and 310 K. Field Cooled (FC) and Zero Field Cooled (ZFC) magnetization measurements under an applied field of 100 Oe and 1000 Oe in the temperature range of 5-375 K were carried out, which shows the blocking temperature of these two samples at around 350 K.

  19. Using a C4 Invasive Grass to Isolate the Role of Detrital Carbon versus Rhizodeposit Carbon in Supplying Soil Carbon Pools

    Science.gov (United States)

    Sokol, N.; Bradford, M.

    2016-12-01

    Plant inputs are the primary sources of carbon (C) to soil organic carbon (SOC) pools. Historically, detrital plant sources were thought to dominate C supply to SOC pools. An emerging body of research highlights the previously underestimated role of root exudates and other rhizodeposits. However, few experimental field studies have directly tracked the relative contributions of rhizodeposits versus detritial C inputs into different SOC pools, due to how methodologically challenging they are to measure in a field setting. Here, I present the first 3 years of data from an experimental field study of the prolific, C4 invasive grass species Microstegium vimineum. I use its unique isotopic signature in plots manipulated to contain detrital-only and rhizodeposit-only inputs, to track their relative contributions into microbial biomass C, particulate organic C (POC; >53 um) and mineral-associated organic C (MIN C; emerging theory on the primacy of the belowground, root-associated pathway in supplying C to soil C pools, this increase is generally assumed to be through the MIN C pool due to 1) the lower molecular weight of rhizodeposit compounds, and 2) the close physical association between rhizodeposits and soil mineral surfaces. Our results point to an underappreciated, central role of the POM C pool as a passageway for both detrital and rhizodeposit C inputs to the soil.

  20. Petrogenesis, detrital zircon SHRIMP U-Pb geochronology, and tectonic implications of the Upper Paleoproterozoic Seosan iron formation, western Gyeonggi Massif, Korea

    Science.gov (United States)

    Kim, Chang Seong; Jang, Yirang; Samuel, Vinod O.; Kwon, Sanghoon; Park, Jung-Woo; Yi, Keewook; Choi, Seon-Gyu

    2018-05-01

    This study involves investigations on the Upper Paleoproterozoic iron formation (viz., Seosan iron formation) from the Seosan Group, Gyeonggi Massif of the southwestern Korean Peninsula. It occurs as thin banded layers within meta-arkosic sandstone, formed by alternating processes of chemical (hydrothermal) and detrital depositions under a shallow marine environment. It mainly consists of alternating layers of iron oxides, mostly hematite, and quartz. Minor amounts of magnetite surrounded by muscovite, clinopyroxene and amphibole indicate hydrothermal alteration since its formation. Meta-arkosic sandstone is composed of recrystallized or porphyroclastic quartz and microcline, with small amounts of hematite and pyrite clusters. The Seosan iron formation has high contents of total Fe2O3 and SiO2 with positive Eu anomalies similar to those of other Precambrian banded iron formations, and its formation is clearly related to hydrothermal alteration since its deposition. Detrital zircon SHRIMP U-Pb geochronology data from a meta-arkosic sandstone (SN-1) and an iron formation (SN-2) show mainly two age groups of ca. 2.5 Ga and ca. 1.9-1.75 Ga. This together with intrusion age of the granite gneiss (ca. 1.70-1.65 Ga) clearly indicate that the iron formations were deposited during the Upper Paleoproterozoic. The dominant Paleoproterozoic detrital zircon bimodal age peaks preserved in the Seosan iron formation compare well with those from the South China Craton sedimentary basins, reflecting global tectonic events related to the Columbia supercontinent in East Asia.

  1. U-Pb detrital zircon geochronology from the basement of the Central Qilian Terrane: implications for tectonic evolution of northeastern Tibetan Plateau

    Science.gov (United States)

    Liu, Changfeng; Wu, Chen; Zhou, Zhiguang; Yan, Zhu; Jiang, Tian; Song, Zhijie; Liu, Wencan; Yang, Xin; Zhang, Hongyuan

    2018-03-01

    The Tuolai Group dominates the Central Qilian Terrane, and there are different opinions on the age and tectonic attribute of the Tuolai Group. Based on large-scale geologic mapping and zircon dating, the Tuolai Group is divided into four parts: metamorphic supracrustal rocks, Neoproterozoic acid intrusive rocks, early-middle Ordovician acid intrusive rocks and middle Ordovician basic intrusive rocks. The metamorphic supracrustal rocks are the redefined Tuolai complex-group and include gneiss and schist assemblage by faulting contact. Zircon U-Pb LA-MC-ICP-MS dating was conducted on these samples of gneiss and migmatite from the gneiss assemblage, quartzite, two-mica schist and slate from the schist assemblage. The five detrital samples possess similar age spectra; have detrital zircon U-Pb main peak ages of 1.7 Ga with youngest U-Pb ages of 1150 Ma. They are intruded by Neoproterozoic acid intrusive rocks. Therefore, the Tuolai Group belonging to late Mesoproterozoic and early Neoproterozoic. With this caveat in mind, we believe that U-Pb detrital zircon dating, together with the geologic constraints obtained from this study and early work in the neighboring regions. We suggest that the formation age of the entire crystalline basement rocks of metasedimentary sequence from the Central Qilian Terrane should be constrained between the Late Mesoproterozoic and the Late Neoproterozoic, but not the previous Paleoproterozoic. The basement of the Central Qilian Terrane contains the typical Grenville ages, which indicates the Centre Qilian Terrane have been experienced the Grenville orogeny event.

  2. Thorough XPS analyses on overlithiated manganese spinel cycled around the 3V plateau

    Energy Technology Data Exchange (ETDEWEB)

    Grissa, R. [IPREM ECP − UMR CNRS 5254, Université de Pau et des Pays de l’Adour, Hélioparc Pau-Pyrénées, 2 Avenue du Président Angot, 64053 Pau Cedex 9 (France); Martinez, H., E-mail: herve.martinez@univ-pau.fr [IPREM ECP − UMR CNRS 5254, Université de Pau et des Pays de l’Adour, Hélioparc Pau-Pyrénées, 2 Avenue du Président Angot, 64053 Pau Cedex 9 (France); Cotte, S.; Galipaud, J.; Pecquenard, B. [CNRS, Université de Bordeaux, ICMCB–UPR 9048 and Bordeaux INP, 87 Avenue du Dr. Schweitzer, F-33600 Pessac (France); Cras, F.Le [CEA LETI, 17 rue des Martyrs, F-38054 Grenoble (France); Université Grenoble Alpes, F-38000 Grenoble (France)

    2017-07-31

    Highlights: • Mn2p XPS spectra of Li{sub 1+x}Mn{sub 2-x}O{sub 4} (0 < x < 0.25) fitted with reference samples. • XPS Mn mean oxidation states agrees with XRD structural study. • Li{sub 1.2}Mn{sub 1.8}O{sub 4} thin films cycled versus lithium arounds 3 V in liquid electrolyte. • Electrochemical results (over 20 cycles) related to Mn oxidation states evolution. • Irreversible capacity explained on the basis of XPS by active material delamination. - Abstract: Lithium-rich spinel Li{sub 1.2}Mn{sub 1.8}O{sub 4} thin film electrodes operated at 3 V/Li{sup +}/Li are studied by means of X-ray photoelectron spectroscopy (XPS), mainly on the basis of the evolution of the Mn2p XPS peak during the electrode cycling. The analysis of this core peak has long been debated in literature given its complex character. Based on manganese oxide references, MnO (Mn{sup 2+}), Mn{sub 2}O{sub 3}(Mn{sup 3+}) and Li{sub 2}MnO{sub 3}(Mn{sup 4+}), we propose a deconvolution method to identify each Mn oxidation state. This method is then used for the deconvolution of Mn2p XPS peaks of bulk lithium-rich spinels Li{sub 1+x}Mn{sub 2-x}O{sub 4} (0 ≤ x ≤ 0.25) for validation before proceeding to the study of cycled Li{sub 1.2}Mn{sub 1.8}O{sub 4} thin film electrodes. Electrochemical measurements exhibit significant capacity loss during the first cycle. Based on XPS analyses, this phenomenon could be explained by mechanical breakup of parts of the electrode. A stable behavior during subsequent cycles is then observed. The presence of Mn{sup 2+} species (XPS) at the most top surface of the electrode and the significant polarization observed during the discharge illustrate the kinetical limitation of the two-phase reaction, despite the reduced thickness of the electrode material.

  3. Identification of multiple detrital sources for Otway Supergroup sedimentary rocks: implications for basin models and chronostratigraphic correlations

    International Nuclear Information System (INIS)

    Mitchell, M.M.

    1997-01-01

    Correlation of apatite chlorine content (wt%) with apatite fission track age (Ma) from Lower Cretaceous Otway Supergroup sediments at present-day low temperatures, allows identification of two characteristic detrital source regions. Apatites from eroded Palaeozoic basement terrains yield low Cl content (generally 0.5 wt%) and syndepositional fission track ages. Where post-depositional thermal annealing ( > 70 degree C) has significantly reduced the fission track age, provenance information is preserved in the apatite Cl composition alone. In the Otway Supergroup, evidence for contemporaneous volcanism was found in both the Eumeralla Formation (Albian-Aptian), and Crayfish Group (Aptian-Berriasian) in samples located towards the central rift, where less sandy facies dominate. Results suggest that Crayfish Group sediments deposited along the northern margin of the basin were predominantly derived from eroding basement material, while the section located towards the central rift contains a greater proportion of volcanogenic detritus. Evidence from this study suggests that volcanogenic detritus was a distal sediment source throughout the entire early rift phase, prior to the main influx of arc-related volcanogenic material during deposition of the Eumeralla Formation. As diagenesis of volcanogenic sediments significantly reduces porosity and permeability of the sandstones, reservoir quality and petroleum potential may be significantly reduced in the Crayfish Group in deeper parts of the basin where a greater proportion of volcanogenic detritus is suggested. The results presented here provide important information regarding Lower Cretaceous Otway Basin stratigraphy and clearly indicate that this methodology may have wider application. (authors)

  4. Spectral slopes of the absorption coefficient of colored dissolved and detrital material inverted from UV-visible remote sensing reflectance.

    Science.gov (United States)

    Wei, Jianwei; Lee, Zhongping; Ondrusek, Michael; Mannino, Antonio; Tzortziou, Maria; Armstrong, Roy

    2016-03-01

    The spectral slope of the absorption coefficient of colored dissolved and detrital material (CDM), S cdm (units: nm -1 ), is an important optical parameter for characterizing the absorption spectral shape of CDM. Although highly variable in natural waters, in most remote sensing algorithms, this slope is either kept as a constant or empirically modeled with multiband ocean color in the visible domain. In this study, we explore the potential of semianalytically retrieving S cdm with added ocean color information in the ultraviolet (UV) range between 360 and 400 nm. Unique features of hyperspectral remote sensing reflectance in the UV-visible wavelengths (360-500 nm) have been observed in various waters across a range of coastal and open ocean environments. Our data and analyses indicate that ocean color in the UV domain is particularly sensitive to the variation of the CDM spectral slope. Here, we used a synthesized data set to show that adding UV wavelengths to the ocean color measurements will improve the retrieval of S cdm from remote sensing reflectance considerably, while the spectral band settings of past and current satellite ocean color sensors cannot fully account for the spectral variation of remote sensing reflectance. Results of this effort support the concept to include UV wavelengths in the next generation of satellite ocean color sensors.

  5. U-Pb and Hf isotope analysis of detrital zircons from Mesozoic strata of the Gravina belt, southeast Alaska

    Science.gov (United States)

    Yokelson, Intan; Gehrels, George E.; Pecha, Mark; Giesler, Dominique; White, Chelsi; McClelland, William C.

    2015-10-01

    The Gravina belt consists of Upper Jurassic through Lower Cretaceous marine clastic strata and mafic-intermediate volcanic rocks that occur along the western flank of the Coast Mountains in southeast Alaska and coastal British Columbia. This report presents U-Pb ages and Hf isotope determinations of detrital zircons that have been recovered from samples collected from various stratigraphic levels and from along the length of the belt. The results support previous interpretations that strata in the western portion of the Gravina belt accumulated along the inboard margin of the Alexander-Wrangellia terrane and in a back-arc position with respect to the western Coast Mountains batholith. Our results are also consistent with previous suggestions that eastern strata accumulated along the western margin of the inboard Stikine, Yukon-Tanana, and Taku terranes and in a fore-arc position with respect to the eastern Coast Mountains batholith. The history of juxtaposition of western and eastern assemblages is obscured by subsequent plutonism, deformation, and metamorphism within the Coast Mountains orogen, but may have occurred along an Early Cretaceous sinistral transform system. Our results are inconsistent with models in which an east-facing subduction zone existed along the inboard margin of the Alexander-Wrangellia terrane during Late Jurassic-Early Cretaceous time.

  6. The application of PIT tags to measure transport of detrital coral fragments on a fringing reef: Majuro Atoll, Marshall Islands

    Science.gov (United States)

    Ford, Murray R.

    2014-06-01

    Passive integrated transponder (PIT) tags are a radio-frequency identification device widely used as a machine-readable identification tool in fisheries research. PIT tags have also been employed, to a lesser extent, to track the movement of gravel-sized clasts within fluvial and coastal systems. In this study, PIT tags were inserted into detrital coral fragments and used to establish source-sink transport pathways on a fringing reef on Majuro Atoll in the Marshall Islands. Results suggest the transport of gravel-sized material on the inter-tidal reef flat is exclusively across-reef towards the lagoon. Considerable variation in the distance travelled by fragments was observed. Fragments were largely intact and visually recognisable after almost 5 months on the reef flat. However, the branches of some recovered fragments had broken off and corallite abrasion was observed in recovered fragments. This study indicates that PIT tags are an inexpensive and powerful new addition to the suite of sediment transport and taphonomic tools for researchers working within coral reef systems.

  7. Detrital U-Pb zircon analysis of an Eocene McMurdo Erratic sandstone, McMurdo Sound, Antarctica

    International Nuclear Information System (INIS)

    Paulsen, T.; Encarnacion, J.; Valencia, V.A.; Roti Roti, J.M.; Rasoazanamparany, C.

    2011-01-01

    Some of the most important Cenozoic sedimentary rocks in Antarctica are glacial erratics of fossiliferous Palaeogene to Neogene siliclastic rocks known as the McMurdo Erratics. Detrital zircon U-Pb isotopic data reported herein provide new information on the provenance of these siliciclastic rocks. The U-Pb age data from a sandstone glacial erratic that is likely of Eocene age show a dominant age cluster that ranges from 488 to 635 Ma, accompanied by subsidiary Neoproterozoic-Archaean peaks. The dominant Neoproterozoic-Ordovician age cluster, in conjunction with the arkosic lithologies of some erratics and the local presence of granitic and metasedimentary clasts, indicates that the Neoproterozoic-Ordovician basement complex of the Transantarctic Mountains likely served as a major source for the Eocene siliciclastic sediments. This is consistent with derivation of the McMurdo Erratics from locations proximal to the Transantarctic Mountains such as the Discovery Deep and/or major mountain outlet glacier areas. (author). 19 refs., 3 figs., 1 tab.

  8. Effect of cutting edge radius on surface roughness in diamond tool turning of transparent MgAl2O4 spinel ceramic

    Science.gov (United States)

    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.

  9. Microscopic origin of the mobility enhancement at a spinel/perovskite oxide heterointerface revealed by photoemission spectroscopy

    DEFF Research Database (Denmark)

    Schuetz, P.; Christensen, Dennis Valbjørn; Borisov, V.

    2017-01-01

    The spinel/perovskite heterointerface γ−Al2O3/SrTiO3 hosts a two-dimensional electron system (2DES) with electron mobilities exceeding those in its all-perovskite counterpart LaAlO3/SrTiO3 by more than an order of magnitude, despite the abundance of oxygen vacancies which act as electron donors a...

  10. Effect of gamma irradiation on the structural and magnetic properties of Co–Zn spinel ferrite nanoparticles

    International Nuclear Information System (INIS)

    Raut, Anil V.; Kurmude, D.V.; Shengule, D.R.; Jadhav, K.M.

    2015-01-01

    Highlights: • Co–Zn ferrite nanoparticles were examined before and after γ-irradiation. • Single phase cubic spinel structure of Co–Zn was confirmed by XRD data. • The grain size was reported in the range of 52–62 nm after γ-irradiation. • Ms, Hc, n B were reported to be increased after gamma irradiation. - Abstract: In this work, the structural and magnetic properties of Co 1−x Zn x Fe 2 O 4 (0.0 ≤ x ≤ 1.0) ferrite nanoparticles were studied before and after gamma irradiation. The as-synthesized samples of Co–Zn ferrite nanoparticles prepared by sol–gel auto-combustion technique were analysed by XRD which suggested the single phase; cubic spinel structure of the material. Crystal defects produced in the spinel lattice were studied before and after Co 60 γ-irradiation in a gamma cell with a dose rate of 0.1 Mrad/h in order to report the changes in structural and magnetic properties of the Co–Zn ferrite nanoparticles. The average crystallite size (t), lattice parameter (α) and other structural parameters of gamma-irradiated and un-irradiated Co 1−x Zn x Fe 2 O 4 spinel ferrite system was calculated from XRD data. The morphological characterizations were performed using scanning electron microscopy (SEM). The magnetic properties were measured using pulse field hysteresis loop tracer by applying magnetic field of 1000 Oe, and the analysis of data obtained revealed that the magnetic property such as saturation magnetization (Ms), coecivity (Hc), magneton number (n B ) etc. magnetic parameters were increased after irradiation

  11. Spinels of Variscan olivine hornblendites related to the Montnegre granitoids revisited (NE Spain): petrogenetic evidence of mafic magma mixing

    Energy Technology Data Exchange (ETDEWEB)

    Galán, G.; Enrique, P.; Butjosa, L.; Fernández-Roig, L.

    2017-07-01

    Olivine hornblendites (cortlandtites) form part of the Montnegre mafic complex related to late-Variscan I-type granitoids in the Catalan Coastal Ranges. Two generations of spinel are present in these hornblendites: Spl1 forms euhedral crystals included in both olivine and Spl2. Spl2 forms euhedral to anhedral crystals associated with phlogopite and fibrous colourless amphibole forming pseudomorphs after olivine. Compositions of Spl1 are picotite-Al chromite (Fe#: 77.78-66.60; Cr#: 30.12-52.22; Fe3+/R3+: 6.99-21.89; 0.10< TiO2%< 0.62). Compositions of Spl2 are pleonaste (Fe#: 37.86-52.12; Cr#: 1.00-15.45; Fe3+/R3+: 0.31-5.21; TiO2% <0.10%). The two types of spinel follow a CrAl trend, mainly due to the substitution (Fe2+)-1Cr-1= MgAl, which is interpreted as the result of mixing between two different mantle-derived melts. The compositions of early Spl1 crystals included in olivine are characteristic of Al-rich basalts. More aluminous Spl2 would result from reaction of olivine with a less evolved, Al and K-rich mantle-derived melt after new refilling of the magma chamber or channel. As a whole, spinels from similar examples of Variscan olivine hronblendites also follow a CrAl trend with high Fe# and starting at higher Cr# than other trends of this type. Cr# heterogeneity in the early spinels from these Variscan hornblendites would be inherited from the variable Al content of the mafic melts involved in their genesis.

  12. Nickel permanganate as a precursor in the synthesis of a NiMn2O4 spinel

    International Nuclear Information System (INIS)

    Schmidt, Jorge A.; Sagua, Aurora E.; Bazan, Julio C.; Prat, Maria R.; Braganza, Maria E.; Moran, Emilio

    2005-01-01

    The present study describes the preparation, characterization, and thermal decomposition of the compound Ni(MnO 4 ) 2 .xH 2 O, which was synthesized by a coprecipitation method at a low temperature. The role of this compound as a precursor in the synthesis of a Ni-Mn spinel was determined via X-ray, TG-DTA, electron diffraction, and EDAX measurements

  13. Effect of gamma irradiation on the structural and magnetic properties of Co–Zn spinel ferrite nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Raut, Anil V., E-mail: nano9993@gmail.com [Vivekanand Arts, Sardar Dalipsingh Commerce and Science College, Aurangabad 431004, (M.S.) India (India); Kurmude, D.V. [Milind College of Science, Aurangabad 431004, (M.S.) India (India); Shengule, D.R. [Vivekanand Arts, Sardar Dalipsingh Commerce and Science College, Aurangabad 431004, (M.S.) India (India); Jadhav, K.M. [Department of Physics, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad 431004, (M.S.) India (India)

    2015-03-15

    Highlights: • Co–Zn ferrite nanoparticles were examined before and after γ-irradiation. • Single phase cubic spinel structure of Co–Zn was confirmed by XRD data. • The grain size was reported in the range of 52–62 nm after γ-irradiation. • Ms, Hc, n{sub B} were reported to be increased after gamma irradiation. - Abstract: In this work, the structural and magnetic properties of Co{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} (0.0 ≤ x ≤ 1.0) ferrite nanoparticles were studied before and after gamma irradiation. The as-synthesized samples of Co–Zn ferrite nanoparticles prepared by sol–gel auto-combustion technique were analysed by XRD which suggested the single phase; cubic spinel structure of the material. Crystal defects produced in the spinel lattice were studied before and after Co{sup 60} γ-irradiation in a gamma cell with a dose rate of 0.1 Mrad/h in order to report the changes in structural and magnetic properties of the Co–Zn ferrite nanoparticles. The average crystallite size (t), lattice parameter (α) and other structural parameters of gamma-irradiated and un-irradiated Co{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} spinel ferrite system was calculated from XRD data. The morphological characterizations were performed using scanning electron microscopy (SEM). The magnetic properties were measured using pulse field hysteresis loop tracer by applying magnetic field of 1000 Oe, and the analysis of data obtained revealed that the magnetic property such as saturation magnetization (Ms), coecivity (Hc), magneton number (n{sub B}) etc. magnetic parameters were increased after irradiation.

  14. Studying magnetic structure of Bi doped Co2MnO4 cubic spinel by neutron diffraction

    International Nuclear Information System (INIS)

    Rajeevan, N.E.; Kaushik, S.D.; Kumar, Ravi

    2016-01-01

    In present work, we studied effect of Bi doped spinel Bi x Co 2-x MnO 4 (x = 0, 0.05, 0.10, 0.15 and 0.20) samples on their crystal as well as magnetic structure by employing neutron diffraction of wavelength 1.48 A using focusing crystal diffractometer of UGC-DAECSR Mumbai Centre at Dhruva, Trombay, Mumbai, India. The analysis of the neutron diffraction using Fullprof program reveals that crystal structure due to Bi doping remains intact and all the samples have been formed in the cubic spinel structure with Fd3m (space group no. 227). The lattice parameter shows the positive thermal expansion upon Bi doping across the temperature range. In order to understand the implication on the spin structure and magnetism in the detail, temperature dependent neutron diffraction study is carried out on some of the samples (x = 0, 0.1) in the series. The ND pattern of x = 0.1 at 2.9K is shown. The experimental finding in terms of modified magnetic structure upon Bi doping are discussed which are understood in terms of variation in the ferroelectric properties, bond lengths and their effect on the CoO 6 polyhedra. Furthermore, Bi substitution in Co 2 MnO 4 spinel brings in the balance of structural distortion, which affects both ferrimagnetism and ferroelectricity

  15. Nanosized spinel oxide catalysts for CO-oxidation prepared via CoMnMgAl quaternary hydrotalcite route

    Energy Technology Data Exchange (ETDEWEB)

    Mokhtar, M., E-mail: mmoustafa@kau.edu.s [Chemistry Department, Faculty of Science, King Abdulaziz University, 21589 Jeddah, P.O. Box 80203 (Saudi Arabia); Basahel, S.N.; Al-Angary, Y.O. [Chemistry Department, Faculty of Science, King Abdulaziz University, 21589 Jeddah, P.O. Box 80203 (Saudi Arabia)

    2010-03-18

    Catalytic activity of the Co-Mn-Mg-Al mixed oxide spinel catalysts was examined in CO oxidation by O{sub 2}. The prepared catalysts were characterized by chemical analysis (ICP), infrared spectroscopy (FTIR), thermal analysis (TG, DTG), powder X-ray diffraction (XRD), surface area measurements, and scanning electron microscopy (SEM).The calcined hydrotalcite-like precursor was composed of spinel-like Co-Mn-Mg-Al mixed oxide as the only XRD crystalline phases. The nanosized spinel oxide catalysts produced by calcination of hydrotalcites showed higher S{sub BET} than CoMn-hydrotalcite samples as calcination led to dehydroxylation and carbonate decomposition of anions in interlayer spaces. All the catalysts showed 100% CO conversion at high temperature even those calcined at 800 {sup o}C. A catalyst with Co/Mn = 4 and calcined at 500 {sup o}C showed 100% CO conversion at 160 {sup o}C. Moreover, this catalyst exhibited quite good durability without deactivation in 60 h stability test.

  16. Power generation using spinel manganese-cobalt oxide as a cathode catalyst for microbial fuel cell applications.

    Science.gov (United States)

    Mahmoud, Mohamed; Gad-Allah, Tarek A; El-Khatib, K M; El-Gohary, Fatma

    2011-11-01

    This study focused on the use of spinel manganese-cobalt (Mn-Co) oxide, prepared by a solid state reaction, as a cathode catalyst to replace platinum in microbial fuel cells (MFCs) applications. Spinel Mn-Co oxides, with an Mn/Co atomic ratios of 0.5, 1, and 2, were prepared and examined in an air cathode MFCs which was fed with a molasses-laden synthetic wastewater and operated in batch mode. Among the three Mn-Co oxide cathodes and after 300 h of operation, the Mn-Co oxide catalyst with Mn/Co atomic ratio of 2 (MnCo-2) exhibited the highest power generation 113 mW/m2 at cell potential of 279 mV, which were lower than those for the Pt catalyst (148 mW/m2 and 325 mV, respectively). This study indicated that using spinel Mn-Co oxide to replace platinum as a cathodic catalyst enhances power generation, increases contaminant removal, and substantially reduces the cost of MFCs. Copyright © 2011 Elsevier Ltd. All rights reserved.

  17. Structural and optical high-pressure study of spinel-type MnIn2S4

    International Nuclear Information System (INIS)

    Manjon, F.J.; Segura, A.; Pellicer-Porres, J.; Sanchez-Royo, J.F.; Amboage, M.; Itie, J.P.; Flank, A.M.; Lagarde, P.; Polian, A.; Ursaki, V.V.; Tiginyanu, I.M.

    2007-01-01

    We report a combined study of the structural and electronic properties of the spinel-type semiconductor MnIn 2 S 4 under high pressures by means of X-ray diffraction (ADXRD), X-ray absorption (XAS), and optical absorption measurements. The three techniques evidence a reversible structural phase transition near 7 GPa, that according to ADXRD measurements is to a double-NaCl structure. XAS measurements evidence predominant tetrahedral coordination for Mn in the spinel phase that does not noticeably change with increasing pressure up to the phase transition. XAS measurements indicate that the static disorder increases considerably when the sample reverts from the double-NaCl phase to the spinel phase. Optical absorption measurements show that the direct gap of MnIn 2 S 4 exhibits a nonlinear behaviour with a positive pressure coefficient at pressures below 2.5 GPa and a negative pressure coefficient between 2.5 and 7 GPa. The pressure behavior of the bandgap seems to be affected by the defect concentration. The double-NaCl phase also exhibits a bandgap with a negative pressure coefficient. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  18. Synthesis and structural characteristics of the spinel-type solid solutions in the Mn-V-Fe-O system

    International Nuclear Information System (INIS)

    Ponomaryov, V.I.; Dubrovina, I.N.; Zakharov, R.G.

    1976-01-01

    The part of the spinel region bounded by the compounds Mn 3 O 4 , Mn 2 VO 4 , Fe 2 VO 4 , and Fe 3 O 4 in the four-component system Mn-V-Fe-O was studied. The compounds were synthesized by ceramic technology. Samples were heated in a CO 2 atmosphere free of oxygen at 1100 0 C for 25-50 hr. It was found that the average composition of the spinel compound in the system had the formula Mnsub(1.00)Fesub(1.33)Vsub(0.67)O 4 . X-ray and neutron radiogrphic analyses were made. Crystallo-chemical formulas of the solid solutions considered are tabulated. The magnetic moments of saturation, calculated by the Neel model, are shown, and their experimental values are presented. The crystallo-chemical formulas of the spinel solid solutions in the Mn-V-Fe-O system are of interest in interpreting the concentration dependence of the physico-chemical properties of solid solutions of oxides based on metals with varying valence

  19. The Effect of Composition on Spinel Crystals Equilibrium in Low-Silica High-Level Waste Glasses

    International Nuclear Information System (INIS)

    Jiricka, Milos; Hrma, Pavel R.; Vienna, John D.

    2003-01-01

    The liquidus temperature (TL) and the equilibrium mass fraction of spinel were measured in the regions of low-silica (less than 42 mass% SiO2) high-level waste borosilicate glasses within the spinel primary phase field as functions of glass composition. The components that varied, one at a time, were Al2O3, B2O3, Cr2O3, Fe2O3, Li2O, MnO, Na2O, NiO, SiO2, and ZrO2. The effects of Al2O3, B2O3, Fe2O3, NiO, SiO2, and ZrO2 on the TL in this region and in glasses with 42 to 56 mass% SiO2 were similar. However, in the low-silica region, Cr2O3 increased the TL substantially less, and Li2O and Na2O decreased the TL significantly less than in the region with 42 to 56 mass% SiO2. The effect of MnO on the TL of the higher SiO2 glasses is not yet understood with sufficient accuracy. The temperature at which the equilibrium mass fraction of spinel was 1 mass% was 25C to 64C below the TL

  20. Inverse spinel transition metal oxides for lithium-ion storage with different discharge/charge conversion mechanisms

    International Nuclear Information System (INIS)

    Wang, Jiawei; Ren, Yurong; Huang, Xiaobing; Ding, Jianning

    2016-01-01

    Highlights: • Inverse spinel structure relieves the irreversible phase transition of electrodes. • Anodes with the same structure show different discharge/charge conversion mechanisms. • High reversible capacity confirms the potential feasibility of composites. - Abstract: Inverse spinel transition metal oxides (Fe 3 O 4 , MnFe 2 O 4 , Fe 3 O 4 /reduced graphene oxide and MnFe 2 O 4 /reduced graphene oxide) are prepared by a facile ethylene-glycol-assisted hydrothermal method. The stability of inverse spinel structure and the high specific surface area of nanoscale provide transition metal oxides with high specific capacity. And the surface modification with reduced graphene oxide improves the poor conductivity of pristine transition metal oxides. Pristine Fe 3 O 4 and MnFe 2 O 4 deliver the high initial discharge capacity of 1137.1 and 1088.9 mAh g −1 , respectively. Fe 3 O 4 /reduced graphene oxide and MnFe 2 O 4 /reduced graphene oxide get the reversible capacity of 645.8 and 720 mAh g −1 , respectively, even after 55 cycles. The different discharge/charge conversion mechanisms make them different capacity stability. The great electrochemical performances of composites offer electrodes with suitable characteristics for high-performance energy storage application.

  1. Magnetic and catalytic properties of inverse spinel CuFe{sub 2}O{sub 4} nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Anandan, S., E-mail: sanand@nitt.edu [Nanomaterials and Solar Energy Conversion Lab, Department of Chemistry, National Institute of Technology, Trichy 620 015 (India); Department of Environmental Engineering and Science, Feng Chia University, Taichung 407, Taiwan (China); Selvamani, T.; Prasad, G. Guru [Nanomaterials and Solar Energy Conversion Lab, Department of Chemistry, National Institute of Technology, Trichy 620 015 (India); Asiri, A.M. [The Center of Excellence for Advanced Materials Research, King Abdulaziz University, P.O. Box 80203, Jeddah 21413 (Saudi Arabia); Wu, J.J., E-mail: jjwu@fcu.edu.tw [Department of Environmental Engineering and Science, Feng Chia University, Taichung 407, Taiwan (China)

    2017-06-15

    Highlights: • Copper ferrite (CuFe{sub 2}O{sub 4}) nanoparticles were synthesized via citrate-nitrate combustion method. • Spectroscopic information’s have found that CuFe{sub 2}O{sub 4} nanoparticles as an inverse spinel structure. • Magnetic study exhibits CuFe{sub 2}O{sub 4} nanoparticles have ferromagnetic behavior. • CuFe{sub 2}O{sub 4} nanoparticles employed for photocatalytic decolourisation of methylene blue under visible light irradiation. - Abstract: In this research, inverse spinel copper ferrite nanoparticles (CuFe{sub 2}O{sub 4} NPs) were synthesized via citrate-nitrate combustion method. The crystal structure, particle size, morphology and magnetic studies were investigated using various instrumental tools to illustrate the formation of the inverse spinel structure. Mossbauer spectrometry identified Fe is located both in the tetrahedral and octahedral site in the ratio (40:60) and the observed magnetic parameters values such as saturation magnetization (M{sub s} = 20.62 emu g{sup −1}), remnant magnetization (M{sub r} = 11.66 emu g{sup −1}) and coercivity (H{sub c} = 63.1 mTesla) revealed that the synthesized CuFe{sub 2}O{sub 4} NPs have a typical ferromagnetic behaviour. Also tested CuFe{sub 2}O{sub 4} nanoparticles as a photocatalyst for the decolourisation of methylene blue (MB) in the presence of peroxydisulphate as the oxidant.

  2. Dielectric relaxation behavior and impedance studies of Cu2+ ion doped Mg - Zn spinel nanoferrites

    Science.gov (United States)

    Choudhary, Pankaj; Varshney, Dinesh

    2018-03-01

    Cu2+ substituted Mg - Zn nanoferrites is synthesized by low temperature fired sol gel auto combustion method. The spinel nature of nanoferrites was confirmed by lab x-ray technique. Williamson - Hall (W-H) analysis estimate the average crystallite size (22.25-29.19 ± 3 nm) and micro strain induced Mg0.5Zn0.5-xCuxFe2O4 (0.0 ≤ x ≤ 0.5). Raman scattering measurements confirm presence of four active phonon modes. Red shift is observed with enhanced Cu concentration. Dielectric parameters exhibit a non - monotonous dispersion with Cu concentration and interpreted with the support of hopping mechanism and Maxwell-Wagner type of interfacial polarization. The ac conductivity of nanoferrites increases with raising the frequency. Complex electrical modulus reveals a non - Debye type of dielectric relaxation present in nanoferrites. Reactive impedance (Z″) detected an anomalous behavior and is related with resonance effect. Complex impedance demonstrates one semicircle corresponding to the intergrain (grain boundary) resistance and also explains conducting nature of nanoferrites. For x = 0.2, a large semicircle is observed revealing the ohmic nature (minimum potential drop at electrode surface). Dielectric properties were improved for nanoferrites with x = 0.2 and is due to high dielectric constant, conductivity and minimum loss value (∼0.009) at 1 MHz.

  3. Nitrophenol chemi-sensor and active solar photocatalyst based on spinel hetaerolite nanoparticles.

    Science.gov (United States)

    Khan, Sher Bahadar; Rahman, Mohammed M; Akhtar, Kalsoom; Asiri, Abdullah M; Rub, Malik Abdul

    2014-01-01

    In this contribution, a significant catalyst based on spinel ZnMn2O4 composite nanoparticles has been developed for electro-catalysis of nitrophenol and photo-catalysis of brilliant cresyl blue. ZnMn2O4 composite (hetaerolite) nanoparticles were prepared by easy low temperature hydrothermal procedure and structurally characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) and UV-visible spectroscopy which illustrate that the prepared material is optical active and composed of well crystalline body-centered tetragonal nanoparticles with average size of ∼ 38 ± 10 nm. Hetaerolite nanoparticles were applied for the advancement of a nitrophenol sensor which exhibited high sensitivity (1.500 µAcm(-2) mM(-1)), stability, repeatability and lower limit of detection (20.0 µM) in short response time (10 sec). Moreover, hetaerolite nanoparticles executed high solar photo-catalytic degradation when applied to brilliant cresyl blue under visible light.

  4. Tailoring the magnetic properties and magnetorheological behavior of spinel nanocrystalline cobalt ferrite by varying annealing temperature.

    Science.gov (United States)

    Sedlacik, Michal; Pavlinek, Vladimir; Peer, Petra; Filip, Petr

    2014-05-14

    Magnetic nanoparticles of spinel nanocrystalline cobalt ferrite were synthesized via the sol-gel method and subsequent annealing. The influence of the annealing temperature on the structure, magnetic properties, and magnetorheological effect was investigated. The finite crystallite size of the particles, determined by X-ray diffraction and the particle size observed via transmission electron microscopy, increased with the annealing temperature. The magnetic properties observed via a vibrating sample magnetometer showed that an increase in the annealing temperature leads to the increase in the magnetization saturation and, in contrast, a decrease in the coercivity. The effect of annealing on the magnetic properties of ferrite particles has been explained by the recrystallization process at high temperatures. This resulted in grain size growth and a decrease in an imposed stress relating to defects in the crystal lattice structure of the nanoparticles. The magnetorheological characteristics of suspensions of ferrite particles in silicone oil were measured using a rotational rheometer equipped with a magnetic field generator in both steady shear and small-strain oscillatory regimes. The magnetorheological performance expressed as a relative increase in the magnetoviscosity appeared to be significantly higher for suspensions of particles annealed at 1000 °C.

  5. Spinel LiMn 2 O 4 Nanorods as Lithium Ion Battery Cathodes

    KAUST Repository

    Kim, Do Kyung; Muralidharan, P.; Lee, Hyun-Wook; Ruffo, Riccardo; Yang, Yuan; Chan, Candace K.; Peng, Hailin; Huggins, Robert A.; Cui, Yi

    2008-01-01

    Spinel LiMn 2O 4 is a low-cost, environmentally friendly, and highly abundant material for Li-ion battery cathodes. Here, we report the hydrothermal synthesis of single-crystalline β-MnO 2 nanorods and their chemical conversion into free-standing single-crystalline LiMn 2O 4 nanorods using a simple solid-state reaction. The LiMn 2O 4 nanorods have an average diameter of 130 nm and length of 1.2 μm. Galvanostatic battery testing showed that LiMn 2O 4 nanorods have a high charge storage capacity at high power rates compared with commercially available powders. More than 85% of the initial charge storage capacity was maintained for over 100 cycles. The structural transformation studies showed that the Li ions intercalated into the cubic phase of the LiMn 2O 4 with a small change of lattice parameter, followed by the coexistence of two nearly identical cubic phases in the potential range of 3.5 to 4.3V. © 2008 American Chemical Society.

  6. Spinel LiMn 2 O 4 Nanorods as Lithium Ion Battery Cathodes

    KAUST Repository

    Kim, Do Kyung

    2008-11-12

    Spinel LiMn 2O 4 is a low-cost, environmentally friendly, and highly abundant material for Li-ion battery cathodes. Here, we report the hydrothermal synthesis of single-crystalline β-MnO 2 nanorods and their chemical conversion into free-standing single-crystalline LiMn 2O 4 nanorods using a simple solid-state reaction. The LiMn 2O 4 nanorods have an average diameter of 130 nm and length of 1.2 μm. Galvanostatic battery testing showed that LiMn 2O 4 nanorods have a high charge storage capacity at high power rates compared with commercially available powders. More than 85% of the initial charge storage capacity was maintained for over 100 cycles. The structural transformation studies showed that the Li ions intercalated into the cubic phase of the LiMn 2O 4 with a small change of lattice parameter, followed by the coexistence of two nearly identical cubic phases in the potential range of 3.5 to 4.3V. © 2008 American Chemical Society.

  7. Synthesis and photo-electrochemical properties of spinel-ferrite-coated hematite for solar water splitting

    Science.gov (United States)

    Selvaraj, Seenivasan; Moon, Hee; Kim, Do-Heyoung

    2018-01-01

    Photo-electrochemical water splitting with hematite photo-anodes under solar irradiation has attracted considerable attention as regards the production of renewable hydrogen energy. However, many challenges remain unresolved, as the full contribution of the catalytic over-layers has not been fully realized. Herein, we incorporate uniform spinel nickel-ferrite over-layers in hematite photo-anodes to obtain an improved understanding of the associated intrinsic changes. We achieve a 1.5-mA/cm2 photo-current density at 1.23 VRHE (RHE: reversible hydrogen electrode) under one-sun illumination conditions, along with a negative shift of 200 mV in the onset potential, for NiFe2O4-coated Sn-doped hematite photo-anodes. Fundamental electrochemical analyses clearly show that the shift in the onset potential is predominantly due to the enhanced photo-voltage development inside the hematite, rather than being purely caused by the interfacial kinetics. These insights reveal a new direction for fundamental research on photo-anodes towards fabrication of more efficient photo-anode systems.

  8. Compositional and structural variabilities of Mg-rich iron oxide spinels from tuffite

    Directory of Open Access Journals (Sweden)

    W. N. Mussel

    1999-12-01

    Full Text Available Maghemite (γFe2O3 from tuffite is exceptionally rich in Mg, relatively to most of those reportedly found in other mafic lithosystems. To investigate in detail the compositional and structural variabilities of this natural magnetic iron oxide, sets of crystals were isolated from samples collected at different positions in a tuffite weathering mantle. These sets of crystal were individually powdered and studied by X-ray diffractometry, Mössbauer spectroscopy, magnetization measurements and chemical analysis. Lattice parameter of the cubic cell (a0 was found to vary from 0.834(1 to 0.8412(1 nm. Lower a0-values are characteristic of maghemite whereas higher ones are related to a magnetite precursor. FeO content ranges up to 17 mass % and spontaneous magnetization ranges from 8 to 32 J T-1 kg-1. Zero-field room temperature Mössbauer spectra are rather complex, indicating that the hyperfine field distributions due to Fe3+ and mixed valence Fe3+/2+ overlap. The structural variabilities of the (Mg, Ti-rich iron oxide spinels is essentially related to the range of chemical composition of its precursor (Mg, Ti-rich magnetite, and probably to the extent to which it has been oxidized during transformation in soil.

  9. 2D Kagome ordering in the 3D frustrated spinel Li2Mn2O4

    International Nuclear Information System (INIS)

    Wiebe, C R; Russo, P L; Savici, A T; Uemura, Y J; MacDougall, G J; Luke, G M; Kuchta, S; Greedan, J E

    2005-01-01

    Muon spin relaxation (μSR) experiments on the geometrically frustrated spinel oxide, Li 2 Mn 2 O 4 , show the development of spin correlations over a range of lengthscales with decreasing temperature. Increased relaxation below ∼150 K is consistent with the onset of spin correlations. Below 50 K, spin order, on a lengthscale which is long range for the μSR probe, appears abruptly in temperature, consistent with prior neutron diffraction results. The oscillations in the zero field asymmetry are analysed using a three frequency model. By locating the muon site, this is shown to be consistent with the unexpected 2Dq=√3x√3 structure on the Kagome planes proposed originally from neutron data. Longitudinal field data demonstrate that some spin dynamics persist even at 2 K. Thus, a very complex magnetic ground state, featuring the coexistence of long lengthscale 2D ordering and significant spin dynamics, is proposed. This is unusual considering the 3D topology of the Mn 3+ spins in this material

  10. Dual field effects in electrolyte-gated spinel ferrite: electrostatic carrier doping and redox reactions.

    Science.gov (United States)

    Ichimura, Takashi; Fujiwara, Kohei; Tanaka, Hidekazu

    2014-07-24

    Controlling the electronic properties of functional oxide materials via external electric fields has attracted increasing attention as a key technology for next-generation electronics. For transition-metal oxides with metallic carrier densities, the electric-field effect with ionic liquid electrolytes has been widely used because of the enormous carrier doping capabilities. The gate-induced redox reactions revealed by recent investigations have, however, highlighted the complex nature of the electric-field effect. Here, we use the gate-induced conductance modulation of spinel ZnxFe₃₋xO₄ to demonstrate the dual contributions of volatile and non-volatile field effects arising from electronic carrier doping and redox reactions. These two contributions are found to change in opposite senses depending on the Zn content x; virtual electronic and chemical field effects are observed at appropriate Zn compositions. The tuning of field-effect characteristics via composition engineering should be extremely useful for fabricating high-performance oxide field-effect devices.

  11. Formation and partial melting of two types of spin-cluster glass behavior in vanadate spinel

    International Nuclear Information System (INIS)

    Huang Yuanjie; Pi Li; Tan Shun; Zhang Yuheng; Yang Zhaorong

    2012-01-01

    We report the doping effect on the various properties of spinels Co 1-x Zn x V 2 O 4 (0 ≤ x ≤ 0.2). For the parent compounds, the rise in magnetization, the valley in thermal conductance, the transition from the ferromagnetic arrangement to non-collinear alignment indicated by the specific heat for the V sublattice, especially the frequency dependence of AC susceptibility around T 1 = 59 K, verify the occurrence of the transition at T 1 besides the ferrimagnetic transition at T C . The ferrimagnetic transition at T C induces the spin-cluster glass behavior and the transition at T 1 yields the new spin-cluster glass (NSCG) behavior. As the Zn 2+ -doped content increases, the above phenomena are gradually weakening to vanishing, but the glassy behavior at T C still exists for all samples. Through the fourth-order perturbation theory, we discuss the reasons for the gradual vanishing of the transition at T 1 . (paper)

  12. Settling of Spinel in A High-Level Waste Glass Melter

    International Nuclear Information System (INIS)

    Pavel Hrma; Pert Schill; Lubomir Nemec

    2002-01-01

    High-level nuclear waste is being vitrified, i.e., converted to a durable glass that can be stored in a safe repository for hundreds of thousands of years. Waste vitrification is accomplished in reactors call melters to which the waste is charged together with glass-forming additives. The mixture is electrically heated to a temperature as high as 1150 degree C (or even higher in advanced melters) to create a melt that becomes glass on cooling. This process is slow and expensive. Moreover, the melters that are currently in use or are going to be used in the U.S. are sensitive to clogging and thus cannot process melt in which solid particles are suspended. These particles settle and gradually accumulate on the melter bottom. Such particles, most often small crystals of spinel ( a mineral containing iron, nickel, chromium, and other minor oxides), inevitably occurred in the melt when the content of the waste in the glass (called waste loading) increases above a certain limit. To avoid the presence of solid particles in the melter, the waste loading is kept rather low, in average 15% lower than in glass formulated for more robust melters

  13. Structural characterisation and physical properties of Li MMnO 4 ( M=Cr, Ti) spinels

    Science.gov (United States)

    Arillo, M. A.; Cuello, G.; López, M. L.; Martín, P.; Pico, C.; Veiga, M. L.

    2005-01-01

    New spinel-type phases of general formula Li MMnO 4 ( M=Cr, Ti), derived from LiMn 2O 4 by substitution of Mn 3+ by Cr 3+ or Mn 4+ by Ti 4+, have been obtained and characterised. Neutron diffraction refinements confirm that both phases crystallise in the Fd3m space group, giving the cation distributions [Li] 8 a[CrMn] 16 dO 4 and [Li 0.66Ti 0.34] 8 a[Li 0.34MnTi 0.66] 16 dO 4. Electrical conductivity has been examined by various techniques showing that these materials behave as semiconductors. The electrochemical behaviour indicates different oxidation-reduction steps in both cases concomitant with the insertion/deinsertion of lithium in non-reversible processes. X-ray diffraction patterns show that the above process is topotactic in LiCrMnO 4. Magnetic data and neutron diffraction measurements show that no long-range magnetic ordering is present, suggesting a spin-glass transition for M=Cr at low temperature, while for M=Ti the presence of non-magnetic ions in the octahedral sublattice provokes an inherent magnetic frustration.

  14. Experimental study on viscosity of spinel-type manganese ferrite nanofluid in attendance of magnetic field

    Energy Technology Data Exchange (ETDEWEB)

    Amani, Mohammad, E-mail: m_amani@sbu.ac.ir [Mechanical and Energy Engineering Department, Shahid Beheshti University, Tehran (Iran, Islamic Republic of); Amani, Pouria, E-mail: pouria.amani@ut.ac.ir [Department of Chemical Engineering, Faculty of Engineering, University of Tehran, Tehran (Iran, Islamic Republic of); Kasaeian, Alibakhsh, E-mail: akasa@ut.ac.ir [Department of Renewable Energies, Faculty of New Science & Technologies, University of Tehran, Tehran (Iran, Islamic Republic of); Mahian, Omid, E-mail: omid.mahian@mshdiau.ac.ir [Young Researchers and Elite Club, Mashhad Branch, Islamic Azad University, Mashhad (Iran, Islamic Republic of); Kasaeian, Fazel, E-mail: f.kasa92@student.sharif.edu [Faculty of Material Science and Engineering, Sharif University of Technology, Tehran (Iran, Islamic Republic of); Wongwises, Somchai, E-mail: somchai.won@kmutt.ac.th [Fluid Mechanics, Thermal Engineering and Multiphase Flow Research Lab (FUTURE), Department of Mechanical Engineering, Faculty of Engineering, King Mongkut' s University of Technology Thonburi (KMUTT), Bangmod, Bangkok (Thailand)

    2017-04-15

    In this paper, an experimental evaluation on the viscosity of water-based manganese ferrite nanofluid with and without magnetic field with 100, 200, 300, and 400 G intensities has been conducted. The Brookfield DV-I PRIME viscometer is implemented to measure the MnFe{sub 2}O{sub 4}/water nanofluid viscosity and to evaluate the influence of different volume concentrations (from 0.25% to 3%) and various temperatures (from 20 to 60 °C) on the viscosity. According to the measurements, viscosity incrementally increases with the augmentation of nanoparticles concentration while it remarkably decreases at higher temperatures under absence and attendance of magnetic field. The maximum viscosity ratio of 1.14 is achieved at 3 vol% of nanoparticles and 20 °C under no magnetic field, whereas it increments to maximum viscosity ratio of 1.75 at 3 vol% of nanoparticles and 40 °C under 400 G magnetic field. Furthermore, new correlation is proposed for determination of viscosity of MnFe{sub 2}O{sub 4}/water nanofluids in terms of magnetic field intensity, volume concentration and temperature. - Highlights: • Viscosity of spinel-type manganese ferrite nanofluids is measured. • Effect of a constant magnetic field on the viscosity is investigated. • A novel correlation is proposed for estimation of the measured viscosity.

  15. Experimental study on viscosity of spinel-type manganese ferrite nanofluid in attendance of magnetic field

    International Nuclear Information System (INIS)

    Amani, Mohammad; Amani, Pouria; Kasaeian, Alibakhsh; Mahian, Omid; Kasaeian, Fazel; Wongwises, Somchai

    2017-01-01

    In this paper, an experimental evaluation on the viscosity of water-based manganese ferrite nanofluid with and without magnetic field with 100, 200, 300, and 400 G intensities has been conducted. The Brookfield DV-I PRIME viscometer is implemented to measure the MnFe 2 O 4 /water nanofluid viscosity and to evaluate the influence of different volume concentrations (from 0.25% to 3%) and various temperatures (from 20 to 60 °C) on the viscosity. According to the measurements, viscosity incrementally increases with the augmentation of nanoparticles concentration while it remarkably decreases at higher temperatures under absence and attendance of magnetic field. The maximum viscosity ratio of 1.14 is achieved at 3 vol% of nanoparticles and 20 °C under no magnetic field, whereas it increments to maximum viscosity ratio of 1.75 at 3 vol% of nanoparticles and 40 °C under 400 G magnetic field. Furthermore, new correlation is proposed for determination of viscosity of MnFe 2 O 4 /water nanofluids in terms of magnetic field intensity, volume concentration and temperature. - Highlights: • Viscosity of spinel-type manganese ferrite nanofluids is measured. • Effect of a constant magnetic field on the viscosity is investigated. • A novel correlation is proposed for estimation of the measured viscosity.

  16. Comparative studies on structural properties and antimicrobial potential of spinel ferrite nanoparticles synthesized using various methods

    Science.gov (United States)

    Baraliya, Jagdish D.; Rakhashiya, Purvi M.; Patel, Pooja P.; Thaker, Vrinda S.; Joshi, Hiren H.

    2017-05-01

    In this study, novel multifunctional magnetic iron-based nanoparticles (CoFe2O4) coated with silica, silica-DEG (diethylene glycol), PEG (polyethylene glycol) were synthesized using Auto Combustion Method (ACM), Co-precipitation Method (COPM), Citrate Precursor Method (CPM), Flash Combustion Method (FCM). These spinel ferrite nanoparticles also contain very high antibacterial properties to fulfill the requirements of a drug delivery system so that the antibiotic concentration could be minimized. A potential delivery system could be based on a ferromagnetic fluid. The effects of various preparation methods on the physical properties of the nanoparticles were examined. The nanoparticles were also tested against four human pathogenic bacteria (Gram negative E.coli, P. aeruginosa, Gram positive S. aureus, S. pyogenus) and two fungi (C. albicans, A.niger). It was revealed that a nanoparticle has strong antibacterial activity as compared to antifungal. Further, Gram positive bacteria are more affected than Gram negative bacteria. It was also clear that different methods of coating have great influence on the antimicrobial properties. It was observed that these nanoparticles have significantly different but potentially very high antimicrobial activities against the tested organisms than found elsewhere by other nanoparticles on the same organisms.

  17. Investigation of ferromagnetic spinel semiconductors by hyperfine interactions of implanted nuclear probes

    CERN Document Server

    Samokhvalov, V; Dietrich, M; Schneider, F; Tiginyanu, I M; Tsurkan, V; Unterricker, S

    2003-01-01

    The semiconducting ferromagnetic spinel compounds CdCr//2Se //4, CdCr //2S//4, HgCr//2Se//4 and CuCr//2Se//4 (metallic) were investigated by the perturbed angular correlations (PAC) method with the radioactive probes **1**1**1In, **1**1**1**mCd, **1**1**1Ag, **1**1**7Cd, **1**9**9**mHg and **7**7Br. The probes were implanted at the ISOLDE on-line separator (CERN-Geneva) into single crystals. From the time dependence of the PAC spectra and the measured hyperfine interaction parameters: electric field gradient and magnetic hyperfine field, the probe positions and the thermal behavior of the probes could be determined. Cd, Ag and Hg are substituted at the A-site, In at the A- and B-site in the semiconducting compounds and Br at the anion position. Electric and magnetic hyperfine fields were used as test quantities for theoretical charge and spin density distributions of LAPW calculations (WIEN97).

  18. Growth of InN films on spinel substrates by pulsed laser deposition

    Energy Technology Data Exchange (ETDEWEB)

    Mitamura, K. [Institute of Industrial Science (IIS), The University of Tokyo, 4-6-1 Komaba, Megruro-ku, Tokyo 153-8505 (Japan); Ohta, J.; Fujioka, H. [Institute of Industrial Science (IIS), The University of Tokyo, 4-6-1 Komaba, Megruro-ku, Tokyo 153-8505 (Japan); Kanagawa Academy of Science and Technology (KAST), 3-2-1 Sakado, Takatsu-ku, Kanagawa 213-0012 (Japan); Oshima, M. [Department of Applied Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)

    2007-10-15

    We have grown InN films on MgAl{sub 2}O{sub 4}(111) substrates with atomically flat surfaces using pulsed laser deposition (PLD) and compared their structural properties with those grown on (Mn,Zn)Fe{sub 2}O{sub 4}(111) substrates. It has been revealed that InN(0001) films grow on MgAl{sub 2}O{sub 4}(111) with an in-plane epitaxial relationship of InN[1 anti 100]//MgAl{sub 2}O{sub 4}[1 anti 10], achieving a lattice mismatch minimum. The InN films exhibited a clear sixfold rotational symmetry, without 30 rotational domains and with a full width at half maximum value of the InN 0002 rocking curve being 17.5 arcmin. Comparison between InN films grown on MgAl{sub 2}O{sub 4} and those on (Mn,Zn)Fe{sub 2}O{sub 4} led us to conclude that suppression of the interfacial reactions between the InN films and the substrate is inherently important to obtain high quality InN on substrates with a spinel structure. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  19. Electron channeling X-ray microanalysis for cation configuration in irradiate magnesium alimate spinel

    International Nuclear Information System (INIS)

    Matsumura, S.; Soeda, T.; Zaluzec, N. J.; Kinoshita, C.

    1999-01-01

    High angular resolution electron channeling X-ray spectroscopy (HARECXS) was examined as a practical tool to locate lattice-ions in spinel crystals. The orientation dependent intensity distribution of emitted X-rays obtained by HARECXS is so sensitive to lattice-ion configuration in the illuminated areas that the occupation probabilities on specific positions in the crystal lattice can be determined accurately through comparison with the theoretical rocking curves. HARECXS measurements have revealed partially disordered cation arrangement in MgO·nAl 2 O 3 with n = 1.0 and 2.4. Most Al 3+ lattice-ions occupy the octahedral (VIII) sites, while Mg 2 lattice-ions reside on both the tetrahedral (IV) and the octahedral (VIII) sites. The structural vacancies are enriched in the IV-sites. Further evacuation of cations from the IV-sites to the VIII-sites is recognized in a disordering process induced by irradiation with 1 MeV Ne + ions up to 8.9 dpa at 870 K

  20. Quasicrystalline Approach to Prediting the Spinel-Nepheline Liquidus: Application to Nuclear Waste Glass Processing

    Energy Technology Data Exchange (ETDEWEB)

    Jantzen, Carol

    2005-10-10

    The crystal-melt equilibria in complex fifteen component melts are modeled based on quasicrystalline concepts. A pseudobinary phase diagram between acmite (which melts incongruently to a transition metal ferrite spinel) and nepheline is defined. The pseudobinary lies within the Al{sub 2}O{sub 3}-Fe{sub 2}O{sub 3}-Na{sub 2}O-SiO{sub 2} quaternary system that defines the crystallization of basalt glass melts. The pseudobinary provides the partitioning of species between the melt and the primary liquidus phases. The medium range order of the melt and the melt-crystal exchange equilibria are defined based on a constrained mathematical treatment that considers the crystallochemical coordination of the elemental species in acmite and nepheline. The liquidus phases that form are shown to be governed by the melt polymerization and the octahedral site preference energies. This quasicrystalline liquidus model has been used to prevent unwanted crystallization in the world's largest high level waste (HLW) melter for the past three years while allowing >10 wt% higher waste loadings to be processed.

  1. Radiation-induced electrical conductivity in MgAl2O4 spinel

    International Nuclear Information System (INIS)

    Pells, G.P.

    1990-12-01

    The d.c. electrical conductivity of high purity, polycrystalline MgAl 2 O 4 spinel of 99.5% theoretical density has been measured during irradiation by 18 MeV protons at reactor relevant ionization dose rates. The radiation-induced conductivity (RIC) at 200 C varied in a slightly sub-linear manner with dose rate. At temperatures between 250-350 C the RIC varied in a complex manner with the dose rate dependence being itself dose rate dependent. At higher temperatures the RIC reverted to an essentially linear variation with dose rate. The complex dose rate dependence is ascribed to the magnesium vacancy concentration introduced by the small Al 2 O 3 excess (MgO:Al 2 O = 1:1.05) and the presence of anti-structure defects producing large concentrations of intrinsic electron and hole traps. There was no evidence that the accumulation of radiation damage influenced the details of radiation-induced conductivity and MgAl 2 O 4 retained reasonable insulating properties at the highest dose rate and temperature. (author)

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

    Science.gov (United States)

    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

  3. Expansion during the formation of the magnesium aluminate spinel (MgAl(2)O(4)) from its basic oxide (MgO and Al(2)O(3)) powders

    Science.gov (United States)

    Duncan, Flavia Cunha

    The extraordinary expansion during the reaction sintering of the magnesium aluminate spinel (MgAl2O4) from its basic oxide (MgO and Al2O3) powders was studied. Experimental series of different size fractions of the reacting materials were formulated to produce the Mg-Al spinel. After batches were prepared, specimens were compacted and fired in air from 1200° to 1700°C for a fixed firing time. A separate set of specimens was fired as a function of time to determine the reaction kinetic parameters. Dimensional changes confirmed that extraordinary expansions of three to four times greater than the prediction from the reaction of solids occur. The solid-state reactions were monitored by X-ray diffraction. The activation energy of the spinel reaction formation was determined to be 280 +/- 20 kJ/mol. It is believed to be associated with the diffusivity of Mg 2+ in either magnesia or spinel during the development of the final spinel structure. New porosity developed in the compacts during the reaction formation of spinel. Scanning electron microscopy confirmed that the magnesia evaporated leaving behind porous magnesia grains, condensed on the alumina particles and reacted to form a shell of spinel. Hollow spinel particles resulted from the original particles of alumina. These porosities generated within the reacting materials influenced the expansions. Final volumetric expansion could potentially reach 56% as a result of the reaction of solids and the porosity generation within MgO and Al2O3. Models of a single alumina particle with and without development of internal porosity were developed. 3-D arrangements of particles showed additional porosity, influencing on the expansions. The decrease in porosity of some specimens fired at higher temperatures indicated that sintering and densification occur simultaneously with the reaction formation of spinel. The decrease in the interparticle porosity limits the full expansion of the particulates to levels lower than the

  4. Water in orthopyroxene from abyssal spinel peridotites of the East Pacific Rise (ODP Leg 147: Hess Deep)

    Science.gov (United States)

    Hesse, Kirsten T.; Gose, Jürgen; Stalder, Roland; Schmädicke, Esther

    2015-09-01

    Abyssal spinel peridotites from Hess Deep, East Pacific Rise (ODP Leg 147) were investigated concerning their major, minor, and trace element mineral chemistry and the incorporation of structural water in orthopyroxene. The rocks are partially serpentinized harzburgites containing primary minerals of olivine, orthopyroxene, clinopyroxene, and spinel. Orthopyroxene is enstatitic with Mg# (Mg/(Mg + Fe)) between 0.90 and 0.92 and Al2O3 from 0.5 to 2.9 wt.%. The residual harzburgite experienced high degrees of melt removal in the spinel peridotite stability field. The average degree of partial melting was calculated to be 17.5% (range: 16.4-17.8%). Trace element data of ortho- and clinopyroxenes reflect this strong depletion, characteristic for the restitic nature of abyssal peridotites. Mantle re-equilibration temperatures around 1000 °C indicate that, after melt extraction and before exhumation to the ocean floor, the rocks experienced significant cooling in the spinel peridotite facies. Water contents of orthopyroxene range from 86 to 233 wt. ppm H2O with an average concentration of 142 wt. ppm H2O. These results represent the first data on water contents in the sub-pacific mantle obtained by direct measurements of sub-oceanic peridotite. The water contents are not related to mineral chemistry, stratigraphy, melting degree, mantle equilibrium conditions or oxidation state. Calculated post-melt peridotite water contents vary between 40 and 100 wt. ppm H2O. Compared to Mid-Atlantic Ridge peridotites, the East Pacific Rise samples of Leg 147 contain somewhat lower water concentrations than samples from Leg 153 and considerably higher contents than those of Leg 209 (Gose et al., 2009; Schmädicke et al., 2011). In Leg 147, the strongest OH absorbtion band occurs at 3420 cm- 1, wheras orthopyroxene from MAR peridotite (Legs 153 and 209) has its strongest absorbtion band at 3566 and 3522 cm- 1. The mantle equilibrium temperature of Leg 147 peridotites is lower than that

  5. Provenance of sediments from Sumatra, Indonesia - Insights from detrital U-Pb zircon geochronology, heavy mineral analyses and Raman spectroscopy

    Science.gov (United States)

    Liebermann, C.; Hall, R.; Gough, A.

    2017-12-01

    The island of Sumatra is situated at the southwestern margin of the Indonesian archipelago. Although it is the sixth largest island in the world, the geology of the Sumatra sedimentary basins and their underlying basement is relatively poorly understood in terms of their provenance. This work is a multi-proxy provenance study utilizing U-Pb detrital zircon dating by LA-ICP-MS combined with optical and Raman spectroscopy-based heavy mineral analysis. It will help to unravel the stratigraphy of Sumatra, contribute to paleogeographic reconstruction of western SE Asia, and aid a wider understanding of Sumatran petroleum plays. Thin section analyses, heavy mineral assemblages, and >3500 concordant U-Pb zircon ages, from samples acquired during two fieldwork seasons indicate a mixed provenance for Cenozoic sedimentary formations, including both local igneous sources and mature basement rocks. Characteristic Precambrian zircon age spectra are found in all analysed Cenozoic sedimentary strata. These can be correlated with zircon age populations found in Sumatran basement rocks; Neoproterozoic and Mesoproterozoic age groups are dominant (c. 500-600 Ma, c. 850-1000 Ma, c. 1050-1200 Ma). Paleoproterozoic to Archaean zircons occur as minor populations. The Phanerozoic age spectra of the Cenozoic formations are characterised by distinct Carboniferous, Permo-Triassic, and Jurassic-Cretaceous zircon populations. Permo-Triassic zircons are interpreted to come from granitoids in the Malay peninsula or Sumatra itself. Eocene to Lower Miocene strata are characterised by ultrastable heavy minerals such as zircon, tourmaline, and rutile, which together with garnet, suggest the principal sources were igneous and metamorphic basement rocks. Cenozoic zircons appear only from the Middle Miocene onwards. This change is interpreted to indicate a new contribution from a local volcanic arc, and is supported by the occurrence of unstable heavy minerals such as apatite and clinopyroxene, and the

  6. U-Pb Detrital Zircon Ages from Sarawak: Changes in Provenance Reflecting the Tectonic Evolution of Southeast Asia

    Science.gov (United States)

    Breitfeld, H. T.; Galin, T.; Hall, R.

    2014-12-01

    Sarawak is located on the northern edge of Sundaland in NW Borneo. Five sedimentary basins are distinguished with ages from Triassic to Cenozoic. New light mineral, heavy mineral and U-Pb detrital zircon ages show differences in provenance reflecting the tectonic evolution of the region. The oldest clastic sediments are Triassic of the Sadong-Kuching Basin and were sourced by a Carnian to Norian volcanic arc and erosion of Cathaysian rocks containing zircons of Paleoproterozoic age. Sandstones of the Upper Jurassic to Cretaceous Bau-Pedawan Basin have distinctive zircon populations indicating a major change of tectonic setting, including initiation of subduction below present-day West Sarawak in the Late Jurassic. A wide range of inherited zircon ages indicates various Cathaysian fragments as major source areas and the arrival of the SW Borneo Block following subduction beneath the Schwaner Mountains in the early Late Cretaceous. After collision of the SW Borneo Block and the microcontinental fragments with Sundaland in the early Late Cretaceous, deep marine sedimentation (Pedawan Formation) ceased, and there was uplift forming the regional Pedawan-Kayan unconformity. Two episodes of extension were responsible for basin development on land from the latest Cretaceous onwards, probably in a strike-slip setting. The first episode formed the Kayan Basin in the Latest Cretaceous (Maastrichtian) to Early Paleocene, and the second formed the Ketungau Basin and the Penrissen Sandstone in the Middle to Late Eocene. Zircons indicate nearby volcanic activity throughout the Early Cenozoic in NW Borneo. Inherited zircon ages indicate an alternation between Borneo and Tin Belt source rocks. A large deep marine basin, the Rajang Basin, formed north of the Lupar Line fault. Zircons from sediments of the Rajang Basin indicate they are of similar age and provenance as the contemporaneous terrestrial sediments to the south suggesting a narrow steep continental Sundaland margin at the

  7. Crayfish impact desert river ecosystem function and litter-dwelling invertebrate communities through association with novel detrital resources.

    Directory of Open Access Journals (Sweden)

    Eric K Moody

    Full Text Available Shifts in plant species distributions due to global change are increasing the availability of novel resources in a variety of ecosystems worldwide. In semiarid riparian areas, hydric pioneer tree species are being replaced by drought-tolerant plant species as water availability decreases. Additionally, introduced omnivorous crayfish, which feed upon primary producers, allochthonous detritus, and benthic invertebrates, can impact communities at multiple levels through both direct and indirect effects mediated by drought-tolerant plants. We tested the impact of both virile crayfish (Orconectes virilis and litter type on benthic invertebrates and the effect of crayfish on detrital resources across a gradient of riparian vegetation drought-tolerance using field cages with leaf litter bags in the San Pedro River in Southeastern Arizona. Virile crayfish increased breakdown rate of novel drought-tolerant saltcedar (Tamarix ramosissima, but did not impact breakdown of drought-tolerant seepwillow (Baccharis salicifolia or hydric Fremont cottonwood (Populus fremontii and Gooding's willow (Salix goodingii. Effects on invertebrate diversity were observed at the litter bag scale, but no effects were found at the cage scale. Crayfish decreased alpha diversity of colonizing macroinvertebrates, but did not affect beta diversity. In contrast, the drought-tolerant litter treatment decreased beta diversity relative to hydric litter. As drought-tolerant species become more abundant in riparian zones, their litter will become a larger component of the organic matter budget of desert streams which may serve to homogenize the litter-dwelling community and support elevated populations of virile crayfish. Through impacts at multiple trophic levels, crayfish have a significant effect on desert stream ecosystems.

  8. Modelling detrital coral grain-size and age: Insights from sediment abrasion process of Yongle Atoll of South China Sea

    Science.gov (United States)

    Li, Y.; Zou, X.; Ge, C.; Tan, M.; Wang, C.

    2017-12-01

    Reef islands situated on the rims of atolls are composed almost exclusively of bioclastic materials locally supplied from adjacent coral reefs. Major skeletal component of these islands include coral, coralline algae, mollusks and foraminifera, produced in adjacent reefs. As the island builder, the bioclastic material is the sedimentary products, which also is the point of penetration to decipher the process. The bioclast of coral islands decrease in size with the transportation process. The grain-size provides a proxy record for the abrasion history of the unconsolidated sediment. The 230Th age of coral record the abrasion time. We hereby present a model to calculate the abrasion rate based on the data of 230Th age and grain-size of Yongle Atoll of Xisha Island, South China Sea. The grain size pattern in Yongle Atoll environment have confirm that the coral article diminution behave exponentially. The sediment composition of Yongle Atoll is identified, coral is dominant sediment constituent and the Th230 age is shown to exert an age distribution characteristics of coral detritus. We illustrate this approach by calculate the coral debris age of Xude Atoll, which located near the Yongle Atoll and then by comparing actual measured age and calculated age and to explore the dependence of the model. Observed 230 Th ages are well matched by predicted ages for medium age sediment. A poorer match for young and old sediment may result from some combination of large analytical uncertainties in the detrital ages and inhomogeneous erosion rates within the atoll. Such mismatches emphasize the need for more accurate kinematic models and for sampling strategies that are adapted to atoll-specific geologic and geomorphic conditions. Results presented constitute important new insights into regional sediment abrasion processed and on the evolution of coral atoll islands.

  9. Liquidus temperature in the spinel primary phase field: A comparison between optical and crystal fraction methods

    Energy Technology Data Exchange (ETDEWEB)

    Riley, Brian J.; Hrma, Pavel; Crum, Jarrod V.; Vienna, John D.; Schweiger, Michael J.; Rodriguez, Carmen P.; Peterson, Jacob A.

    2018-03-01

    Liquidus temperature (TL) was measured for simulated high-level waste borosilicate glasses covering a Hanford composition region, using an optical method and a crystal-fraction extrapolation method with X-ray diffraction data from isothermal heat treatments. The 38 glasses encompassed a one-component-at-a-time variation of a 16-component matrix. The TL values ranged from 1006°C to 1603°C. First-order polynomial models were fitted to data to obtain coefficients in terms of the effect of 1 mass% component addition on the TL: TL-increasing oxides Cr2O3 (264°C), “Others” (minor components, 163°C), oxides of noble metals (137°C), NiO (91°C), Al2O3 and Fe2O3 (~19–21°C); TL-decreasing oxides K2O (-26°C), Na2O (-41°C), and Li2O (-68°C); oxides of little effect MnO, P2O5, ZrO2, F, Bi2O3, SiO2, B2O3, and CaO (9 to -12°C). Also presented are temperatures (T1%) at which glasses contain 1 vol% of spinel as these values are considered relevant to the Hanford Tank Waste Treatment and Immobilization Plant. The measured and estimated values are compared and contrasted and the effect of TL and T1% on glass formulation is discussed.

  10. Hf-Nd isotope decoupling in the oceanic lithosphere: constraints from spinel peridotites from Oahu, Hawaii

    Science.gov (United States)

    Bizimis, Michael; Sen, Gautam; Salters, Vincent J. M.

    2004-01-01

    We present a detailed geochemical investigation on the Hf, Nd and Sr isotope compositions and trace and major element contents of clinopyroxene mineral separates from spinel lherzolite xenoliths from the island of Oahu, Hawaii. These peridotites are believed to represent the depleted oceanic lithosphere beneath Oahu, which is a residue of a MORB-related melting event some 80-100 Ma ago at a mid-ocean ridge. Clinopyroxenes from peridotites from the Salt Lake Crater (SLC) show a large range of Hf isotopic compositions, from ɛHf=12.2 (similar to the Honolulu volcanics series) to extremely radiogenic, ɛHf=65, at nearly constant 143Nd/ 144Nd ratios ( ɛNd=7-8). None of these samples show any isotopic evidence for interaction with Koolau-type melts. A single xenolith from the Pali vent is the only sample with Hf and Nd isotopic compositions that falls within the MORB field. The Hf isotopes correlate positively with the degree of depletion in the clinopyroxene (e.g. increasing Mg#, Cr#, decreasing Ti and heavy REE contents), but also with increasing Zr and Hf depletions relative to the adjacent REE in a compatibility diagram. The Lu/Hf isotope systematics of the SLC clinopyroxenes define apparent ages of 500 Ma or older and these compositions cannot be explained by mixing between any type of Hawaiian melts and the depleted Pacific lithosphere. Metasomatism of an ancient (e.g. 1 Ga or older) depleted peridotite protolith can, in principle, explain these apparent ages and the Nd-Hf isotope decoupling, but requires that the most depleted samples were subject to the least amount of metasomatism. Alternatively, the combined isotope, trace and major element compositions of these clinopyroxenes are best described by metasomatism of the 80-100 Ma depleted oceanic lithosphere by melts products of extensive mantle-melt interaction between Honolulu Volcanics-type melts and the depleted lithosphere.

  11. Novel low temperature synthesis of spinel nano-magnesium chromites from secondary resources

    Energy Technology Data Exchange (ETDEWEB)

    El-Sheikh, S.M., E-mail: selsheikh2001@gmail.com [Nanostructured Materials Laboratory, Advanced Material Department, Central Metallurgical R and D Institute (CMRDI), P.O. Box 78, Helwan, 11421 Cairo (Egypt); Rabbah, M., E-mail: mahmoud.rabah@ymail.com [Electrochemical and Chemical Treatment Laboratory, Minerals Department, Central Metallurgical R and D Institute (CMRDI), P.O. Box 78, Helwan, 11421 Cairo (Egypt)

    2013-09-20

    Graphical abstract: FE-SEM micrograph and TEM image of magnesium chromite sample heated at 500 °C. - Highlights: • No study has been reported to prepare spinel magnesium chromite form waste resources. • Novel low synthesis temperature of magnesium chromite. • Selective removal of Ca ions from industrial waste tannery solution is rarely reported. • The method applied is simple and safe. - Abstract: A novel low temperature method for synthesis of nano-crystalline magnesium chromites from the tannery waste solution was investigated. Magnesium and chromium hydroxides gel was co-precipitated at pH 8.5 using ammonia solution. MgCr{sub 2}O{sub 4} was obtained by heating the gel formed at different temperatures 300–500 °C for to 8 h. FT-IR, TG-DTG-DTA, FE-SEM and TEM were used to investigate the produced materials. XRD patterns of the primary oxides revealed the formation of amorphous oxide phase by heating at 300 °C. Heating at 400 °C produces nano-crystallite magnesium chromites partly having the structure MgCrO{sub 4} and mainly MgCr{sub 2}O{sub 4} and traces of Cr{sub 2}O{sub 3}{sup +} 500 °C MgCrO{sub 4} mostly decomposed into MgCr{sub 2}O{sub 4} structure{sub .} After 8 h of heating at 500 °C, Cr{sub 2}O{sub 3} completely disappeared. A high surface area about 42.6 m{sup 2}/g and mesoporous structure was obtained for the produced sample at 500 °C for 8 h. A thermodynamic model has been suggested to explain the findings.

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

    Science.gov (United States)

    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.

  13. Effect of MgCl2 addition on the sintering behavior of MgAl2O4 spinel and formation of nano-particles

    Directory of Open Access Journals (Sweden)

    Mohammadi F.

    2014-01-01

    Full Text Available In this paper, the effect of MgCl2 addition on the sintering behavior of MgAl2O4 spinel produced via oxide mixture method was investigated. For this reason, the stoichiometric mixture of magnesite and calcined alumina as raw materials was calcined at 1100°C. The calcined mixture was milled, pressed and then, fired at 1300 and 1500°C after addition of various amounts of MgCl2. Besides, the physical properties, phase composition and microstructure of fired samples were investigated. The results showed that MgCl2 addition has great effect on the densification and particle size of spinel. Besides, MgCl2 addition increases the amount of spinel phase at all firing temperatures. Due to the decomposition of MgCl2 and then formation of ultra-fine MgO particles, the nano-sized spinel is formed on the surface of the larger spinel particles.

  14. Structural, dielectric and gas sensing behavior of Mn substituted spinel MFe{sub 2}O{sub 4} (M=Zn, Cu, Ni, and Co) ferrite nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Ranjith Kumar, E., E-mail: ranjueaswar@gmail.com [Department of Physics, Dr. NGP Institute of Technology, Coimbatore 641048, Tamil Nadu (India); Siva Prasada Reddy, P.; Sarala Devi, G. [Inorganic and Physical Chemistry Division, Indian Institute Chemical Technology, Hyderabad 500607 (India); Sathiyaraj, S. [Department of Chemistry, Dr. NGP Institute of Technology, Coimbatore 641048, Tamil Nadu (India)

    2016-01-15

    Spinel ferrite (MnZnFe{sub 2}O{sub 4}, MnCuFe{sub 2}O{sub 4}, MnNiFe{sub 2}O{sub 4} and MnCoFe{sub 2}O{sub 4}) 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-Fe{sub 2}O{sub 3} 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 MFe{sub 2}O{sub 4} ferrite nanoparticles were measured by exposing the materials to reducing gas like liquefied petroleum gas (LPG). - Highlights: • The egg white support to achieve sample with shorter reaction time. • Manganese plays a significant role in sensor response. • Nature of the ferrites was affected with increasing annealing temperature.

  15. Structural, dielectric and gas sensing behavior of Mn substituted spinel MFe2O4 (M=Zn, Cu, Ni, and Co) ferrite nanoparticles

    Science.gov (United States)

    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).

  16. DT fusion neutron irradiation of BNL--LASL superconductor wires, LASL YAG, Al2O3 and Spinel, LASL-IIT MgO, YAG, Al2O3 and Spinel, and NRL GeO2 crystals, December 28, 1977

    International Nuclear Information System (INIS)

    MacLean, S.C.

    1978-01-01

    The DT fusion neutron irradiation of eleven BNL-LAST superconductor wires, six NRL GeO 2 crystals, two YAG, two Spinel and two Al 2 O 3 crystals for LASL and four LASL high purity single crystals of MgO, YAG, Spinel and Al 2 O 3 is described. The sample position, beam-on time, and neutron dose record are given. The maximum fluence on any sample was 1.51 x 10 16 neutrons/cm 2

  17. Diagenetic versus detrital origin of the magnetic susceptibility variations in some carbonate Frasnian-Famennian boundary sections from Northern Africa and Western Europe: implications for paleoenvironmental reconstructions

    Science.gov (United States)

    Riquier, Laurent; Averbuch, Olivier; Devleeschouwer, Xavier; Tribovillard, Nicolas

    2010-10-01

    To provide a new insight into the diagenetic versus detrital origin of the magnetic susceptibility variations in ancient carbonate sequences, a study was conducted within four Frasnian-Famennian platform carbonate sections from Germany, France and Morocco. The study includes along-section magnetic susceptibility and carbonate content measurements complemented by analyses of magnetic hysteresis parameters, inorganic geochemistry and clay mineralogy. Our results show that the magnetic susceptibility evolution is dominantly controlled by the variations in the concentration of low-coercivity ferromagnetic magnetite grains and, to a lesser extent, of paramagnetic clays. In more detail, hysteresis ratios suggest the coexistence of two magnetite populations with significantly different grain size: (1) a dominantly coarse-grained detrital fraction including a mixture of multi-domain and single-domain particles (2) an authigenic fine-grained fraction composed of a mixture of single-domain and superparamagnetic particles. Despite a diagenetic imprint on the clay assemblages, no relationship is established between magnetic susceptibility and illite crystallinity, therefore discarding a noticeable distortion of primary within-section magnetic susceptibility evolution. The overall inherited character of the magnetic susceptibility fluctuations is corroborated by a significant correlation of magnetic susceptibility with terrigenous proxies (Zr, Th). The poorer correlation of magnetic susceptibility with the Fe content is consistent with the existence of a very fine-grained authigenic magnetite component that possibly induces a global magnetic susceptibility increase at the section scale, but no distortion of the within-section evolution. The magnetic susceptibility curves presented here provide a general record of climate-driven detrital influx and carbonate productivity through Frasnian-Lower Famennian times.

  18. Using Detrital Zircon Geochronology to Constrain Paleogene Provenance and Its Relationship to Rifting in the Zhu 1 Depression, Pearl River Mouth Basin, South China Sea

    Science.gov (United States)

    Wang, Wei; Ye, Jiaren; Bidgoli, Tandis; Yang, Xianghua; Shi, Hesheng; Shu, Yu

    2017-11-01

    Paleogene syn-rift successions in the South China Sea are poorly understood and systematic provenance analysis, which could provide clues to their history, is lacking. Here we report 409 new concordant U-Pb ages from detrital zircons separated from the Paleogene Wenchang, Enping, and Zhuhai formations in the Zhu 1 depression, Pearl River Mouth Basin. The new data, combined with the published age data from the region, document changes in the provenance of syn-rift successions. Detrital zircons from the Eocene Wenchang Formation are unimodal, with Jurassic-Cretaceous (180-80 Ma) ages making up >80% of grains. The ages are consistent with the geochronology of intrabasinal highs, dominated by igneous rocks emplaced during the Yanshanian orogeny, and suggest local provenance. By contrast, detrital zircons from the upper Eocene to lower Oligocene Enping Formation form three well-recognized age-clusters, with peaks at 150, 254, and 438 Ma that match documented tectonomagmatism in South China Block (SCB). Combined with increasing numbers of Precambrian zircons, the data suggest increasing influence of regional provenance of the SCB. Similar age peaks are also recognized from the limited number of zircons analyzed from the upper Oligocene Zhuhai Formation and comparability with modern shelf and river sediment indicates the unit was mainly sourced from the SCB and likely transported by a paleo-Pearl River. We infer that the change in provenance, from local uplifts within the Zhu 1 to the SCB, is related to distinct phases of PRMB rift development; however, later changes are best explained by SCB drainage evolution.

  19. Recognition of the Kaweka Terrane in northern South Island, New Zealand : preliminary evidence from Rb-Sr metamorphic and U-Pb detrital zircon ages

    International Nuclear Information System (INIS)

    Adams, C.J.; Mortimer, N.; Campbell, H.J.; Griffin, W.L.

    2011-01-01

    Detrital zircon U-Pb ages and Rb-Sr metamorphic ages from low-grade Torlesse Supergroup metasedimentary rocks from North Canterbury and Marlborough provide preliminary evidence for a continuation of the Kaweka Terrane of the central North Island into the Torlesse Composite Terrane of the South Island. This would extend from the south side of the Wairau Fault in the upper Wairau River valley southwards to the Lake Tennyson and Lake Sumner areas, and as far as Hawarden. Rb-Sr ages indicate Jurassic metamorphism, 170±24 Ma, with initial 87 Sr/ 86 Sr ratios at that time 0.7073 ± 0.0007 i.e. similar to their North Island counterparts. These Kaweka Terrane rocks have detrital zircon ages that follow the distinctive pattern of the Torlesse rocks in general, i.e. substantial (>30%) Permian-Triassic and Precambrian-Early Palaeozoic groupings, but they also have minor youngest age components c. 175-165 Ma which constrain a maximum Early-Middle Jurassic depositional age. In detail, significant, older zircon components are Late Permian-Early Triassic (260-240 Ma) and Late Triassic (220-210 Ma), but the Precambrian-Early Palaeozoic detrital zircon ages are more scattered. The Kaweka Terrane thus forms a linear belt (c. 500 km) along the length of the Torlesse Composite Terrane in both North and South Islands. In the South Island it coincides with the Esk Head Belt, i.e. east of the Rakaia Terrane (Triassic-Late Permian) and west of the Pahau Terrane (Early Cretaceous-Late Jurassic). (author). 61 refs., 4 figs., 2 tabs.

  20. How Diverse Detrital Environments Influence Nutrient Stoichiometry between Males and Females of the Co-Occurring Container Mosquitoes Aedes albopictus, Ae. aegypti, and Culex quinquefasciatus.

    Science.gov (United States)

    Yee, Donald A; Kaufman, Michael G; Ezeakacha, Nnaemeka F

    2015-01-01

    Allocation patterns of carbon and nitrogen in animals are influenced by food quality and quantity, as well as by inherent metabolic and physiological constraints within organisms. Whole body stoichiometry also may vary between the sexes who differ in development rates and reproductive allocation patterns. In aquatic containers, such as tree holes and tires, detrital inputs, which vary in amounts of carbon and nitrogen, form the basis of the mosquito-dominated food web. Differences in development times and mass between male and female mosquitoes may be the result of different reproductive constraints, which could also influence patterns of nutrient allocation. We examined development time, survival, and adult mass for males and females of three co-occurring species, Aedes albopictus, Ae. aegypti, and Culex quinquefasciatus, across environments with different ratios of animal and leaf detritus. We quantified the contribution of detritus to biomass using stable isotope analysis and measured tissue carbon and nitrogen concentrations among species and between the sexes. Development times were shorter and adults were heavier for Aedes in animal versus leaf-only environments, whereas Culex development times were invariant across detritus types. Aedes displayed similar survival across detritus types whereas C. quinquefasciatus showed decreased survival with increasing leaf detritus. All species had lower values of 15N and 13C in leaf-only detritus compared to animal, however, Aedes generally had lower tissue nitrogen compared to C. quinquefasciatus. There were no differences in the C:N ratio between male and female Aedes, however, Aedes were different than C. quinquefasciatus adults, with male C. quinquefasciatus significantly higher than females. Culex quinquefasciatus was homeostatic across detrital environments. These results allow us to hypothesize an underlying stoichiometric explanation for the variation in performance of different container species under similar

  1. Detrital zircon U-Pb geochronological and sedimentological study of the Simao Basin, Yunnan: Implications for the Early Cenozoic evolution of the Red River

    Science.gov (United States)

    Chen, Yi; Yan, Maodu; Fang, Xiaomin; Song, Chunhui; Zhang, Weilin; Zan, Jinbo; Zhang, Zhiguo; Li, Bingshuai; Yang, Yongpeng; Zhang, Dawen

    2017-10-01

    The paleo-Red River is suggested to have been a continental-scale drainage system connecting the Tibetan Plateau to the South China Sea. However, the evolution of the paleo-Red River is still under debate. This study presents new results from sedimentological analyses and detrital zircon U-Pb geochronologic data from fluvial sedimentary rocks of Paleocene to Oligocene age of the Simao Basin to constrain the nature of the paleo-drainage system of the Red River. The detrital zircon U-Pb results reveal multiple age groups at 190-240 Ma, 260-280 Ma, 450-540 Ma, 1700-1900 Ma and 2400-2600 Ma for the Paleocene to late Eocene Denghei Formation (Fm.), but only one conspicuous peak at 220-240 Ma for the late Eocene-Oligocene Mengla Fm. Provenance analyses illustrate that the former likely had source areas that included the Hoh-Xil, Songpan-Ganzi, northern Qiangtang, Yidun and western Yangtze Terranes, which are consistent with the catchments of the Upper and Lower Jinshajiang Segments, whereas the latter mainly transported material from a limited number of sources, such as the Lincang granitic intrusions west of the Simao Basin. Integrated with available detrital zircon U-Pb geochronologic and paleogeographic data, our study suggests the existence of a paleo-Red River during the Paleocene to late Eocene that was truncated and lost its northern sources after approximately 35 Ma, due to left-lateral strike-slip faulting of the Ailao Shan-Red River and clockwise rotation of the Lanping-Simao Terrane.

  2. Oxidation Characteristics and Electrical Properties of Doped Mn-Co Spinel Reaction Layer for Solid Oxide Fuel Cell Metal Interconnects

    Directory of Open Access Journals (Sweden)

    Pingyi Guo

    2018-01-01

    Full Text Available To prevent Cr poisoning of the cathode and to retain high conductivity during solid oxide fuel cell (SOFC operation, Cu or La doped Co-Mn coatings on a metallic interconnect is deposited and followed by oxidation at 750 °C. Microstructure and composition of coatings after preparation and oxidation is analyzed by X-ray diffraction (XRD and scanning electron microscopy (SEM. High energy micro arc alloying process, a low cost technique, is used to prepare Cu or La doped Co-Mn coatings with the metallurgical bond. When coatings oxidized at 750 °C in air for 20 h and 100 h, Co3O4 is the main oxide on the surface of Co-38Mn-2La and Co-40Mn coatings, and (Co,Mn3O4 spinel continues to grow with extended oxidation time. The outmost scales of Co-33Mn-17Cu are mainly composed of cubic MnCo2O4 spinel with Mn2O3 after oxidation for 20 h and 100 h. The average thickness of oxide coatings is about 60–70 μm after oxidation for 100 h, except that Co-40Mn oxide coatings are a little thicker. Area-specific resistance of Cu/La doped Co-Mn coatings are lower than that of Co-40Mn coating. (Mn,Co3O4/MnCo2O4 spinel layer is efficient at blocking the outward diffusion of chromium and iron.

  3. The variation of cationic microstructure in Mn-doped spinel ferrite during calcination and its effect on formaldehyde catalytic oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Xiaoliang [CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou 510640 (China); Liu, Peng [CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou 510640 (China); He, Hongping, E-mail: hehp@gig.ac.cn [CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou 510640 (China); Wei, Gaoling [Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Chen, Tianhu [School of Resources and Environmental Engineering, Hefei University of Technology, Hefei 230009 (China); Tan, Wei; Tan, Fuding [CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou 510640 (China); Zhu, Jianxi; Zhu, Runliang [CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou 510640 (China)

    2016-04-05

    Highlights: • Calcination causes the activity variation of Mn-doped ferrites for HCHO oxidation. • The variation of catalytic activity of ferrites by calcination is non-linear. • Mn enriches on the calcinated ferrite surface in the valence of +3 and +4. • The reduction temperature of surface Mn{sup 4+} species is well correlated to T50. - Abstract: In this study, a series of Mn substituted spinel ferrites calcinated at different temperatures were used as catalysts for the oxidation of formaldehyde (HCHO). X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and H{sub 2} temperature-programmed reduction were conducted to characterize the structure and physico-chemical properties of catalysts, which were affected by calcination in the range of 200–600 °C. Results show that all the ferrites were with spinel structure, and those calcinated in the range of 300–600 °C were in the phase of maghemite. The calcination changed the valence and distribution of Mn and Fe on the ferrite surface, and accordingly the reducibility of ferrites. The HCHO catalytic oxidation test showed that with the increase of calcination temperature, the activity was initially improved until 400 °C, but then decreased. The variation of HCHO conversion performance was well positively correlated to the variation of reduction temperature of surface Mn{sup 4+} species. The remarkable effect of calcination on the catalytic activity of Mn-doped spinel ferrites for HCHO oxidation was discussed in view of reaction mechanism and variations in cationic microstructure of Mn-doped ferrites.

  4. Compositional Variation of Chrome Spinels in the Ore-bearing Zones of the Kraka Ophiolite and the Chromitite Origin

    Directory of Open Access Journals (Sweden)

    D. E. Saveliev

    2017-07-01

    Full Text Available The article considers a chemical variation of accessory and ore-forming chrome spinels from the Kraka ultramafic massif at the different scales, from the deposit to the thin section. A correlation analysis of compositional and structural features of ultramafic rocks and ores was performed. The ultramafic rocks and chromitites in the studied massif show the distinct deformation structures and tectonite olivine fabric. A typical chemical gap (i.e. Cr#=Cr/(Cr+Al was observed between peridotite, on the one hand, and dunite and chromitite, on the other hand, on the scale of deposits and ore-bearing zones. The location and size of this gap depend on the type of deposit. The gap becomes wider from the disseminated tabular bodies to the typical podiform ones. It has been found that in the thin initial dunite veinlets in peridotite the chrome spinels chemistry changes gradually and there is no Cr# gap between peridotite and dunite. The dunite venlets show a strong olivine fabric, which is an evidence of their high-temperature plastic flow origin. It has been revealed that new chrome spinel grains previously formed as rods or needles and then coarsened. We explained this observation as the result of impurity segregation, coalescence and spheroidization induced by the plastic deformation of olivine. It is inferred that a solid crystal flow is the main requirement for the dunite and chromitite body formation in the Kraka ophiolite massif. In the solid stream, the mineral phase separation takes place. For example, olivine and orthopyroxene grains of parental peridotite separate from one another, and weaker (more mobile olivine grains form dunite bodies in which chromitite appears as a result of impurity segregation.

  5. The variation of cationic microstructure in Mn-doped spinel ferrite during calcination and its effect on formaldehyde catalytic oxidation

    International Nuclear Information System (INIS)

    Liang, Xiaoliang; Liu, Peng; He, Hongping; Wei, Gaoling; Chen, Tianhu; Tan, Wei; Tan, Fuding; Zhu, Jianxi; Zhu, Runliang

    2016-01-01

    Highlights: • Calcination causes the activity variation of Mn-doped ferrites for HCHO oxidation. • The variation of catalytic activity of ferrites by calcination is non-linear. • Mn enriches on the calcinated ferrite surface in the valence of +3 and +4. • The reduction temperature of surface Mn"4"+ species is well correlated to T50. - Abstract: In this study, a series of Mn substituted spinel ferrites calcinated at different temperatures were used as catalysts for the oxidation of formaldehyde (HCHO). X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and H_2 temperature-programmed reduction were conducted to characterize the structure and physico-chemical properties of catalysts, which were affected by calcination in the range of 200–600 °C. Results show that all the ferrites were with spinel structure, and those calcinated in the range of 300–600 °C were in the phase of maghemite. The calcination changed the valence and distribution of Mn and Fe on the ferrite surface, and accordingly the reducibility of ferrites. The HCHO catalytic oxidation test showed that with the increase of calcination temperature, the activity was initially improved until 400 °C, but then decreased. The variation of HCHO conversion performance was well positively correlated to the variation of reduction temperature of surface Mn"4"+ species. The remarkable effect of calcination on the catalytic activity of Mn-doped spinel ferrites for HCHO oxidation was discussed in view of reaction mechanism and variations in cationic microstructure of Mn-doped ferrites.

  6. Detrital fission-track-compositional signature of an orogenic chain-hinterland basin system: The case of the late Neogene Quaternary Valdelsa basin (Northern Apennines, Italy)

    Science.gov (United States)

    Balestrieri, M. L.; Benvenuti, M.; Tangocci, F.

    2013-05-01

    Detrital thermochronological data collected in syn-tectonic basin deposits are a promising tool for deciphering time and processes of the evolution of orogenic belts. Our study deals with the Valdelsa basin, one of the wider basins of central Tuscany, Italy. The Valdelsa basin is located at the rear of the Northern Apennines, a collisional orogen whose late Neogene Quaternary development is alternatively attributed to extensional and compressional regimes. These contrasting interpretations mostly rely on different reconstructions of the tectono-sedimentary evolution of several basins formed at the rear of the chain since the late Tortonian. Here, we explore the detrital thermochronological-compositional signature of tectonic and surface processes during the Valdelsa basin development. For this aim, detrital apatite fission-track analysis of 21 sand samples from the latest Messinian Gelasian fluvial to shallow marine basin deposits, has been accompanied by a clast composition analysis of 7 representative outcrops of the conglomerate facies. The grain-age distributions of the sediment samples are generally characterized by two distinct components, one younger peak (P1) varying between 5.5 ± 2.8 and 9.5 ± 1.0 Ma and one older peak (P2) varying from 15.0 ± 8.0 to 41.0 ± 10 Ma. By comparison with some bedrock ages obtained from the E-NE basin shoulder, we attributed the P2 peak to the Ligurian Units and the P1 peak to the Macigno Formation (Tuscan Units). These units are arranged one upon the other in the complex nappe pile forming the Northern Apennines orogen. While the gravel composition indicates a predominant feeding from the Ligurian units all along the sedimentary succession with a subordinate occurrence of Macigno pebbles slightly increasing upsection, the P1 peak is present even in the oldest collected sandy sediments. The early P1 occurrence reveals that the Macigno was exposed in the E-NE basin shoulder since at least the latest Messinian-early Zanclean

  7. Detrital Zircons From the Jack Hills and Mount Narryer, Western Australia: Geochronological, Morphological, and Geochemical Evidence for Diverse >4000 Ma Source Rocks

    Science.gov (United States)

    Crowley, J. L.; Myers, J. S.; Sylvester, P. J.; Cox, R. A.

    2004-05-01

    Detrital zircons from all major clastic units in the Jack Hills and Mount Narryer metasedimentary belts, Western Australia, were analyzed for morphology, internal zoning, inclusion mineralogy, age, and trace element concentrations (latter two obtained by laser-ablation microprobe ICPMS). The results show that zircons were derived from a wide diversity of rocks, including previously described, >4000 Ma grains that are older than any known terrestrial rocks. In three metaconglomerate samples from the western Jack Hills, 4200-3800 Ma zircons ("old grains") comprise 14% of the population, 3800-3600 Ma grains form only 2%, and 3550-3250 Ma zircons ("young grains") are dominant with a significant peak at 3380 Ma. Old and young grains are interpreted as being from similar rock types because they are indistinguishable in trace element concentrations, size (several hundred microns), morphology (subequant, typically fragmented), internal zoning (typically both oscillatory and sector), and U concentration (50-200 ppm). Many of these properties suggest an intermediate plutonic source, whereas an evolved granitic source was previously interpreted from rare-earth element and oxygen isotope data. Detrital zircons in quartzites and metaconglomerates at Mount Narryer differ significantly from zircons from the western Jack Hills. Old grains comprise only 3% (most of which are 4200-4100 Ma), 3800-3600 Ma zircons form 31%, and there are peaks at 3650, 3600, and 3500 Ma. Old and young grains have similar properties that suggest granitic sources, such as elongate prismatic morphology, oscillatory zoning, high U concentrations (100-600 ppm), and xenotime and monazite inclusions. Trace element concentrations are broadly similar to those in Jack Hills zircons, with notable exceptions being generally higher U, smaller Ce and Eu anomalies, and lower Nb/Ta. It is considered unlikely that Jack Hills zircons were derived from granitic gneisses that surround the metasedimentary belts because

  8. Lithium ion adsorptive properties of spinel-type manganese oxide obtained from MnOOH and Li2CO3

    International Nuclear Information System (INIS)

    Ooi, Kenta; Miyai, Yoshitaka; Katoh, Shunsaku; Abe, Mitsuo.

    1991-01-01

    Spinel-type manganese oxides were prepared by heating a mixture of MnOOH and Li 2 CO 3 (Li/Mn = 0.5) at different temperatures followed by an acid treatment with a HCl solution. Their adsorptive properties for alkali metal ions were investigated by measurement of distribution coefficient (Kd) and by pH titration. The adsorptive properties varied depending on the heating temperature. The sample obtained at 400degC showed the highest Li + adsorptivity from seawater. (author)

  9. Effect of the preparation method on the structural and catalytic properties of spinel cobalt-iron oxide

    Energy Technology Data Exchange (ETDEWEB)

    Hammiche-Bellal, Yasmina, E-mail: yasminahammiche@gmail.com [Laboratoire des Matériaux Catalytiques et Catalyse en Chimie Organique, Faculté de Chimie, USTHB, BP32 El Alia, Bab Ezzouar, 16111, Alger (Algeria); Djadoun, Amar [Laboratoire de Géophysique, FSTGAT, USTHB, BP32 El Alia, Bab Ezzouar, 16111, Alger (Algeria); Meddour-Boukhobza, Laaldja; Benadda, Amel [Laboratoire des Matériaux Catalytiques et Catalyse en Chimie Organique, Faculté de Chimie, USTHB, BP32 El Alia, Bab Ezzouar, 16111, Alger (Algeria); Auroux, Aline [Université Lyon 1, CNRS, UMR 5256, IRCELYON, Institut de Recherches sur la Catalyse et l' Environnement de Lyon, 2 Avenue Albert Einstein, F-69626, Villeurbanne (France); Berger, Marie-Hélène [Centre des Matériaux PIERRE-MARIE Fourt, UMR 7633, Paris (France); Mernache, Fateh [UDEC-CRND, COMENA, BP 43 Draria, 16050, Alger (Algeria)

    2016-07-01

    Spinel cobalt-iron oxide was synthesized by co-precipitation and hydrothermal routes. The effect of the co-precipitation experimental conditions, the calcination temperature and the hydrothermal synthesis time and temperature on the properties of the solids was studied. The prepared powders were evaluated as catalysts in the ethanol combustion reaction, and were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM/EDX), nitrogen adsorption–desorption isotherms (BET, BJH) and temperature programmed reduction (TPR) techniques. Using chloride salts as starting materials and sodium hydroxide as precipitating agent, the CoFe{sub 2}O{sub 4} prepared powders displayed a mesoporous structure with a pore distribution strongly dependent on the experimental conditions. A monophasic spinel phase in the case of the calcined solids was obtained while the hydrothermal process led to the formation of a mixture of single oxides in addition to the spinel phase. The variation of the crystallite size and the lattice parameter as a function of calcination temperature was similar, whereas this variation found to be irregular when the synthesis residence time in autoclave was increased. The hydrothermally treated solids show the best catalytic performance in the total oxidation of ethanol. The catalytic behavior was correlated with the crystallite size and the reduction temperature of cobalt species determined by the TPR analysis. - Highlights: • Pure CoFe{sub 2}O{sub 4} phase is obtained by co-precipitation method at calcination temperatures 500–900 °C. • The temperature of co-precipitation procedure influences strongly the growth of the solids during the calcination step. • The hydrothermal synthesis gives a mixture of oxides; CoFe{sub 2}O{sub 4} is the predominant phase. • The CoFe{sub 2}O{sub 4} spinel showed a good catalytic reactivity in the ethanol combustion reaction. • The catalysts prepared by hydrothermal process are more reactive and

  10. IN-SITU SYNCHROTRON PXRD STUDY OF SPINEL TYPE LiMn2O4 NANOCRYSTAL FORMATION

    DEFF Research Database (Denmark)

    Birgisson, Steinar; Jensen, Kirsten Marie Ørnsbjerg; Christiansen, Troels Lindahl

    Many solvothermal reactions have a great potential for environmentally friendly and easily scalable way for producing nanocrystalline materials on an industrial scale. Here we study hydrothermal formation of spinel LiMn2O4 which is a well-known cathode material for Li-ion batteries. The LiMn2O4...... nanoparticles are formed by reducing KMnO4 in an aqueous solution containing Li-ions. The reducing agent is an alcohol (here ethanol) and the reaction takes place under high pressure and temperature. The LiMn2O4 nanocrystals are unstable towards further reduction to Mn3O4 nanocrystals. Proposed reaction route...

  11. Atomic Structure of a Spinel-like Transition Al2O3 (100) Surface

    DEFF Research Database (Denmark)

    Jensen, Thomas Nørregaard; Meinander, Kristoffer; Helveg, Stig

    2014-01-01

    We study a crystalline epitaxial alumina thin film with the characteristics of a spinel-type transition Al2O3(100) surface by using atom-resolved noncontact atomic force microscopy and density functional theory. It is shown that the films are terminated by an Al-O layer rich in Al vacancies......, exhibiting a strong preference for surface hydroxyl group formation in two configurations. The transition alumina films are crystalline and perfectly stable in ambient atmospheres, a quality which is expected to open the door to new fundamental studies of the surfaces of transition aluminas....

  12. Comparative Study of Optical and Magneto-Optical Properties of Normal, Disordered and Inverse Spinel Type Oxides

    OpenAIRE

    Zviagin, Vitaly; Richter, Peter; Böntgen, Tammo; Lorenz, Michael; Ziese, Michael; Zahn, Dietrich R. T.; Salvan, Georgeta; Grundmann, Marius; Schmidt-Grund, Rüdiger

    2015-01-01

    Co$_3$O$_4$, ZnFe$_2$O$_4$, CoFe$_2$O$_4$, ZnCo$_2$O$_4$, and Fe$_3$O$_4$ thin films were fabricated by pulsed laser deposition at high and low temperatures resulting in crystalline single-phase normal, inverse, as well as disordered spinel oxide thin films with smooth surface morphology. The dielectric function, determined by spectroscopic ellipsometry in a wide spectral range from 0.5 eV to 8.5 eV, is compared with the magneto-optical response of the dielectric tensor, investigated by magne...

  13. Multiple Nebular Gas Reservoirs Recorded by Oxygen Isotope Variation in a Spinel-rich CAI in CO3 MIL 090019

    Science.gov (United States)

    Simon, J. I.; Simon, S. B.; Nguyen, A. N.; Ross, D. K.; Messenger, S.

    2017-01-01

    We conducted NanoSIMS O-isotopic imaging of a primitive spinel-rich CAI spherule (27-2) from the MIL 090019 CO3 chondrite. Inclusions such as 27-2 are proposed to record inner nebula processes during an epoch of rapid solar nebula evolution. Mineralogical and textural analyses suggest that this CAI formed by high temperature reactions, partial melting, and condensation. This CAI exhibits radial O-isotopic heterogeneity among multiple occurrences of the same mineral, reflecting interactions with distinct nebular O-isotopic reservoirs.

  14. Allogenic and Autogenic Signals in the Detrital Zircon U-Pb Record of the Deep-Sea Bengal Fan

    Science.gov (United States)

    Blum, M. D.; Rogers, K. G.; Gleason, J. D.; Najman, Y.

    2017-12-01

    The Himalayan-sourced Ganges-Brahmaputra river system and the deep-sea Bengal Fan represent Earth's largest sediment-dispersal system. This presentation summarizes a new detrital zircon U-Pb (DZ) provenance record from the Bengal Fan from cores collected during IODP Expedition 354, with coring sites located 1350 km downdip from the shelf margin. Each of our 15 samples were collected from medium- to fine-grained turbidite sand and, based on shipboard biostratigraphic analyses, our samples are late Miocene to late Pleistocene in age. Each sample was analyzed by LA-ICPMS at the Arizona Laserchron facility, with an average of n=270 concordant U-Pb ages per sample. Our goals are to use these data to evaluate the influence of allogenic controls vs. autogenic processes on signal propagation from source-to-sink. At the first order, large-scale sediment transfer to the Bengal Fan clearly records the strong tectonic and climatic forcing associated with the Himalayas and Ganges-Brahmaputra system: after up to 2500 km of river transport, and 1350 km of transport in turbidity currents, the DZ record faithfully represents Himalayan source terrains. The sand-rich turbidite part of the record is nevertheless biased towards glacial periods when rivers extended across the shelf in response to climate-forced sea-level fall, and discharged directly to slope canyons. However, only part of the Bengal Fan DZ record represents either the Ganges or the Brahmaputra, with most samples representing varying degrees of mixing of sediments from the two systems: this mixing, or the lack thereof, represents the signal of autogenic avulsions on the delta plain that result in the two river systems delivering sediment separately to the shelf margin, or together as they do today. Within the allogenic framework established by tectonic processes, the climatic system, and global climate-forced sea-level change, the DZ U-Pb record of sediment mixing or the lack thereof provides a fingerprint of autogenic

  15. Early to Middle Jurassic tectonic evolution of the Bogda Mountains, Northwest China: Evidence from sedimentology and detrital zircon geochronology

    Science.gov (United States)

    Ji, Hongjie; Tao, Huifei; Wang, Qi; Qiu, Zhen; Ma, Dongxu; Qiu, Junli; Liao, Peng

    2018-03-01

    The Bogda Mountains, as an important intracontinental orogenic belt, are situated in the southern part of the Central Asian Orogenic Belt (CAOB), and are a key area for understanding the Mesozoic evolution of the CAOB. However, the tectonic evolution of the Bogda Mountains remains controversial during the Mesozoic Era, especially the Early to Middle Jurassic Periods. The successive Lower to Middle Jurassic strata are well preserved and exposed along the northern flank of the Western Bogda Mountains and record the uplift processes of the Bogda Mountains. In this study, we analysed sedimentary facies combined with detrital zircon U-Pb geochronology at five sections of Lower to Middle Jurassic strata to detect the tectonic evolution and changes of provenance in the Bogda area. During Early to Middle Jurassic times, the fluvial, deltaic and lacustrine environments dominated in the western section of the Bogda area. The existence of Early Triassic peak age indicates that the Bogda Mountains did not experience uplift during the period of early Badaowan Formation deposition. The Early Triassic to Late Permian granitoid plutons and Carboniferous volcanic rocks from the Barkol and Santanghu areas were the main provenances. The significant change in the U-Pb age spectrum implies that the Eastern Bogda Mountains initiated uplift in the period of late Badaowan Formation deposition, and the Eastern Junggar Basin and the Turpan-Hami Basin were partially partitioned. The Eastern Bogda Mountains gradually became the major provenance. From the period of early Sangonghe to early Toutunhe Formations deposition, the provenance of the sediments and basin-range frame were similar to that of late Badaowan. However, the Eastern Bogda Mountains suffered intermittent uplift three times, and successive denudation. The uplifts respectively happened in early Sangonghe, late Sangonghe to early Xishanyao, and late Xishanyao to early Toutunhe. During the deposition stage of Toutunhe Formation, a

  16. Specific heat and magnetic properties of single-crystalline ZnxDyyCrzSe4 spinels

    International Nuclear Information System (INIS)

    Jendrzejewska, Izabela; Groń, Tadeusz; Maciążek, Ewa; Duda, Henryk; Kubisztal, Marian; Ślebarski, Andrzej; Pietrasik, Ewa; Fijałkowski, Marcin

    2016-01-01

    The crystal structure, magnetic isotherm, magnetic susceptibility, electrical conductivity and specific heat measurements for single-crystalline Zn x Dy y Cr z Se 4 (where x+y+z≈3) spinels are presented. A semiconducting behavior with the activation energy of 0.53 eV, an antiferromagnetic order with a Néel temperature T N =22 K and a strong ferromagnetic exchange evidenced by a positive Curie–Weiss temperature θ=79, 71 and 70 K with increasing Dy-content in the sequence 0.05, 0.13 and 0.19 were established. Below T N the magnetic field dependence of magnetization, M(H), shows two peaks at critical fields H c1 and H c2 . The values of H c1 decrease slightly with temperature, especially for the larger Dy-content, while the values of H c2 drop rapidly with temperature. The magnetic contribution to the specific heat displays a sharp peak at T N , which is strongly shifted to much lower temperatures in the applied magnetic fields. Similar behavior was found for the temperature dependence of the specific heat C(T) plotted as C(T)/T vs. T. The value of the magnetic and phonon contribution to the entropy at T N and at H=0 is only ∼4.8, ∼4.4 and ∼4.2 J mol −1 K −1 /Cr 3+ for y=0.05, 0.13 and 0.19, respectively, much lower than the average magnetic contribution S m =(z/2)Rln(2S+1)=12.33 J mol −1 K −1 /Cr 3+ calculated for Cr 3+ ion with S=3/2, as the dysprosium one is paramagnetic. - Highlights: • Dy-substitution does not affect the Cr 3+ 3d 3 electronic configuration and AFM order. • The larger Dy-content, the smaller FM short-range interactions. • The magnetic and phonon contribution to the entropy decreases as Dy-content increases.

  17. Quantum dot sensitized solar cells fabricated by means of a novel inorganic spinel nanoparticle

    Science.gov (United States)

    Jalali-Moghadam, Elnaz; Shariatinia, Zahra

    2018-05-01

    A novel inorganic spinel compound with formula Zn0.5184La0.7859Ce0.3994Al1.0026O4 (ZLCA) was synthesized by the gel combustion method and its exact formula was approved by the XPS analysis. The TEM image exhibited that the ZLCA NPs were very fine, spherical and slightly agglomerated particles with their particle size changed in the range of ∼5-20 nm. Then, several quantum dot-sensitized solar cells (QDSSCs) were fabricated using this new compound which was doped into the TiO2 pastes of photoanodes and subsequently the CdS, CdS and ZnS layers were deposited on the ZLCA-doped TiO2 layer by the SILAR and the CBD methods. Results indicated that the photovoltaic parameters of the optimized cell (η = 3.50%, JSC = 11.690 mA·cm-2) were boosted compared with those of the reference cell which was free of ZLCA NPs (η = 2.14%, JSC = 7.075 mA·cm-2) indicating rather high improvements of approximately 64 and 65% in the efficiency and short-circuit current density, respectively. The UV-Vis absorption spectra of all nanocomposite photoanodes revealed broad absorption bands between ∼320 and 600 nm. The lowest intensity of the photoluminescence peak for the CdSe cell fabricated using 0.6%ZLCA suggested that it had the least charge recombination and the easiest electron transfer which was confirmed by the J-V and efficiency results. The Electrochemical impedance spectra (EIS) illustrated that the charge transfer resistances (RCT) of cells were dropped by addition of the ZLCA into the TiO2 compared with that of the cell made without using ZLCA NPs. The RCT resistance was 1900 Ω for pure TiO2 but it was decreased to 81.6 Ω in the optimized cell containing 0.6%wt of ZLCA. Thus, it could be decided that doping 0.6%wt ZLCA was appropriate to attain suitable photocurrent efficiency for the QDSSCs because it was used in a minimum quantity to accelerate the electron transport, decrease the recombination and increase the cell efficiency.

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

    Science.gov (United States)

    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.

  19. Solution-combustion synthesized aluminium-doped spinel (LiAl(subx)Mn(sub2-x)O(sub4) as a high-performance lithium-ion battery cathode material

    CSIR Research Space (South Africa)

    Kebede, MA

    2015-06-01

    Full Text Available High-performing (LiAl(subx)Mn(sub2-x)O(sub4) (x = 0, 0.125, 0.25, 0.375, and 0.5) spinel cathode materials for lithium-ion battery were developed using a solution combustion method. The as-synthesized cathode materials have spinel cubic structure...

  20. Microwave-assisted synthesis of high-voltage nanostructured LiMn1.5Ni0.5O4 spinel: tuning the Mn3+ content and electrochemical performance

    CSIR Research Space (South Africa)

    Jafta, CJ

    2013-08-01

    Full Text Available on the Mn3+ concentration and electrochemistry of the LiMn1.5Ni0.5O4 spinel. It is shown that microwave is capable of tuning the Mn3+ content of the spinel for enhanced electrochemical performance (high capacity, high capacity retention, excellent rate...

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

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Jianming; Yan, Pengfei; Kan, Wang Hay; Wang, Chong M.; Manthiram, Arumugam

    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 discharging 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.

  2. Synthesis and characterization of mesoporous spinel NiCo2O4 using surfactant-assembled dispersion for asymmetric supercapacitors

    Science.gov (United States)

    Hsu, Chun-Tsung; Hu, Chi-Chang

    2013-11-01

    A simple and scalable process has been developed for synthesizing spinel NiCo2O4 nanocrystals through a thermal decomposition method. The introduction of hexadecyltrimethylammonium bromide (CTAB, (C16H33)N(CH3)3Br) into precursor solutions significantly enhances the homogeneity and porosity of spinel NiCo2O4. The porosity and high specific surface area of NiCo2O4 preserves the brilliant pseudo-capacitive performances due to providing smooth paths for electrolyte penetration and ion diffusion into inner active sites. Morphologies and microstructures of the active materials are examined by transmission electron microscopic (TEM) and X-ray diffraction (XRD) analyses. Thermogravimetric analysis (TGA) is used to evaluate the thermal properties of precursor solutions. The electrochemical performances of NiCo2O4 are systematically characterized by cyclic voltammetry and charge-discharge tests. Asymmetric supercapacitors are assembled with these brilliant binary oxides as the positive electrode and activated carbon as the negative electrode. The highly porous NiCo2O4 exhibits superior capacitive performances, i.e., high specific capacitance (764 F g-1 at 2 mV s-1) and long cycle life.

  3. The characterization of Co xZn7-xSb2O12 spinel obtained by the pechini method

    Directory of Open Access Journals (Sweden)

    Deiby Santos Gouveia

    2005-06-01

    Full Text Available Oxides with spinel structures have been studied for many decades as they have been used in a variety of applications like pigments and refractories. They have also been used as a model structure to evaluate the relative stability of ions in octahedral and tetrahedral sites. Zinc- antimony spinels (Zn7Sb2O12 were synthesized by the Pechini method and the cation Zn2+ was substituted by Co2+, taking into consideration the stoichiometry of Co xZn7-xSb2O12 (x = 0 - 7. Characterization of the thermal properties of pyrolyzed powders was carried out with a TG/DTA analyzer, and mass losses were determined as a function of the cobalt content in the resin. The powders were calcined at temperatures in the range 600 to 1000 °C and characterized by XRD, BET and IR spectroscopy. Maximum cristalinity was obtained in powders calcined at 1000 °C. Materials with x = 5 - 7 revealed the presence of a secondary phase (Co, ZnSb2O6. Infrared analysis facilitated in the determination of the possible sites of Zn2+, Co2+ and Sb2+ ions in the lattice.

  4. The effect of dolomite type and Al2O3 content on the phase composition in aluminous cements containing spinel

    Directory of Open Access Journals (Sweden)

    R. Naghizadeh

    2011-06-01

    Full Text Available In this paper, the effect of dolomite type and Al2O3 content on the phase composition in aluminous cements containing MA spinel is investigated. For this reason, the raw and calcined dolomites are used as raw materials along with calcined alumina in the preparation of the cement. Then, different compositions are prepared at 1350°C using the sintering method and their mineralogical compositions are investigated using the diffractometric technique. Also, their microstructures arre evaluated. The results indicate that raw materials used have great effect on the type and amount of formed phases in cement composition. Independently of the dolomite type used, a mixed phase product consisting of spinel accompanied by CA and CA2 is obtained. The content of CA phase in the cement composition is decreased with increasing of Al2O3 in the raw materials composition. On the other hand, the content of CA2 phase is increased with the addition of Al2O3. In addition, the results show that the formation of C12A7 is favored by use of calcined dolomite.

  5. Study of electron transition energies between anions and cations in spinel ferrites using differential UV–vis absorption spectra

    International Nuclear Information System (INIS)

    Xue, L.C.; Wu, L.Q.; Li, S.Q.; Li, Z.Z.; Tang, G.D.; Qi, W.H.; Ge, X.S.; Ding, L.L.

    2016-01-01

    It is very important to determine electron transition energies (E_t_r) between anions and different cations in order to understand the electrical transport and magnetic properties of a material. Many authors have analyzed UV–vis absorption spectra using the curve (αhν)"2 vs E, where α is the absorption coefficient and E(=hν) is the photon energy. Such an approach can give only two band gap energies for spinel ferrites. In this paper, using differential UV–vis absorption spectra, dα/dE vs E, we have obtained electron transition energies (E_t_r) between the anions and cations, Fe"2"+ and Fe"3"+ at the (A) and [B] sites and Ni"2"+ at the [B] sites for the (A)[B]_2O_4 spinel ferrite samples Co_xNi_0_._7_−_xFe_2_._3O_4 (0.0≤x≤0.3), Cr_xNi_0_._7Fe_2_._3_−_xO_4 (0.0≤x≤0.3) and Fe_3O_4. We suggest that the differential UV–vis absorption spectra should be accepted as a general analysis method for determining electron transition energies between anions and cations.

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

    Science.gov (United States)

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

    2014-01-01

    Cr is a ubiquitous and relatively abundant minor element in basaltic, planetary magmas. At the reduced oxidation states (spinel, clinopyroxene, and olivine. However, understanding the Cr valence in quenched melts has historically been plagued with analytical issues, and only recently has reliable methodology for quantifying Cr valence in quenched melts been developed. Despite this substantial difficulty, the pioneering works of Hanson and Jones and Berry and O'Neill provided important insights into the oxidation state of Cr in in silicate melts. Here we present a series of 1-bar gas mixing experiments performed with a Fe-rich basaltic melt in which have determined the Cr redox ratio of the melt at over a range of fO2 values by measuring this quantity in olivine with X-ray Absorption Near Edge Spectroscopy (XANES). The measured Cr redox ratio of the olivine phenocrysts can be readily converted to the ratio present in the conjugate melt via the ratio of crystal-liquid partition coefficients for Cr3+ and Cr2+. We have applied these results to modeling Cr spinel stability and Cr redox ratios in a primitive, iron-rich martian basalt.

  7. Incorporation of zinc for fabrication of low-cost spinel-based composite ceramic membrane support to achieve its stabilization.

    Science.gov (United States)

    Li, Lingling; Dong, Xinfa; Dong, Yingchao; Zhu, Li; You, Sheng-Jie; Wang, Ya-Fen

    2015-04-28

    In order to reduce environment risk of zinc, a spinel-based porous membrane support was prepared by the high-temperature reaction of zinc and bauxite mineral. The phase evolution process, shrinkage, porosity, mechanical property, pore size distribution, gas permeation flux and microstructure were systematically studied. The XRD results, based on a Zn/Al stoichiometric composition of 1/2, show a formation of ZnAl2O4 structure starting from 1000°C and then accomplished at 1300°C. For spinel-based composite membrane, shrinkage and porosity are mainly influenced by a combination of an expansion induced by ZnAl2O4 formation and a general densification due to amorphous liquid SiO2. The highest porosity, as high as 44%, is observed in ZnAl4 membrane support among all the investigated compositions. Compared with pure bauxite (Al), ZnAl4 composite membrane support is reinforced by ZnAl2O4 phase and inter-locked mullite crystals, which is proved by the empirical strength-porosity relationships. Also, an increase in average pore diameter and gas flux can be observed in ZnAl4. A prolonged leaching experiment reveals the zinc can be successfully incorporated into ceramic membrane support via formation of ZnAl2O4, which has substantially better resistance toward acidic attack. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Ab initio calculation of the electronic structure and spectroscopic properties of spinel γ-Sn3N4

    International Nuclear Information System (INIS)

    Ching, W. Y.; Rulis, Paul

    2006-01-01

    The electronic structure and physical properties of γ-Sn 3 N 4 in the spinel structure are investigated by first-principles calculations. The calculated band structure, electronic bonding, and optical properties are compared with two well-studied spinel nitrides γ-Si 3 N 4 and γ-Ge 3 N 4 . γ-Sn 3 N 4 is a semiconductor with a direct band gap of 1.40 eV and an attractive small electron effective mass of 0.17. Its optical properties are different from that of γ-Si 3 N 4 and γ-Ge 3 N 4 because of the difference in the conduction band minimum. The Sn K, Sn L 3 , Sn M 5 , and N K edges of the x-ray-absorption near-edge structure spectra in γ-Sn 3 N 4 are calculated using a supercell approach and are found to be rich in structures. These spectra are discussed in the context of the electronic structure of the unoccupied conduction band in the presence of the electron core-hole interaction. These calculated spectra can be used for the characterization of this novel compound

  9. First-principle investigation on stability of Co-doped spinel λ-Mn4-xCoxO8

    Institute of Scientific and Technical Information of China (English)

    HUANG Ke-long; CHEN Chun-an; LIU Su-qin; LUO Qiong; LIU Zhi-guo

    2007-01-01

    The mechanism of stability of Co-doped spinel λ-MnO2 that is referred to as spinel LiχMn2O4 (χ=0) was studied by using the first-principle calculation method. The total energy and formation enthalpy can be decreased remarkably due to the Co substation,resulting in a more stable structure of λ-MnχCr2-χO4. The bond order and DOS analysis were given in detail to explain the nature of stability improvement. The calculated results show that as the content of Co dopant increases, the bond order of Mn-O becomes larger and the peak of density of states around Fermi level shifts toward lower energy. The charge density distribution illustrates that the Mn-O bonding is ionic and partially covalent, and the covalent Mn-O bonding becomes stronger with the increase of Co dopant content. The results confirm that the Co-doping will enhance the stability of λ-MnO2 and hence improve the electrochemistry performance of LiχMn2O4.

  10. Cellulose-precursor synthesis of nanocrystalline Co0.5Cu0.5Fe2O4 spinel ferrites

    International Nuclear Information System (INIS)

    Ounnunkad, Kontad; Phanichphant, Sukon

    2012-01-01

    Highlights: ► Synthesis of spinel copper cobalt nanoferrite particles from a cellulose precursor for the first time. Control of nanosize and properties of nanoferrites can take place by varying the calcining temperature. The simple, low cost, easy cellulose process is a choice of nanoparticle processing technology. -- Abstract: Nanocrystalline Cu 0.5 Co 0.5 Fe 2 O 4 powders were prepared via a metal-cellulose precursor synthetic route. Cellulose was used as a fuel and a dispersing agent. The resulting precursors were calcined in the temperature range of 450–600 °C. The phase development of the samples was determined by using Fourier transform infrared (FT-IR) spectroscopy and powder X-ray diffraction (XRD). The field-dependent magnetizations of the nanopowders were measured by vibrating sample magnetometer (VSM). All XRD patterns are of a spinel ferrite with cubic symmetry. Microstructure of the ferrites showed irregular shapes and uniform particles with agglomeration. From XRD data, the crystallite sizes are in range of 16–42 nm. Saturation magnetization and coercivity increased with increasing calcining temperature due to enhancement of crystallinity and reduction of oxygen vacancies.

  11. Mesoporous Spinel Li4Ti5O12 Nanoparticles for High Rate Lithium-ion Battery Anodes

    International Nuclear Information System (INIS)

    Liu, Weijian; Shao, Dan; Luo, Guoen; Gao, Qiongzhi; Yan, Guangjie; He, Jiarong; Chen, Dongyang; Yu, Xiaoyuan; Fang, Yueping

    2014-01-01

    Graphical abstract: - Highlights: • Mesoporous Li 4 Ti 5 O 12 nanoparticles were prepared by a simple hydrothermal method. • The mesoporous Li 4 Ti 5 O 12 nanoparticles exhibited a diameter of 40 ± 5 nm and a pore-size distribution of 6 - 8 nm. • Cells with the mesoporous Li 4 Ti 5 O 12 anode showed excellent high rate electrochemical properties. - Abstract: Mesoporous spinel lithium titanate (Li 4 Ti 5 O 12 ) nanoparticles with the diameter of 40 ± 5 nm and the pore-size distribution of 6 - 8 nm were prepared by a simple hydrothermal method. As an anode material for lithium-ion batteries, these spinel Li 4 Ti 5 O 12 mesoporous nanoparticles exhibited desirable lithium storage properties with an initial discharge capacity of 176 mAh g −1 at 1 C rate and a capacity of approximately 145 mAh g −1 after 200 cycles at a high rate of 20 C. These excellent electrochemical properties at high charge/discharge rates are due to the mesoporous nano-scale structures with small size particles, uniform mesopores and larger electrode/electrolyte contact area, which shortens the diffusion path for both electrons and Li + ions, and offers more active sites for Li + insertion-extraction process

  12. Generation of Silicic Melts in the Early Izu-Bonin Arc Recorded by Detrital Zircons in Proximal Arc Volcaniclastic Rocks From the Philippine Sea

    Science.gov (United States)

    Barth, A. P.; Tani, K.; Meffre, S.; Wooden, J. L.; Coble, M. A.; Arculus, R. J.; Ishizuka, O.; Shukle, J. T.

    2017-10-01

    A 1.2 km thick Paleogene volcaniclastic section at International Ocean Discovery Program Site 351-U1438 preserves the deep-marine, proximal record of Izu-Bonin oceanic arc initiation, and volcano evolution along the Kyushu-Palau Ridge (KPR). Pb/U ages and trace element compositions of zircons recovered from volcaniclastic sandstones preserve a remarkable temporal record of juvenile island arc evolution. Pb/U ages ranging from 43 to 27 Ma are compatible with provenance in one or more active arc edifices of the northern KPR. The abundances of selected trace elements with high concentrations provide insight into the genesis of U1438 detrital zircon host melts, and represent useful indicators of both short and long-term variations in melt compositions in arc settings. The Site U1438 zircons span the compositional range between zircons from mid-ocean ridge gabbros and zircons from relatively enriched continental arcs, as predicted for melts in a primitive oceanic arc setting derived from a highly depleted mantle source. Melt zircon saturation temperatures and Ti-in-zircon thermometry suggest a provenance in relatively cool and silicic melts that evolved toward more Th and U-rich compositions with time. Th, U, and light rare earth element enrichments beginning about 35 Ma are consistent with detrital zircons recording development of regional arc asymmetry and selective trace element-enriched rear arc silicic melts as the juvenile Izu-Bonin arc evolved.

  13. Ages of detrital zircon from siliciclastic sucessions of the Brasilia belt, southern border of Sao Francisco craton: Implications for the evolution of proterozoic basins

    International Nuclear Information System (INIS)

    Valladares, C.S; Machado, N; Ribeiro, A.; Paciullo, F.V.P; Heilbron, M; Gauthier, G

    2001-01-01

    The determination of the age distribution of detrital zircon suites from greenschist and amphibolite facies metassedimentary rocks using 207 Pb/ 206 Pb laser-ablation inductively couple plasma mass spectometry (LA-ICPMS) was previously discussed by Machado and Gauthier (1996) and is an useful tool on determinating the ages interval of the source area. Although 207 Pb/ 206 Pb ages are, in principle, mimimum ages, Feng et al. (1993) and Machado and Gauthier (1996) showed that these ages are identical within error to U-Pb ages. The advantage of the method for sedimentary provenance studies is that the number of grains that can be analysed per day (ca. 50) on the same sample, providing a stastically meaningful age distribution. The most significant limitations of the method used in this work are the inability to yield reliable U-Pb values and the large analytical error of, at least, 1-10%. Neverthless, in provenance studies high precision are not required. In this work we report ages of detrital zircon from from lower greenschist metamorphic facies quartzites from the Proterozoic Sao Joao del Rei and Andrelandia basin successions. The data yield information about the ages of the source areas and provide an approach for constraining sedimentation ages in these basins (au)

  14. Evidence From Detrital Zircon U-Pb Analysis for Suturing of Pre-Mississippian Terranes in Arctic Alaska

    Science.gov (United States)

    Moore, T. E.; Potter, C. J.; O'Sullivan, P. B.; Aleinikoff, J. N.

    2007-12-01

    Detrital zircon U-Pb ages of pre-Mississippian sandstones were determined using SHRIMP and LA-ICPMS techniques for four key geographic parts of the Arctic Alaska terrane, northern Alaska. In the northeastern Brooks Range, a sample of quartz-rich turbidites from the Proterozoic Neroukpuk Quartzite yielded zircon ages ranging from 980 Ma to 2.9 Ga with clusters at 980-1100 Ma, 1680-1850 Ma and 2220-2660 Ma. Quartz and chert-bearing sandstone in the Tulageak well from Ordovician-Silurian argillite in basement beneath the North Slope yielded a broad spectrum of ages between 1.0 to 2.1 Ga and 2.8 Ga, including peaks at 1.0-1.2 and 1.5-1.7 Ga. Paleozoic zircons cluster at 390 and 440 Ma in this sample, indicating it is Devonian. Lithic sandstone from the Silurian Iviagik Group at Cape Dyer on the Lisburne Peninsula yielded a variety of ages from 450 to 1600 Ma, with a large peak at 475-600 Ma and several grains between 1.9 and 2.5 Ga. In contrast to the broad distributions of the latter two samples, zircons in metamorphosed Proterozoic-Cambrian(?) lithic sandstone from the an unnamed metagraywacke unit near Mt. Snowden on the Dalton Highway in the southern Brooks Range are largely 600-650 Ma with lesser clusters at 1050-1200 Ma and 1600-1900 Ga. Samples of quartz-rich Mississippian sandstone at the base of the unconformably overlying Mississippian to Triassic Ellesmerian sequence near three of the pre-Mississippian sample locations were also analyzed. Mississippian sandstones from the West Dease well (near the Tulageak well) and at Cape Dyer on the Lisburne Peninsula display zircon distributions similar to those found in the underlying pre-Mississippian samples, indicating the Mississippian clastic strata are locally derived and that the observed zircon distributions are representative of a broad area. However, the Mississippian Kekiktuk Conglomerate, which rests on the Neroukpuk Quartzite in the northeastern Brooks Range, also contains a variety of ages between 560 and

  15. What can zircon ages from the Jack Hills detrital zircon suite really tell us about Hadean geodynamics?

    Science.gov (United States)

    Whitehouse, Martin; Nemchin, Alexander

    2015-04-01

    As the only direct sample of the Hadean Earth, detrital zircon grains from the Jack Hills, Western Australia, have been the subject of intense investigation over the almost three decades since their discovery. A wide variety of geochemical and isotopic analyses of these grains, as well as their mineral inclusions, have been used variously to support two fundamentally different models for Hadean geodynamics: (i) Some form of (not necessarily modern-style) plate recycling generating felsic (continental-type?) crust at the boundaries [1, 2], or conversely (ii) the persistence of a long-lived, stagnant basaltic lid within which magmatism occurred as a result of internal temperature perturbations and/or impacts [3, 4], a model also generally consistent with a wide range of observations from post-Hadean geochemical reservoirs. Despite the considerable time and resources expended, the majority of these studies uncritically accept the individual U-Pb zircon ages, even though their veracity is key to many of the interpretations [5, 6]. We report here the results of an in-depth evaluation of all published (and new) U-Pb ages from the Jack Hills zircon suite in order to define age populations that can be used with a high degree of confidence in geodynamic interpretations. A notable problem in the interpretation of U-Pb data from ancient zircon grains (including those as young as the Neoarchean) is that disturbance of the systematics even several 100 Ma after crystallization causes data to spread along the concordia curve without becoming discernably discordant within the relatively large error bounds associated with U/Pb ages from in situ dating methods (e.g. SIMS). While 207Pb/206Pb ages are typically more precise, individually they provide no means to detect Pb-loss-induced younging. However, if two or preferably more analyses have been made in the same zircon growth zone, a reasonable evaluation of the possibility of Pb-loss can be made. In the available Jack Hills zircon

  16. Characterization of Li4Ti5O12 and LiMn2O4 spinel materials treated with aqueous acidic solutions

    NARCIS (Netherlands)

    Simon, D.R.

    2007-01-01

    In this thesis an investigation of two spinel materials, Li4Ti5O12 and LiMn2O4 used for Li-ion battery applications is performed interms of formation and reactivity towards acidic solutions. Subsequent characterizations such as structural, magnetic, chemical, and electrochemical characterizations

  17. Nature of the Electrochemical Properties of Sulphur Substituted LiMn2O4 Spinel Cathode Material Studied by Electrochemical Impedance Spectroscopy

    Directory of Open Access Journals (Sweden)

    Monika Bakierska

    2016-08-01

    Full Text Available In this work, nanostructured LiMn2O4 (LMO and LiMn2O3.99S0.01 (LMOS1 spinel cathode materials were comprehensively investigated in terms of electrochemical properties. For this purpose, electrochemical impedance spectroscopy (EIS measurements as a function of state of charge (SOC were conducted on a representative charge and discharge cycle. The changes in the electrochemical performance of the stoichiometric and sulphur-substituted lithium manganese oxide spinels were examined, and suggested explanations for the observed dependencies were given. A strong influence of sulphur introduction into the spinel structure on the chemical stability and electrochemical characteristic was observed. It was demonstrated that the significant improvement in coulombic efficiency and capacity retention of lithium cell with LMOS1 active material arises from a more stable solid electrolyte interphase (SEI layer. Based on EIS studies, the Li ion diffusion coefficients in the cathodes were estimated, and the influence of sulphur on Li+ diffusivity in the spinel structure was established. The obtained results support the assumption that sulphur substitution is an effective way to promote chemical stability and the electrochemical performance of LiMn2O4 cathode material.

  18. Study of Mn dissolution from LiMn{sub 2}O{sub 4} spinel electrodes using rotating ring-disk collection experiments

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Li-Fang; Ou, Chin-Ching; Striebel, Kathryn A.; Chen, Jenn-Shing

    2003-07-01

    The goal of this research was to measure Mn dissolution from a thin porous spinel LiMn{sub 2}O{sub 4} electrode by rotating ring-disk collection experiments. The amount of Mn dissolution from the spinel LiMn{sub 2}O{sub 4} electrode under various conditions was detected by potential step chronoamperometry. The concentration of dissolved Mn was found to increase with increasing cycle numbers and elevated temperature. The dissolved Mn was not dependent on disk rotation speed, which indicated that the Mn dissolution from the disk was under reaction control. The in situ monitoring of Mn dissolution from the spinel was carried out under various conditions. The ring currents exhibited maxima corresponding to the end-of-charge (EOC) and end-of-discharge (EOD), with the largest peak at EOC. The results suggest that the dissolution of Mn from spinel LiMn{sub 2}O{sub 4} occurs during charge/discharge cycling, especially in a charged state (at >4.1 V) and in a discharged state (at <3.1 V). The largest peak at EOC demonstrated that Mn dissolution took place mainly at the top of charge. At elevated temperatures, the ring cathodic currents were larger due to the increase of Mn dissolution rate.

  19. Formation of graphene-like 2D spinel MnCo2O4 and its lithium storage properties

    DEFF Research Database (Denmark)

    Huang, Guoyong; Guo, Xueyi; Cao, Xiao

    2017-01-01

    Two-dimensional (2D) materials fulfill the requirements for fast lithium storage due to the large exposed surface area and the open shortened path for Li insertion/extraction. Novel graphene-like 2D spinel MnCo2O4 powders have been synthesized, which inherit the morphology and structure of specia...

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

    Science.gov (United States)

    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.

  1. Immiscible melt droplets in garnet, as represented by ilmenite-magnetite-spinel spheroids in an eclogite-garnet peridotite association, Blanský les Granulite Massif, Czech Republic

    Czech Academy of Sciences Publication Activity Database

    Vrána, S.; Ackerman, Lukáš; Erban, V.; Halodová, P.

    2016-01-01

    Roč. 101, č. 1 (2016), s. 82-92 ISSN 0003-004X Institutional support: RVO:67985831 Keywords : eclogite * Fe-Ti-rich melt * garnet peridotite * garnetite * Ilmenite-magnetite-spinel * Invited Centennial article * Moldanubian Zone * UHP crystallization Subject RIV: DD - Geochemistry Impact factor: 2.021, year: 2016

  2. Two Contrasting Fabric Patterns of Olivine Observed in Garnet and Spinel Peridotite from a Mantle-derived Ultramafic Mass Enclosed in Felsic Granulite, the Moldanubian Zone, Czech Republic

    Czech Academy of Sciences Publication Activity Database

    Kamei, A.; Obata, M.; Michibayashi, K.; Hirajima, T.; Svojtka, Martin

    2010-01-01

    Roč. 51, 1/2 (2010), s. 101-123 ISSN 0022-3530 Institutional research plan: CEZ:AV0Z30130516 Keywords : garnet peridotite * spinel peridotite * olivine fabrics * Bohemian Massif Subject RIV: DB - Geology ; Mineralogy Impact factor: 3.842, year: 2010

  3. Electronic structure and physical properties of the spinel-type phase of BeP2N4 from all-electron density functional calculations

    International Nuclear Information System (INIS)

    Ching, W. Y.; Aryal, Sitram; Rulis, Paul; Schnick, Wolfgang

    2011-01-01

    Using density-functional-theory-based ab initio methods, the electronic structure and physical properties of the newly synthesized nitride BeP 2 N 4 with a phenakite-type structure and the predicted high-pressure spinel phase of BeP 2 N 4 are studied in detail. It is shown that both polymorphs are wide band-gap semiconductors with relatively small electron effective masses at the conduction-band minima. The spinel-type phase is more covalently bonded due to the increased number of P-N bonds for P at the octahedral sites. Calculations of mechanical properties indicate that the spinel-type polymorph is a promising superhard material with notably large bulk, shear, and Young's moduli. Also calculated are the Be K, P K, P L 3 , and N K edges of the electron energy-loss near-edge structure for both phases. They show marked differences because of the different local environments of the atoms in the two crystalline polymorphs. These differences will be very useful for the experimental identification of the products of high-pressure syntheses targeting the predicted spinel-type phase of BeP 2 N 4 .

  4. Structural and magnetic properties of Zn.sub.x./sub.Mn.sub.3-x./sub.O.sub.4./sub. spinels

    Czech Academy of Sciences Publication Activity Database

    Nádherný, L.; Maryško, Miroslav; Sedmidubský, D.; Martin, C.

    2016-01-01

    Roč. 413, Sep (2016), s. 89-96 ISSN 0304-8853 Institutional support: RVO:68378271 Keywords : Zn-Mn-O spinels * solid-state reaction * ferrimagnetic clusters * ZnO Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.630, year: 2016

  5. Constraints of detrital zircon U-Pb ages and Hf isotopes on the provenance of the Triassic Yidun Group and tectonic evolution of the Yidun Terrane, Eastern Tibet

    Science.gov (United States)

    Wang, Bai-Qiu; Wang, Wei; Chen, Wei Terry; Gao, Jian-Feng; Zhao, Xin-Fu; Yan, Dan-Ping; Zhou, Mei-Fu

    2013-05-01

    Eastern Tibet to the west of the Yangtze Block consists of the Yidun and Songpan-Ganzi Terranes, separated by the Ganzi-Litang suture zone. The Yidun Terrane includes the Zhongza Massif to the west, but the eastern part of the Yidun terrane is covered by the Yidun Group extending from the south (Shangri-La region) to the north (Changtai region). The Yidun Group, from the base upward, includes the Lieyi, Qugasi, Tumugou and Lanashan formations, which are mainly composed of volcanic-flysch successions. Based on the ages of volcanic interlayers and plutonic intrusions, depositional ages of the Qugasi and Tumugou formations are considered to be slightly older than 230 Ma and ca. 220-230 Ma respectively, which are prominently older than the previous estimates. The Yidun Group in the Changtai region has two prominent detrital zircon age peaks at 400-480 and 880-980 Ma and a minor peak at 2.45-2.50 Ga. This pattern suggests a detritus source from the Zhongza Massif, which was a micro-continent separated from the western Yangtze Block. In contrast, the Yidun Group in the Shangri-La region has various zircon age spectra among different formations. The Qugasi Formation in this region has detrital zircon age patterns similar to the Yidun Group in the Changtai region. However, the overlying Tumugou Formation shows distinct age peaks at Triassic (220-240 Ma), Neoproterozoic (~ 720-880 Ma), and Paleoproterozoic (~ 1.75-1.90 Ga). This age pattern is similar to that of the Xikang Group of the Songpan-Ganzi Terrane to the east. The detrital zircon age difference between the Qugasi and Tumugou formations in this region indicates a transition of sedimentary sources from the Zhongza Massif to locally distributed Triassic magmatic rocks at ~ 230 Ma. It is thus suggested that the Songpan-Ganzi Terrane may have been connected to or collided with the southern part of the Yidun Terrane during the Late Triassic, whereas the Songpan-Ganzi Terrane and the northern part of the Yidun Terrane

  6. The behavior of mineral inclusions during host decomposition. A SEM-STEM study of rutile inclusions at a natural propagating corundum-spinel interface.

    Science.gov (United States)

    Baldwin, Lisa; Li, Chen; Habler, Gerlinde; Abart, Rainer

    2017-04-01

    When two neighbor phases are not in chemical equilibrium, they may react and produce a reaction rim at their interface, separating the mutually incompatible phases. At constant P-T-X conditions, such a reaction will continue until one of the reactants is completely consumed. Reaction rim growth involves transfer of chemical components across the growing rim by long-range diffusion and localized interface reactions on either side of the growing rim. Consequently, the thickness of the reaction rim will be a function of time. Yet, in order to quantify and interpret such corona structures and to define a reaction rate law, the kinetics and mechanism of rim formation must be well constrained. In particular, the coupling between long-range diffusion, and interface reaction must be known. In this contribution we focus on potential complexities associated with interface reactions. Many natural minerals contain inclusions of other phases, which in turn may influence the reaction interface propagation kinetics during host phase decomposition (Ashby et al. 1969), as a propagating reaction interface dissipates more free energy when bypassing a mineral inclusion, resulting in a locally decelerated reaction rate. Here, we report results of a SEM-STEM study of the interface between natural rutile-bearing corundum and a polycrystalline ferromagnesio-aluminate spinel that grew topotactically with respect to the corundum precursor as a consequence of its reaction with FeO and MgO from basaltic melt. Electron Backscatter Diffraction (EBSD) crystal orientation imaging revealed that the spinel rim is polycrystalline and exhibits (111) twinning that is parallel to the corundum (0001) plane. The rutile inclusions in corundum are elongated perpendicular to the corundum [0001] axis and are randomly oriented in the (0001) plane. Furthermore, they follow an oscillatory grain size distribution zonation with grain sizes being either a few tens of nanometers, or about 500 to 800 nanometers in

  7. The effects of stress concentrations on reaction progress: an example from experimental growth of magnesio-aluminate spinel at corundum - periclase interfaces under uniaxial load

    Science.gov (United States)

    Jerabek, Petr; Abart, Rainer; Rybacki, Erik; Habler, Gerlinde

    2014-05-01

    The study aims to understand the reaction progress and chemical, microstructural and textural evolution of magnesio-aluminate spinel reaction rims formed at varying experimental settings (load, temperature and experiment duration). The spinel rims were grown at the contacts between periclase and corundum at temperatures of 1250°C to 1350°C and dry atmosphere, maintained by a constant argon gas flow, under uniaxial load of 0.026 and 0.26 kN per 9 mm2 of initial contact area. Single crystals of periclase with [100] and of corundum with [0001] perpendicular to the polished reaction interface as well as polycrystalline corundum were used as starting materials. Two loading procedures, immediate application of the load before heating and loading after the desired temperature had been reached, were used. An important byproduct of our experiments stemmed from the immediate application of the load, which led to deformation twinning and fracturing of corundum. This internal deformation of corundum disturbed the reaction interface and introduced loci of concentrated stress due to opening of void spaces in between the reactant crystals. Whenever cracks formed in the initial stages of an experiment, the void space opened immediately and no spinel formed along these interface segments. In the case of deformation twinning, the decreased rim thickness indicates later opening of void spaces. This is because next to twins, the reaction interface is characterized by tight physical contact on the one side and less tight contact on the other side of the twin individual. The tight contacts are characterized by enhanced reaction progress which together with the overall positive volume change of the reaction and limits on plasticity of the studied phases led to the opening of void spaces at places characterized by less tight contacts. The thickness variations are less pronounced in our high load (0.26 kN) experiments where periclase behaves plastically and to some extent reduces the

  8. Ab initio investigation of the thermodynamics of cation distribution and of the electronic and magnetic structures in the LiMn2O4 spinel

    Science.gov (United States)

    Santos-Carballal, David; Ngoepe, Phuti E.; de Leeuw, Nora H.

    2018-02-01

    The spinel-structured lithium manganese oxide (LiMn2O4 ) is a material currently used as cathode for secondary lithium-ion batteries, but whose properties are not yet fully understood. Here, we report a computational investigation of the inversion thermodynamics and electronic behavior of LiMn2O4 derived from spin-polarized density functional theory calculations with a Hubbard Hamiltonian and long-range dispersion corrections (DFT+U-D3). Based on the analysis of the configurational free energy, we have elucidated a partially inverse equilibrium cation distribution for the LiMn2O4 spinel. This equilibrium degree of inversion is rationalized in terms of the crystal field stabilization effects and the difference between the size of the cations. We compare the atomic charges with the oxidation numbers for each degree of inversion. We found segregation of the Mn charge once these ions occupy the tetrahedral and octahedral sites of the spinel. We have obtained the atomic projections of the electronic band structure and density of states, showing that the normal LiMn2O4 has half-metallic properties, while the fully inverse spinel is an insulator. This material is in the ferrimagnetic state for the inverse and partially inverse cation arrangement. The optimized lattice and oxygen parameters, as well as the equilibrium degree of inversion, are in agreement with the available experimental data. The partial equilibrium degree of inversion is important in the interpretation of the lithium ion migration and surface properties of the LiMn2O4 spinel.

  9. Origin of peraluminous minerals (corundum, spinel, and sapphirine) in a highly calcic anorthosite from the Sittampundi Layered Complex, Tamil Nadu, India

    Science.gov (United States)

    Karmakar, Shreya; Mukherjee, Subham; Sanyal, Sanjoy; Sengupta, Pulak

    2017-08-01

    The highly calcic anorthosite (An>95) from the Sittampundi Layered Complex (SLC) develops corundum, spinel and sapphirine that are hitherto not reported from any anorthositic rocks in the world. Petrological observations indicate the following sequence of mineral growth: plagioclasematrix → corundum; clinopyroxene → amphibole; corundum + amphibole → plagioclasecorona + spinel; and spinel + corundum → coronitic sapphirine. Phase relations in the CaO-Na2O-Al2O3-SiO2-H2O (CNASH) system suggest that corundum was presumably developed through vapour present incongruent melting of the highly calcic plagioclase during ultra-high temperature (UHT) metamorphism ( T ≥ 1000 °C, P ≥ 9 kbar). Topological constraints in parts of the Na2O-CaO-MgO-Al2O3-SiO2-H2O (NCMASH) system suggest that subsequent to the UHT metamorphism, aqueous fluid(s) permeated the rock and the assemblage corundum + amphibole + anorthite + clinozoisite was stabilized during high-pressure (HP) metamorphism (11 ± 2 kbar, 750 ± 50 °C). Constraints of the NCMASH topology and thermodynamic and textural modeling study suggest that coronitic plagioclase and spinel formed at the expense of corundum + amphibole during a steeply decompressive retrograde P- T path (7-8 kbar and 700-800 °C) in an open system. Textural modeling studies combined with chemical potential diagrams (μSiO2-μMgO) in the MASH system support the view that sapphirine also formed from due to silica and Mg metasomatism of the precursor spinel ± corundum, on the steeply decompressive retrograde P- T path, prior to onset of significant cooling of the SLC. Extremely channelized fluid flow and large positive solid volume change of the stoichiometrically balanced sapphirine forming reaction explains the localized growth of sapphirine.

  10. Atomic-deficient nanostructurization in water-sorption alumomagnesium spinel ceramics MgAl2O4

    Science.gov (United States)

    Ingram, A.

    2018-02-01

    Atomic-deficient nanostructurization in alumomagnesium MgAl2O4 ceramics sintered at 1100-1400 °C caused by water sorption are studied employing positron annihilation lifetime spectroscopy. Detected PAL spectra are reconstructed from unconstrained x4-term decomposition, and further transformed to x3-term form to be applicable for analysis with x3-x2-CDA (coupling decomposition algorithm). It is proved that water-immersion processes reduce positronium (Ps) decaying in large-size holes of ceramics (1.70-1.84 nm in radius) at the expense of enhanced trapping in tiny ( 0.2 nm in radius) Ps-traps. The water sorption is shown to be more pronounced in structurally imperfect ceramics sintered at T s = 1100-1200 °C due to irreversible transformations between constituting phases, while reversible physical-sorption processes are dominated in structurally uniform ceramics composed of main spinel phase.

  11. Magnetic ordering and electrical resistivity in Co0.2Zn0.8Fe2O4 spinel oxide

    International Nuclear Information System (INIS)

    Bhowmik, R.N.; Ranganathan, R.; Ghosh, B.; Kumar, S.; Chattopadhyay, S.

    2008-01-01

    We report the magnetic, Moessbauer spectroscopy and resistivity measurements in order to understand the electronic behaviour of bulk Co 0.2 Zn 0.8 Fe 2 O 4 spinel oxide. The effect of magnetic order on electrical behaviour is observed from the resistivity measurements in the absence and presence of magnetic field. The analysis of Moessbauer spectra suggests the absence of Fe 2+ ions in the system, which implies that complete hopping of charge carriers between localized Fe 3+ /Co 2+ and Fe 2+ /Co 3+ pair of ions in B sublattice is not the favourable mechanism in Co 0.2 Zn 0.8 Fe 2 O 4 . We suggest that electrical behaviour of the present sample may be consistent with a model of fractional charge transfer via Fe B 3+ -O 2- -Co B 2+ superexchange path

  12. The effect of bismuth on the structure, magnetic and electric properties of Co2MnO4 spinel multiferroic

    Science.gov (United States)

    Chouaya, H.; Smari, M.; Walha, I.; Dhahri, E.; Graça, M. P. F.; Valente, M. A.

    2018-04-01

    Mixed Co2Mn1-xBixO4 (x = 0, x = 0.05 and x = 0.1) samples were prepared by the sol-gel method using the citric acid route and characterized by various techniques. The X-ray diffraction (XRD) and Raman spectroscopic analyses confirmed the formation of inverse spinel cubic structure with Fd 3 ‾ m space group. The introduction of Bismuth (Bi) into Co2MnO4 did not modify the ferrimagnetic character of the parent compound Co2MnO4, whereas the field-cooled magnetizations MFC and the Curie temperature Tc decreased when increasing the Bi content. The electrical properties showed an activation energy (Ea) increase caused by the decrease of the double-exchange interaction following the substitution of Mn3+ by Bi3+. Eventually, the temperature coefficient of resistance (TCR) shows significant values for all samples can be investigated also as good candidates for bolometer applications.

  13. Magnetic properties of magnetic Co1-xMgxFe2O4 spinel by HTSE method

    International Nuclear Information System (INIS)

    Hamedoun, M.; Benyoussef, A.; Bousmina, M.

    2011-01-01

    Magnetic properties and exchange-coupling interactions of diluted magnetic spinels A 1-x A' x B 2 X 4 , where A and B are magnetic ions, namely Co 1-x Mg x Fe 2 O 4 , were investigated using the high-temperature series expansion method (HTSE) and the distribution method of magnetic cations in the range 0≤x≤1. The magnetic phase diagram and transition temperature versus dilution x were determined using the Pade approximants method along with HTSE. The critical exponent associated with the magnetic susceptibility γ was then deduced. The obtained results are in good agreement with experimental results and critical exponent values are consistent with those suggested by the universality hypothesis.

  14. Study of the crystallographic and magnetic properties of cubic manganite spinels NiMn2O4

    International Nuclear Information System (INIS)

    Boucher, B.

    1969-01-01

    We study the variation of the crystallographic properties (inversion degree, position parameters and short range order) of the cubic spinel Mn ν Ni 1-ν [Mn 2ν Ni ν ]O 4 , as a function of the thermal treatment applied to the sample. ν lies between 0. 74 and 0. 93; the slower the sample is cooled the more inverse it is. We show, in a molecular field theory, that a system of three magnetic sublattices can afford a 'star' configuration. We establish the conditions of stability of such a structure and its evolution as a function of temperature is foreseen. Neutron diffraction measurements show that the magnetic structure of NiMn 2 O 4 at 4.2 K is a 'star' configuration and that with increasing temperature it becomes a collinear structure in agreement with the theory. Furthermore, we find an anomaly in the value of specific heat at the transition temperature between 'star' and collinear structures. (author) [fr

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

    Science.gov (United States)

    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.

  16. Melt growth of zinc aluminate spinel single crystal by the micro-pulling down method under atmospheric pressure

    Science.gov (United States)

    Kamada, K.; Shoji, Y.; Yamaji, A.; Kurosawa, S.; Yokota, Yuui; Ohashi, Y.; Kim, Kyoung Jin; Ivanov, M.; Kochurikhin, V. V.; Yoshikawa, A.

    2018-06-01

    ZnAl2O4 crystals were grown using few starting compositions with various ZnO:AlO3/2 ratio using an Ir wire seed and Ir + Re crucible under ordinary pressure with Ar + 2%O2 atmosphere by the radiofrequency heating μ-PD furnace. The ZnAl2O4 spinel single crystal with 4 mm diameter could be successfully grown by the μ-PD method by optimization of starting melt composition considering with Zinc oxide evaporation. During 10 min of growth under normal pressure the formation of ZnAl2O4 single phase observed even at high vapor pressure of ZnO. The transmittance spectra and X-ray locking curve were measured for evaluating of grown ZnAl2O4 crystals quality.

  17. The reduction of Winterveld chrome spinel at 1300 degrees Celsius under an argon atmosphere in the presence of carbon

    International Nuclear Information System (INIS)

    Kuecuekkaragoz, C.S.; Algie, S.H.; Finn, C.W.P.

    1984-01-01

    The reduction of a mixture of particles of gangue-free spinel in the size range 106 to 90 μm and particles of graphite in the same size range was studied by the use of a recording thermobalance. The partially reduced material was analysed chemically, as well as by X-ray diffraction, optical microscopy, and electron-microprobe analysis. The reaction is shown to be sequential, the ferric iron being reduced to ferrous iron before a metallic reduction product appears. Almost one-half of the iron is reduced before the reduction of chromium becomes significant, and, by the time about one-half of the chromium has been reduced, almost no unreduced iron remains in the oxide. Carbon appears in the reduced material after the reduction of chromium has started. The carbon content rises as the reaction proceeds, and beyond the stage at which all the iron has been reduced, the reduced product is an iron-chromium carbide. The product is therefore in a state of near equilibrium with the partially reduced spinel. This indicates that, up to about 60 per cent reduction, the transfer of carbon to the oxide is a controlling factor in the reduction. This conclusion is supported by the observation that the reduced product is confined to the surface of the chromite particle, which retains its external shape while becoming progressively more porous as reduction proceeds. Under hydrogen, a metallic reduction product is formed within the internal pores as well as on the surface. The second half of the reduction proceeds at a reproducible decreasing rate that can be modelled on the basis of the diffusion of chromium from within the particle to the surface. The initial reduction rate is slow but accelerating, and is not reproducible. Further investigation of this stage of the reduction process is recommended

  18. Preparation and characterization of porous reduced graphene oxide based inverse spinel nickel ferrite nanocomposite for adsorption removal of radionuclides

    Energy Technology Data Exchange (ETDEWEB)

    Lingamdinne, Lakshmi Prasanna; Choi, Yu-Lim [Department of Environmental Engineering, Kwangwoon University, Seoul, 139-701 (Korea, Republic of); Kim, Im-Soon [Graduate School of Environmental Studies, Kwangwoon University, Seoul, 139-701 (Korea, Republic of); Yang, Jae-Kyu [Ingenium College of Liberal Arts, Kwangwoon University, Seoul, 139-701 (Korea, Republic of); Koduru, Janardhan Reddy, E-mail: reddyjchem@gmail.com [Graduate School of Environmental Studies, Kwangwoon University, Seoul, 139-701 (Korea, Republic of); Chang, Yoon-Young, E-mail: yychang@kw.ac.kr [Department of Environmental Engineering, Kwangwoon University, Seoul, 139-701 (Korea, Republic of)

    2017-03-15

    Highlights: • Novel porous Ferromagnetic, GONF and Superparamagnetic, rGONF preparation. • The nanosize particles GONF (41.14 nm) and rGONF (32.16 nm) preparation. • Adsorption mechanism and modeling developments for radionuclides. • Zeta potential and surface site density of nanocomposites for comparison. - Abstract: For the removal of uranium(VI) (U(VI)) and thorium(IV) (Th(IV)), graphene oxide based inverse spinel nickel ferrite (GONF) nanocomposite and reduced graphene oxide based inverse spinel nickel ferrite (rGONF) nanocomposite were prepared by co-precipitation of GO with nickel and iron salts in one pot. The spectral characterization analyses revealed that GONF and rGONF have a porous surface morphology with an average particle size of 41.41 nm and 32.16 nm, respectively. The magnetic property measurement system (MPMS) studies confirmed the formation of ferromagnetic GONF and superparamagnetic rGONF. The adsorption kinetics studies found that the pseudo-second-order kinetics was well tune to the U(VI) and Th(IV) adsorption. The results of adsorption isotherms showed that the adsorption of U(VI) and Th(IV) were due to the monolayer on homogeneous surface of the GONF and rGONF. The adsorptions of both U(VI) and Th(IV) were increased with increasing system temperature from 293 to 333 ± 2 K. The thermodynamic studies reveal that the U(VI) and Th(IV) adsorption onto GONF and rGONF was endothermic. GONF and rGONF, which could be separated by external magnetic field, were recycled and re-used for up to five cycles without any significant loss of adsorption capacity.

  19. About the Compatibility between High Voltage Spinel Cathode Materials and Solid Oxide Electrolytes as a Function of Temperature.

    Science.gov (United States)

    Miara, Lincoln; Windmüller, Anna; Tsai, Chih-Long; Richards, William D; Ma, Qianli; Uhlenbruck, Sven; Guillon, Olivier; Ceder, Gerbrand

    2016-10-12

    The reactivity of mixtures of high voltage spinel cathode materials Li 2 NiMn 3 O 8 , Li 2 FeMn 3 O 8 , and LiCoMnO 4 cosintered with Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 and Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 electrolytes is studied by thermal analysis using X-ray-diffraction and differential thermoanalysis and thermogravimetry coupled with mass spectrometry. The results are compared with predicted decomposition reactions from first-principles calculations. Decomposition of the mixtures begins at 600 °C, significantly lower than the decomposition temperature of any component, especially the electrolytes. For the cathode + Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 mixtures, lithium and oxygen from the electrolyte react with the cathodes to form highly stable Li 2 MnO 3 and then decompose to form stable and often insulating phases such as La 2 Zr 2 O 7 , La 2 O 3 , La 3 TaO 7 , TiO 2 , and LaMnO 3 which are likely to increase the interfacial impedance of a cathode composite. The decomposition reactions are identified with high fidelity by first-principles calculations. For the cathode + Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 mixtures, the Mn tends to oxidize to MnO 2 or Mn 2 O 3 , supplying lithium to the electrolyte for the formation of Li 3 PO 4 and metal phosphates such as AlPO 4 and LiMPO 4 (M = Mn, Ni). The results indicate that high temperature cosintering to form dense cathode composites between spinel cathodes and oxide electrolytes will produce high impedance interfacial products, complicating solid state battery manufacturing.

  20. Order-disorder transition in the complex lithium spinel Li2CoTi3O8

    International Nuclear Information System (INIS)

    Reeves, Nik; Pasero, Denis; West, Anthony R.

    2007-01-01

    Li 2 CoTi 3 O 8 has an ordered Li 2 BB' 3 O 8 spinel structure, space group P4 3 32, at room temperature with 3:1 ordering of Ti and Li on the octahedral sites, and Li, Co disordered over the tetrahedral site. Rietveld refinement of variable temperature neutron powder diffraction data has shown an order-disorder phase transition in Li 2 CoTi 3 O 8 which commences at ∼500 deg. C with Li and Co mixing on the tetrahedral and 4-fold octahedral sites and is complete at a first order structural discontinuity at ∼915 deg. C. The fraction of Ti on the 12-fold octahedral site exhibits a small decrease with increasing temperature, which may suggest that the disordering involves all three cations. Above 930 deg. C, the structure, space group Fd3-barm, has Li, Co and Ti sharing a single-octahedral site and Li, Co sharing a tetrahedral site, although Co still exhibits a preference for tetrahedral coordination. A labelling scheme for ordered and partially ordered 3:1 spinels is devised which focuses on the occupancy of the Li,B cations. - Graphical abstract: Rietveld refinement of variable temperature neutron powder diffraction data shows an order-disorder phase transition in Li 2 CoTi 3 O 8 commencing at ∼500 deg. C with Li,Co mixing on tetrahedral and octahedral sites. This becomes complete at a first-order structural discontinuity at ∼915 deg. C. Above 930 deg. C, the structure, space group Fd3-barm, has Li, Co and Ti sharing a single-octahedral site and Li, Co sharing a tetrahedral site

  1. Detrital mode and whole-rock geochemistry of the fluvial succession, Pishin Belt, Pakistan: Implications on provenance and source area weathering in periferal foreland basins

    DEFF Research Database (Denmark)

    Kasi, Aimal Khan; Kassi, Akhtar Muhammad; Friis, Henrik

    2016-01-01

    Detrital mode and geochemical composition of sandstones and mudstones of the Miocene Dasht Murgha Group (DMG) and Pliocene Malthanai Formation (MF) of the Pishin Belt, north-western Pakistan have been examined to identify their provenance and source area weathering. Sandstones of the Dasht Murgha...... Group and Malthanai Formation are lithic to sublith- arenites, rich in quartz, and metamorphic and sedimentary lithic fragments, indicating a recycled orogenic source. LmLvLs plots show that the Dasht Murgha Group is rich in sedimentary and metamorphic lithic fragments (Lm35Lv18Ls47), while samples...... of the Malthanai Formation are overwhelmingly rich in sedimentary fragments (Lm14Lv10Ls76). Eocene Nisai Formation and Oligocene Khojak Formation within the Pishin Belt were mainly providing the sedimentary/metasedimentary detritus. High content of monocrystalline quartz (DMG: 28.21%; MF: 30.7), and higher SiO2/Al...

  2. The earth's oldest known crust - A geochronological and geochemical study of 3900-4200 Ma old detrital zircons from Mt. Narryer and Jack Hills, Western Australia

    Science.gov (United States)

    Maas, Roland; Kinny, Peter D.; Williams, Ian S.; Froude, Derek O.; Compston, William

    1992-03-01

    Trace element characteristics were analyzed and inclusions were identified within a suite of pre-3.9 Ga detritral zircons from western Australia representing the earth's oldest-known minerals. A diversity of trace-element compositions was found, particularly in the REE compositions of the old Mt. Narryer zircons, implying a variety of source-rock compositions and hence, the presence of a differentiated crust in the earth 4.15-4.20 Ga ago. Comparisons drawn with data obtained from younger detrital zircons occurring within the same deposits indicate nothing unique about the chemical compositions of the old grains. A number of interelement covariations were observed among the analyzed grains which were independent of age and isotopic characteristics, most notably that occurring between Lu and Hf. A general positive correlation between total LREE and the U + Th contents is also apparent. The findings indicate an origin in felsic igneous rocks, which has implications for early-Archaean crustal evolution.

  3. PALEOTECTONIC AND PALEOGEOGRAPHIC CONDITIONS FOR THE ACCUMULATION OF THE LOWER RIPHEAN AI FORMATION IN THE BASHKIR UPLIFT (SOUTHERN URALS: THE TERRANECHRONE® DETRITAL ZIRCON STUDY

    Directory of Open Access Journals (Sweden)

    T. V. Romanyuk

    2018-01-01

    Full Text Available The TerraneChrone® (LA-ICP-MS technique has been applied to carry out an integrated study of detrital zircons in sandstones sampled from the basal horizons of the stratotypical Riphean sequence in the Southern Urals, specifically the Navysh and Chudin suites of the Ai Formation of the Burzyan Group in the Bashkir Uplift. The concentrations of trace elements in the detrital zircons suggest that the role of oceanic or marginal-marine complexes among the primary sources of zircons was insignificant, and show a better agreement with the intra-continental rather than passive-margin origin of the Riphean basin, whose basal levels are composed by the Ai Formation. The U/Pb ages of zircons from samples K13-206 and M08-16-1 are generally similar: the Paleoproterozoic zircons predominate (the dominant peaks are actually coincident, 2063 and 2055 Ma, and only a few grains of the Archean age are present. Despite the similar U/Pb ages of the detrital zircons, these two samples considerably differ in their Hf isotopic features and the concentrations of trace elements, which means that the zircons in the studied sandstones are of different geodynamic origin. The characteristics of these zircons can be explained by a model showing the Ai Formation in the Navysh graben that is a rift structure and a predecessor of the Kama-Belaya aulacogene in the inner Volga-Ural region of the Paleoproterozoic supercontinent Columbia. At the initial stage of rifting, the granitoid complexes with a lower total silicic acidity, which composed the graben walls, had been eroded; as a result of erosion, coarse clastic rocks accumulated within the Navysh graben and formed the Navysh suite. A specific “carbonatitic” complex containing zircons (about 2.0, 2.5, 2.85 and 3.6 Ga and the Palaeoarchean crustal material in the substrate of their parent rocks was also eroded. In the final stage of rifting, already at the initial stages of the development of the Kama-Belaya aulacogen

  4. Recycling of Amazonian detrital zircons in the Mixteco terrane, southern Mexico: Paleogeographic implications during Jurassic-Early Cretaceous and Paleogene times

    Science.gov (United States)

    Silva-Romo, Gilberto; Mendoza-Rosales, Claudia Cristina; Campos-Madrigal, Emiliano; Morales-Yáñez, Axél; de la Torre-González, Alam Israel; Nápoles-Valenzuela, Juan Ivan

    2018-04-01

    In the northeastern Mixteco terrane of southern Mexico, in the Ixcaquixtla-Atzumba region, the recycling of Amazonian detrital zircons records the paleogeography during the Mesozoic period in the context of the breakup of Pangea, a phenomenon that disarticulated the Sanozama-La Mora paleo-river. The clastic units of southern Mexico in the Ayuquila, Otlaltepec and Zapotitlán Mesozoic basins, as well as in the Atzumba Cenozoic basin, are characterized by detrital zircon contents with ages specific to the Amazonian craton, ranging between 3040 and 1278 Ma. The presence of zircons of Amazonian affinity suggests a provenance by recycling from carrier units such as the La Mora Formation or the Ayú Complex. In the area, the Ayú and Acatlán complexes form the Cosoltepec block, a paleogeographic element that during Early Cretaceous time acted as the divide between the slopes of the paleo-Gulf of Mexico and the paleo-Pacific Ocean. The sedimentological characteristics of the Jurassic-Cenozoic clastic successions in the Ixcaquixtla-Atzumba region denote relatively short transport in braided fluvial systems and alluvial fans. In this way, several basins are recognized around the Cosoltepec block. At the southeastern edge of the Cosoltepec block, the Ayuquila and Tecomazúchil formations accumulated in the Ayuquila continental basin on the paleo-Pacific Ocean slope. On the other hand, within the paleo-Gulf of Mexico slope, in the Otlaltepec continental basin, the Piedra Hueca and the Otlaltepec formations accumulated. The upper member of the Santa Lucía Formation accumulated in a transitional environment on the southwestern shoulder of the Zapotitlán basin, as well as on the paleo-Gulf of Mexico slope. In the Ayuquila basin, a marine transgression is recognized that advanced from south to north during the Late Jurassic. At the northeastern edge of the Cosoltepec block, we propose that the Santa Lucía formation attests to a transgression from the paleo-Gulf of Mexico

  5. Chemical, structural, and electrochemical characterization of 5 V spinel and complex layered oxide cathodes of lithium ion batteries

    Science.gov (United States)

    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

  6. Palynology and detrital zircon geochronology of the Carboniferous Fenestella Shale Formation of the Tethyan realm in Kashmir Himalaya: Implications for global correlation and floristic evolution

    Science.gov (United States)

    Agnihotri, Deepa; Pandita, Sundeep K.; Tewari, Rajni; Ram-Awatar; Linnemann, Ulf; Pillai, S. Suresh K.; Joshi, Arun; Gautam, Saurabh; Kumar, Kamlesh

    2018-05-01

    First palynological data, supplemented by detrital zircon U-Pb ages, from the Fenestella Shale Formation near the Gund Village in the Banihal area of Jammu and Kashmir State, India, provide new insights into the floristic evolution of Gondwana during the Late Palaeozoic, especially in India, from where the Carboniferous-Permian macro- and microfloral records are impoverished. We also present a first approach to the palynological correlation of the Carboniferous-Permian palynoassemblages described from the various Gondwana countries. The palynomorphs from the Fenestella Shale Formation are fairly well preserved and diversified and include 11 genera and 18 species. While the trilete spores and striate bisaccate pollen grains are scarce, monosaccate pollen taxa mainly - Parasaccites, Plicatipollenites and Potonieisporites are dominant. The assemblage is most similar to the Parasaccites korbaensis palynozone of the Lower Gondwana basins of the Indian peninsula and the Stage 2 palynozone of the late Carboniferous of east Australia. Besides, it is comparable with the known Carboniferous assemblages of Pakistan, Yemen and South America; Carboniferous-early Permian assemblages of South Africa and Permian assemblages of Antarctica. The sediment source of the siliciclastic shelf and delta deposits intercalated in the Fenestella Shale Formation is a hinterland in which Precambrian rocks dominantly were exposed and the Th-U ratios of detrital zircons suggest, that most rocks exposed on the erosion level in the hinterland had a felsic composition. The youngest U-Pb zircon age of the investigated fossiliferous strata is 329 ± 16 Ma (late Visean to early Serpukhovian), providing a maximum age of deposition of the studied succession. Based on the affinities of the palynofloral assemblage and earlier palaeontological records, a warm, temperate and arid climate has been inferred for the Fenestella Shale Formation.

  7. Pervasive remagnetization of detrital zircon host rocks in the Jack Hills, Western Australia and implications for records of the early geodynamo

    Science.gov (United States)

    Weiss, Benjamin P.; Maloof, Adam C.; Tailby, Nicholas; Ramezani, Jahandar; Fu, Roger R.; Hanus, Veronica; Trail, Dustin; Bruce Watson, E.; Harrison, T. Mark; Bowring, Samuel A.; Kirschvink, Joseph L.; Swanson-Hysell, Nicholas L.; Coe, Robert S.

    2015-11-01

    It currently is unknown when Earth's dynamo magnetic field originated. Paleomagnetic studies indicate that a field with an intensity similar to that of the present day existed 3.5 billion years ago (Ga). Detrital zircon crystals found in the Jack Hills of Western Australia are some of the very few samples known to substantially predate this time. With crystallization ages ranging from 3.0-4.38 Ga, these zircons might preserve a record of the missing first billion years of Earth's magnetic field history. However, a key unknown is the age and origin of magnetization in the Jack Hills zircons. The identification of >3.9 Ga (i.e., Hadean) field records requires first establishing that the zircons have avoided remagnetization since being deposited in quartz-rich conglomerates at 2.65-3.05 Ga. To address this issue, we have conducted paleomagnetic conglomerate, baked contact, and fold tests in combination with U-Pb geochronology to establish the timing of the metamorphic and alteration events and the peak temperatures experienced by the zircon host rocks. These tests include the first conglomerate test directly on the Hadean-zircon bearing conglomerate at Erawandoo Hill. Although we observed little evidence for remagnetization by recent lightning strikes, we found that the Hadean zircon-bearing rocks and surrounding region have been pervasively remagnetized, with the final major overprinting likely due to thermal and/or aqueous effects from the emplacement of the Warakurna large igneous province at ∼1070 million years ago (Ma). Although localized regions of the Jack Hills might have escaped complete remagnetization, there currently is no robust evidence for pre-depositional (>3.0 Ga) magnetization in the Jack Hills detrital zircons.

  8. Phanerozoic polyphase orogenies recorded in the northeastern Okcheon Belt, Korea from SHRIMP U-Pb detrital zircon and K-Ar illite geochronologies

    Science.gov (United States)

    Jang, Yirang; Kwon, Sanghoon; Song, Yungoo; Kim, Sung Won; Kwon, Yi Kyun; Yi, Keewook

    2018-05-01

    We present the SHRIMP U-Pb detrital zircon and K-Ar illite 1Md/1M and 2M1 ages, suggesting new insight into the Phanerozoic polyphase orogenies preserved in the northeastern Okcheon Belt, Korea since the initial basin formation during Neoproterozoic rifting through several successive contractional orogens. The U-Pb detrital zircon ages from the Early Paleozoic strata of the Taebaeksan Zone suggest a Cambrian maximum deposition age, and are supported by trilobite and conodont biostratigraphy. Although the age spectra from two sedimentary groups, the Yeongwol and Taebaek Groups, show similar continuous distributions from the Late Paleoproterozoic to Early Paleozoic ages, a Grenville-age hiatus (1.3-0.9 Ga) in the continuous stratigraphic sequence from the Taebaek Group suggests the existence of different peripheral clastic sources along rifted continental margin(s). In addition, we present the K-Ar illite 1Md/1M ages of the fault gouges, which confirm fault formation/reactivation during the Late Cretaceous to Early Paleogene (ca. 82-62 Ma) and the Early Miocene (ca. 20-18 Ma). The 2M1 illite ages, at least those younger than the host rock ages, provide episodes of deformation, metamorphism and hydrothermal effects related to the tectonic events during the Devonian (ca.410 Ma) and Permo-Triassic (ca. 285-240 Ma). These results indicate that the northeastern Okcheon Belt experienced polyphase orogenic events, namely the Okcheon (Middle Paleozoic), Songrim (Late Paleozoic to Early Mesozoic), Daebo (Middle Mesozoic) and Bulguksa (Late Mesozoic to Early Cenozoic) Orogenies, reflecting the Phanerozoic tectonic evolution of the Korean Peninsula along the East Asian continental margin.

  9. Proterozoic to Mesozoic evolution of North-West Africa and Peri-Gondwana microplates: Detrital zircon ages from Morocco and Canada

    Science.gov (United States)

    Marzoli, Andrea; Davies, Joshua H. F. L.; Youbi, Nasrrddine; Merle, Renaud; Dal Corso, Jacopo; Dunkley, Daniel J.; Fioretti, Anna Maria; Bellieni, Giuliano; Medina, Fida; Wotzlaw, Jörn-Frederik; McHone, Greg; Font, Eric; Bensalah, Mohamed Khalil

    2017-05-01

    The complex history of assemblage and disruption of continental plates surrounding the Atlantic Ocean is in part recorded by the distribution of detrital zircon ages entrained in continental sedimentary strata from Morocco (Central High Atlas and Argana basins) and Canada (Grand Manan Island, New Brunswick). Here we investigate detrital zircon from the latest Triassic (ca. 202 Ma) sedimentary strata directly underlying lava flows of the Central Atlantic magmatic province or interlayered within them. SHRIMP (Sensitive High-Resolution Ion MicroProbe) and LA-ICP-MS (Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry) U-Pb ages for zircon range from Paleozoic to Archean with a dominant Neoproterozoic peak, and significant amounts of ca. 2 Ga zircon. These ages suggest a prevailing West African (Gondwanan) provenance at all sampling sites. Notably, the Paleoproterozoic zircon population is particularly abundant in central Morocco, north of the High Atlas chain, suggesting the presence of Eburnean-aged rocks in this part of the country, which is consistent with recent geochronologic data from outcropping rocks. Minor amounts of late Mesoproterozoic and early Neoproterozoic zircon ages (ca. 1.1-0.9 Ga) in Moroccan samples are more difficult to interpret. A provenance from Avalonia or Amazonia, as proposed by previous studies is not supported by the age distributions observed here. An involvement of more distal source regions, possibly located in north-eastern Africa (Arabian Nubian Shield) would instead be possible. Paleozoic zircon ages are abundant in the Canadian sample, pointing to a significant contribution from Hercynian aged source rocks. Such a signal is nearly absent in the Moroccan samples, suggesting that zircon-bearing Hercynian granitic rocks of the Moroccan Meseta block were not yet outcropping at ca. 200 Ma. The only Moroccan samples that yield Paleozoic zircon ages are those interlayered within the CAMP lavas, suggesting an increased dismantling

  10. The Comparison of Detrital Zircon Ages to Point Count Provenance Analysis for the Pottsville Sandstone in the Northern Appalachian Foreland Basin Venango County, Pennsylvania

    Science.gov (United States)

    Loveday, S.; Harris, D. B.; Schiappa, T.; Pecha, M.

    2017-12-01

    The specific sources of sediments deposited in the Appalachian basin prior to and immediately following the Alleghenian orogeny has long been a topic of debate. Recent advances in U-Pb dating of detrital zircons have greatly helped to determine some of the sources of these sediments. For this study, sandstone samples were collected from the Pottsville Formation in the northern Appalachian Foreland Basin, Venango County, Pennsylvania to provide supplementary data for previous work that sought to describe the provenance of the same sediments by point counts of thin sections of the same units. Results of this previous work established that the provenance for these units was transitional recycled orogenic, including multiple recycled sediments, and that a cratonic contribution was not able to be determined clearly. The previous results suggested that the paleoenvironment was a fluvial dominated delta prograding in the northern direction. However, no geochronologic data was found during this study to confirm this interpretation. We sought to verify these results by U-Pb analysis of detrital zircons. Samples were collected from the areas where the previous research took place. U-Pb ages were found from sample at the highest elevation and lowest elevation. In the first sample, sample 17SL01 (younger sample stratigraphically), the zircons yield U-Pb age range peaks at 442-468 ma and 1037-1081 ma. The probability density plot for this specific sample displays a complete age gap from 500 ma to 811 ma. In the second sample, sample 17SL03 (older rock stratigraphically), the zircons yield U-Pb ages range peaks of 424-616 ma and 975-1057 ma. This sample doesn't show any ages younger than 424 ma and it doesn't display the sample age gap as sample 17SL01 does. The ages of zircons are consistent with thin section point counting provenance results from previous research suggesting zircon transport from the northern direction.

  11. Rietveld structure refinement and elastic properties of MgAlxCrxFe2-2xO4 spinel ferrites

    Science.gov (United States)

    Thummer, K. P.; Tanna, Ashish R.; Joshi, Hiren H.

    2017-05-01

    MgAlxCrxFe2-2xO4 (x = 0.1, 03 & 0.6) ferrites are synthesized by solid state reaction method. The Rietveld refinement of X-ray diffraction (XRD) data confirms the cubic spinel structure with Fd3m space group. The Fourier Transform Infrared Transmission Spectroscopy (FTIR) is employed to study elastic properties of present systems at 300K. The force constants for tetrahedral (A) and octahedral (B) sites of the spinel lattice are determined by infrared spectral and X-ray diffraction analysis. The elastic constants like bulk modulus, rigidity modulus, Young's modulus, Poisson's ratio and Debye temperature are determined. The vibrational frequency of both the interstitial sites increases as Al-Cr content increases hence the force constant and elastic moduli for all the samples are found to increase for the present ferrite system.

  12. Experimental Determination of Spinel/Melt, Olivine/Melt, and Pyroxene/Melt Partition Coefficients for Re, Ru, Pd, Au, and Pt

    Science.gov (United States)

    Righter, K.; Campbell, A. J.; Humayun, M.

    2003-01-01

    Experimental studies have identified spinels as important hosts phases for many of the highly siderophile elements (HSE). Yet experimental studies involving chromite or Cr-rich spinel have been lacking. Experimental studies of partitioning of HSEs between silicate, oxides and silicate melt are plagued by low solubilities and the presence of small metallic nuggets at oxygen fugacities relevant to magmas, which interfere with analysis of the phases of interest. We have circumvented these problems in two ways: 1) performing experiments at oxidized conditions, which are still relevant to natural systems but in which nuggets are not observed, and 2) analysis of run products with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), allowing a combination of high sensitivity and good spatial resolution.

  13. Spinel + quartz-bearing ultrahigh-temperature granulites from Xumayao, Inner Mongolia Suture Zone, North China Craton: Petrology, phase equilibria and counterclockwise p-T path

    Directory of Open Access Journals (Sweden)

    Huatian Zhang

    2012-09-01

    Our phase equilibria modeling indicates two main stages during the metamorphic evolution of these rocks: 1 near-isobaric cooling from 975 °C to 875 °C around 8 kbar, represented by the formation of garnet porphyroblasts from spinel and quartz; and 2 cooling and decompression from 850 °C, 8 kbar to below 750 °C, 6.5 kbar, represented by the break-down of garnet. The spinel + quartz assemblage is considered to have been stable at peak metamorphism, formed through the break-down of cordierite, indicating a near isothermal compression process. Our study confirms the regional extent of UHT metamorphism within the IMSZ associated with the Paleoproterozoic subduction-collision process.

  14. Surface enrichment of Pt in stable Pt-Ir nano-alloy particles on MgAl 2 O 4 spinel in oxidizing atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Li, Weizhen; Nie, Lei; Chen, Ying; Kovarik, Libor; Liu, Jun; Wang, Yong

    2017-04-01

    With the capability of MgAl2O4 spinel {111} nano-facets in stabilizing small Rh, Ir and Pt particles, bimetallic Ir-Pt catalysts on the same support were investigated, aiming at further lowering the catalyst cost by substituting expensive Pt with cheaper Ir in the bulk. Small Pt-Ir nano-alloy particles (< 2nm) were successfully stabilized on the spinel {111} nano-facets as expected. Interestingly, methanol oxidative dehydrogenation (ODH) rate on the surface Pt atoms increases with oxidizing aging but decreases upon reducing treatment, where Ir is almost inactive under the same reaction conditions. Up to three times enhancement in Pt exposure was achieved when the sample was oxidized at 800 °C in air for 1 week and subsequently reduced by H2 for 2 h, demonstrating successful surface enrichment of Pt on Pt-Ir nano-alloy particles. A dynamic stabilization mechanism involving wetting\

  15. Forecasting of chalcogenide spinels of the general formula AB2X4 using the method of training of an electronic computer

    International Nuclear Information System (INIS)

    Kiseleva, N.N.; Savitskij, E.M.

    1979-01-01

    Experimental evidence on the existence of AB 2 X 4 compounds in A-B-X systems (A and B are any elements of the periodic system, in particular, rare earth elements, X is S or Se) and the data on the properties of elements and simple sulphides (selenides) were used for an attempt to find the probability of formation of AB 2 X 4 compounds as a function of the component properties. The experimental evidence was analyzed by a computer employing algorithms of concept formation training. The results were used to predict new AB 2 X 4 compounds. The computer training method proved an efficient means of revealing the connection between probability of spinel type compounds existence with the component properties. Certain compounds of general formula AB 2 X 4 were predicted and the probability that they possess spinel structure was evaluated

  16. Physical investigations on NiMn{sub 2}O{sub 4} sprayed magnetic spinel for sensitivity applications

    Energy Technology Data Exchange (ETDEWEB)

    Larbi, T.; Amara, A.; Ouni, B. [Unité de physique des dispositifs a semi-conducteurs, Faculté des sciences de Tunis, Tunis El Manar University, 2092 Tunis (Tunisia); Inoubli, A. [Faculté des Sciences de Bizerte Laboratoire de Physique des Matériaux Département de Physique, Zarzouna, 7021 Bizerte (Tunisia); Karyaoui, M. [Laboratoire de photovoltaïque, Centre de Recherches et des Technologies de l’Énergie, Technopole de Borj-Cédria BP 95, 2050 Hammam-Lif (Tunisia); Yumak, A. [Physics Department, Faculty of Arts and Sciences, Marmara University, Göztepe, 34722 Istanbul (Turkey); Saadallah, F. [Phothermal laboratory IPEIN, Mrezka, BP 62, 8000 Nabeul (Tunisia); Boubaker, K., E-mail: mmbb11112000@yahoo.fr [Unité de physique des dispositifs a semi-conducteurs, Faculté des sciences de Tunis, Tunis El Manar University, 2092 Tunis (Tunisia); Amlouk, M. [Unité de physique des dispositifs a semi-conducteurs, Faculté des sciences de Tunis, Tunis El Manar University, 2092 Tunis (Tunisia)

    2015-08-01

    NiMn{sub 2}O{sub 4} ternary nickel manganese oxide thin films spinels have been grown on glass substrates at 350 °C through spray pyrolysis technique. X-ray diffraction and Raman spectroscopy analyses show that the synthesized film has mainly cubic spinel structure with a preferred orientation along (111) plane. Some optical constants such as the refractive index (n), extinction coefficient (k), Urbach energy (E{sub U}=342 eV) and optical energy band gap (E{sub g}=1.07 eV) have been calculated from reflection-transmission spectra. The mirage effect technique has been used to estimate the thermal conductivity (K{sub c}). Its value is K{sub c}=25 W m{sup −1} K{sup −1}. The real part of the ac the conductivity behaviour has been investigated in the frequency range 100 Hz to 1 MHz. It was found that the real conductivity follows a power law (Aω{sup s}). The dc conductivity has been studied in the temperature range from 250 °C to 375 °C and supports the variable range hopping model proposed by Mott. The activation energy value estimated from the relaxation frequency is Ea~0.32 eV. Moreover, the temperature dependency of the resistance indicates that conduction was well described by a variable range hopping model, in which electron transfer takes place between Mn{sup 3+} and Mn{sup 4+} ions. - Highlights: • The nickel manganese oxide (NiMn{sub 2}O{sub 4}) has been prepared by the low-cost spray pyrolysis technique. • The optical band gap of this ternary oxide is around 1 eV and the crystallites are oriented preferentially along (111) direction. • Presenting an accurate technique “Mirage effect” for original investigation of thermal properties. • DC and AC conductivity can be both attributed to a hopping transport, while at high frequency a metallic-like behavior is observed. • A deep analysis within correlated barrier hopping (CBH) model was carried out. • Outlining a correlation between Magnetic and electrical properties.

  17. Magnetic, dielectric and microwave absorption properties of rare earth doped Ni–Co and Ni–Co–Zn spinel ferrites

    Energy Technology Data Exchange (ETDEWEB)

    Stergiou, Charalampos, E-mail: stergiou@cperi.certh.gr

    2017-03-15

    In this article we analyze the electromagnetic properties of rare earth substituted Ni–Co and Ni–Co–Zn cubic ferrites in the microwave band, along with their performance as microwave absorbing materials. Ceramic samples with compositions Ni{sub 0.5}Co{sub 0.5}Fe{sub 2−x}R{sub x}O{sub 4} and Ni{sub 0.25}Co{sub 0.5}Zn{sub 0.25}Fe{sub 2−x}R{sub x}O{sub 4} (R=Y and La, x=0, 0.02), fabricated with the solid state reaction method, were characterized with regard to the complex permeability μ*(f) and permittivity ε*(f) up to 20 GHz. The rare earth substitutions basically affect the microwave μ*(f) spectra and the dynamic magnetization mechanisms of domain wall motion and magnetization rotation. Key parameters for this effect are the reduced magnetocrystalline anisotropy and the created crystal inhomogeneities. Moreover, permittivity is increased with the Y and La content, due to the enhancement of the dielectric orientation polarization. Regarding the electromagnetic wave attenuation, the prepared ferrites exhibit narrowband return losses (RL) by virtue of the cancellation of multiple reflections, when their thickness equals an odd multiple of quarter-wavelength. Interestingly, the zero-reflection conditions are satisfied in the vicinity of the ferromagnetic resonance. As the rare earth doping shifts this mechanism to lower frequencies, loss peaks with RL>46 dB occur at 4.1 GHz and 5 GHz for Y and La-doped Ni–Co–Zn spinels, whereas peaks with RL>40 dB appear at 18 GHz and 19 GHz for Y and La-doped Ni–Co spinels, respectively. The presented experimental findings underline the potential of cubic ferrites with high Co concentration in the suppression of electromagnetic reflections well above the 1 GHz region. - Highlights: • Due to cation distribution, magnetic anisotropy drops in Y and La doped samples. • Microwave permeability spectra shift to lower frequencies with rare earth doping. • Permittivity is increased due to crystal modifications

  18. Lithium-deficient Li YMn2O4 spinels (0.9 ≤ Y < 1): Lithium content, synthesis temperature, thermal behaviour and electrochemical properties

    International Nuclear Information System (INIS)

    Pascual, Laura; Perez-Revenga, M. Luz; Rojas, Rosa M.; Rojo, Jose M.; Amarilla, J. Manuel

    2006-01-01

    Lithium-deficient Li Y Mn 2 O 4 spinels (LD-Li Y Mn 2 O 4 ) with nominal composition (0.9 ≤ Y 2 O 3 and LiNO 3 at temperatures ranging from 700 deg. C to 850 deg. C. X-ray diffraction data show that LD-Li Y Mn 2 O 4 spinels are obtained as single phases in the range Y = 0.975-1 at 700 deg. C and 750 deg. C. Morphological characterization by transmission electron microscopy shows that the particle size of LD-Li Y Mn 2 O 4 spinels increases on decreasing the Li-content. The influence of the Li-content and the synthesis temperature on the thermal and electrochemical behaviours has been systematically studied. Thermal analysis studies indicate that the temperature of the first thermal effect in the differential thermal analysis (DTA)/thermogravimetric (TG) curves, T C1 , linearly increases on decreasing the Li-content. The electrochemical properties of LD-Li Y Mn 2 O 4 spinels, determined by galvanostatic cycling, notably change with the synthesis conditions. So, the first discharge capacity, Q disch. , at C rate increases on rising the Li-content and the synthesis temperature. The sample Li 0.975 Mn 2 O 4 synthesized at 700 deg. C has a Q disch. = 123 mAh g -1 and a capacity retention of 99.77% per cycle. This LD-Li Y Mn 2 O 4 sample had the best electrochemical characteristics of the series

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

    Science.gov (United States)

    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.

  20. The Formation of Lithiated Ti-Doped {alpha}-Fe{sub 2}O{sub 3} Nanocrystalline Particles by Mechanical Milling of Ti-Doped Lithium Spinel Ferrite

    Energy Technology Data Exchange (ETDEWEB)

    Widatallah, H. M., E-mail: hisham@ictp.trieste.it [Khartoum University, Department of Physics (Sudan); Gismelseed, A. M.; Bouziane, K. [Sultan Qaboos University, Department of Physics (Oman); Berry, F. J. [Open University, Department of Chemistry (United Kingdom); Al Rawas, A. D.; Al-Omari, I. A.; Yousif, A. A.; Elzain, M. E. [Sultan Qaboos University, Department of Physics (Oman)

    2004-12-15

    The milling of spinel-related Ti-doped Li{sub 0.5}Fe{sub 2.5}O{sub 4} for different times is studied with XRD, Moessbauer spectroscopy and magnetic measurements. Milling converts the material to Li-Ti-doped {alpha}-Fe{sub 2}O{sub 3} nanocrystalline particles via an intermediate {gamma}-LiFeO{sub 2}-related phase. The role played by the dopant Ti-ion in the process is emphasized.

  1. The Formation of Lithiated Ti-Doped α-Fe2O3 Nanocrystalline Particles by Mechanical Milling of Ti-Doped Lithium Spinel Ferrite

    International Nuclear Information System (INIS)

    Widatallah, H. M.; Gismelseed, A. M.; Bouziane, K.; Berry, F. J.; Al Rawas, A. D.; Al-Omari, I. A.; Yousif, A. A.; Elzain, M. E.

    2004-01-01

    The milling of spinel-related Ti-doped Li 0.5 Fe 2.5 O 4 for different times is studied with XRD, Moessbauer spectroscopy and magnetic measurements. Milling converts the material to Li-Ti-doped α-Fe 2 O 3 nanocrystalline particles via an intermediate γ-LiFeO 2 -related phase. The role played by the dopant Ti-ion in the process is emphasized.

  2. Irradiation effects and behaviour of fission products in zirconia and spinel; Effets d'irradiation et comportement des produits de fission dans la zircone et le spinelle

    Energy Technology Data Exchange (ETDEWEB)

    Gentils, A

    2003-10-01

    Crystalline oxides, such as zirconia (ZrO{sub 2}) and spinel (MgAl{sub 2}O{sub 4}), are promising inert matrices for the transmutation of plutonium and minor actinides. This work deals with the study of the physico-chemical properties of these matrices, more specifically their behaviour under irradiation and their capacity to retain fission products. Irradiations at low energy and incorporation of stable analogs of fission products (Cs, I, Xe) into yttria-stabilized zirconia and magnesium-aluminate spinel single crystals were performed by using the ion implanter IRMA (CSNSM-Orsay). Irradiations at high energy were made on several heavy ion accelerators (GANIL-Caen, ISL-Berlin, HIL-Warsaw). The damage induced by irradiation and the release of fission products were monitored by in situ Rutherford Backscattering Spectrometry experiments. Transmission electron microscopy was also used in order to determine the nature of the damage induced by irradiation. The results show that irradiation of ZrO{sub 2} and MgAl{sub 2}O{sub 4} with heavy ions (about hundred keV and about hundred MeV) induces a huge structural damage in crystalline matrices. Total disorder (amorphization) is however never reached in zirconia, contrary to what is observed in the case of spinel. The results also emphasize the essential role played by the concentration of implanted species on their retention capacity. A dramatic release of fission products was observed when the concentration exceeds a threshold of a few atomic percent. Irradiation of implanted samples with medium-energy noble-gas ions leads to an enhancement of the fission product release. The exfoliation of spinel crystals implanted at high concentration of Cs ions is observed after a thermal treatment at high temperature. (author)

  3. Detrital zircon provenance from three turbidite depocenters of the Middle-Upper Triassic Songpan-Ganzi complex, central China: Record of collisional tectonics, erosional exhumation, and sediment production

    Science.gov (United States)

    Weislogel, A.L.; Graham, S.A.; Chang, E.Z.; Wooden, J.L.; Gehrels, G.E.

    2010-01-01

    To test the idea that the voluminous upper Middle to Upper Triassic turbidite strata in the Songpan-Ganzi complex of central China archive a detrital record of Dabie ultrahigh-pressure (UHP) terrane unroofing, we report 2080 single detrital U-Pb zircon ages by sensitive high-resolution ion microprobe-reverse geometry (SHRIMP-RG) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analysis from 29 eastern Songpan-Ganzi complex sandstone samples. Low (Th/U zircons, consistent with crystallization under UHP conditions, are rare in eastern Songpan-Ganzi complex zircon, and U-Pb ages of low Th/U zircons are incompatible with a Dabie terrane source. An unweighted pair group method with arithmetic mean nearest-neighbor analysis of Kolmogorov-Smirnov two-sample test results reveals that the eastern Songpan-Ganzi complex is not a single contiguous turbidite system but is instead composed of three subsidiary depocenters, each associated with distinct sediment sources. The northeastern depocenter contains zircon ages characterized by Paleozoic and bimodally distributed Precambrian zircon populations, which, together with south-to southeast-directed paleocurrent data, indicate derivation from the retro-side of the Qinling-Dabie (Q-D) collisional orogen wedge. In the central depocenter, the dominantly Paleozoic detrital zircon signature and south-to southwest-oriented paleocurrent indicators reflect a profusion of Paleozoic zircon grains. These data are interpreted to reflect an influx of material derived from erosion of Paleozoic supra-UHP rocks of the Dabie terrane in the eastern Qinling-Dabie orogen, which we speculate may have been enhanced by development of a monsoonal climate. This suggests that erosional unroofing played a significant role in the initial phase of UHP exhumation and likely influenced the petrotectonic and structural evolution of the Qinling-Dabie orogen, as evidenced by compressed Triassic isotherms/grads reported in the Huwan

  4. Studies on densification, mechanical, micro-structural and structure–properties relationship of magnesium aluminate spinel refractory aggregates prepared from Indian magnesite

    International Nuclear Information System (INIS)

    Ghosh, Chandrima; Ghosh, Arup; Haldar, Manas Kamal

    2015-01-01

    The present work intends to study the development of magnesium aluminate spinel aggregates from Indian magnesite in a single firing stage. The raw magnesite has been evaluated in terms of chemical analysis, differential thermal analysis, thermogravimetric analysis, infrared spectroscopy, and X-ray diffraction. The experimental batch containing Indian magnesite and calcined alumina has been sintered in the temperature range of 1550 °C–1700 °C. The sintered material has been characterized in terms of physico-chemical properties like bulk density, apparent porosity, true density, relative density and thermo-mechanical/mechanical properties like hot modulus of rupture, thermal shock resistance, cold modulus of rupture and structural properties by X-ray diffraction in terms of phase identification and evaluation of crystal structure parameters of corresponding phases by Rietveld analysis. The microstructures developed at different temperatures have been analyzed by field emission scanning electron microscope study and compositional analysis of the developed phase has been carried out by energy dispersive X-ray study. - Highlights: • The studies have been done to characterize the developed magnesium aluminate spinel. • The studies reveal correlation between refractory behavior of spinel and developed microstructures. • The studies show the values of lattice parameters of developed phases

  5. Thermodynamic investigation on the formation of inclusions containing MgAl2O4 spinel during 16Cr-14Ni austenitic stainless steel manufacturing processes

    International Nuclear Information System (INIS)

    Park, J.H.

    2008-01-01

    The formation mechanism of the inclusions containing the spinel crystals has been developed based on the experimental results for the equilibrium between the Fe-16%Cr-14%Ni stainless steel melts and the inclusions as well as the compositions of the inclusions in the plant samples. In the laboratory experiments, the molar content of alumina in the inclusions linearly increases with increasing content of aluminum according to the theoretical expectation and the composition of the inclusions could be described as a function of the activity of aluminum and silicon. From the analysis of the plant samples, the content of MgO and Al 2 O 3 in the calcium silicate type inclusions continuously increases as the steel melts transfer from AOD converter to LT processes and thus, the spinel phase could be crystallized and grown in the calcium silicate matrix during cooling through tundish to cast slabs. On the other hand, the manganese silicate type inclusions were observed after tapping molten steel to the ladle, and then the MnO and Cr 2 O 3 (and SiO 2 ) in the inclusions were reduced by silicon and aluminum through LT to CC mold. The fraction of the inclusions containing spinel crystals at cast slabs was null at (Al 2 O 3 ) 2 O 3 ) > 20 mass%

  6. Preparation of Layered-Spinel Microsphere/Reduced Graphene Oxide Cathode Materials for Ultrafast Charge-Discharge Lithium-Ion Batteries.

    Science.gov (United States)

    Luo, Dong; Fang, Shaohua; Yang, Li; Hirano, Shin-Ichi

    2017-12-22

    Although Li-rich layered oxides (LLOs) have the highest capacity of any cathodes used, the rate capability of LLOs falls short of meeting the requirements of electric vehicles and smart grids. Herein, a layered-spinel microsphere/reduced graphene oxide heterostructured cathode (LS@rGO) is prepared in situ. This cathode is composed of a spinel phase, two layered structures, and a small amount of reduced graphene oxide (1.08 wt % of carbon). The assembly delivers a considerable charge capacity (145 mA h g -1 ) at an ultrahigh charge- discharge rate of 60 C (12 A g -1 ). The rate capability of LS@rGO is influenced by the introduced spinel phase and rGO. X-ray absorption and X-ray photoelectron spectroscopy data indicate that Cr ions move from octahedral lattice sites to tetrahedral lattice sites, and that Mn ions do not participate in the oxidation reaction during the initial charge process. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Electrochemical evaluation of the a carbon-paste electrode modified with spinel manganese(IV) oxide under flow conditions for amperometric determination of lithium

    International Nuclear Information System (INIS)

    Raymundo-Pereira, Paulo A.; Martin, Cibely S.; Bergamini, Marcio F.; Bocchi, Nerilso; Teixeira, Marcos F.S.

    2011-01-01

    The participation of cations in redox reactions of manganese oxides provides an opportunity for development of chemical sensors for non-electroactive ions. This paper describes the amperometric determination of lithium ions using carbon-paste electrode modified with spinel manganese(IV) oxide under flow conditions. Systematic investigations were made to optimize the experimental parameters for lithium sensor by flow injection analysis. The detection was based on the measurement of anodic current generated by oxidation of Mn(III) to Mn(IV) at the surface of the electrode and consequently the lithium ions extraction into the spinel structure. An operating potential of 0.50 V (vs. Ag/AgCl/3 KCl mol/L) was exploited for amperometric monitoring. The amperometric signal was linearly dependent on the lithium ions concentration over the range 4.0 x 10 -5 to 1.0 x 10 -3 mol L -1 . The equilibrium constant of insertion/extraction of the lithium ion in the spinel structure, apparent Gibbs energy of insertion, and surface coverage of the electrode with manganese oxide, were calculated by peak charge (Q) in different concentration under flow conditions. Considering selectivity, the peak charge of the sensor was found to be linearly dependent on the ionic radius of the alkaline and earth-alkaline cations.

  8. The Effects of Oxygen Partial Pressure on Liquidus Temperature of a High-Level Waste Glass with Spinel as the Primary Phase

    International Nuclear Information System (INIS)

    Izak, Pavel; Hrma, Pavel R.; Wilson, Benjamin K.; Vienna, John D.

    2000-01-01

    The redox state of iron affects spinal crystallization in vitrified high-level waste (HLW) glass. Simulated HLW glass with spinel as the primary crystalline phase field was heat treated at constant temperatures within the interval from 850 C to 1300 C under varying atmospheres with oxygen partial pressure, Po2, ranging from 1x10-16 kPa (pure CO) to 101 kPa (pure O2). Liquidus temperature (TL) of glass increased with decreasing Po2 up to Po2 > 3 x 10-9 kPa. At Po2 < 3 x 10-9 kPa, Ni-Fe alloy precipitated from the glass, and TL decreased. Samples were analyzed with optical microscope and scanning electron microscope. The mass fraction of spinel in glass was determined using quantitative X-ray diffraction. Spinel composition was investigated with energy disperse spectroscopy. Ferrous-ferric equilibrium at TL was calculated in a HLW glass as a function of temperature and Po2, based on the previous studies by Schreiber. TL/FeO over the interval 0.0063 < gFeO < 0.051 (1x10-2 kPa < Po2 < 3x10-9 kPa) was estimated from calculated ferrous-ferric equilibrium at TL as 1835 C

  9. Rapid synthesis of monodispersed highly porous spinel nickel cobaltite (NiCo{sub 2}O{sub 4}) electrode material for supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Naveen, A. Nirmalesh, E-mail: nirmalesh.naveen@gmail.com; Selladurai, S. [Ionics Laboratory, Department of Physics, Anna University, Chennai-600025 (India)

    2015-06-24

    Monodispersed highly porous spinel nickel cobaltite electrode material was successfully synthesized in a short time using combustion technique. Single phase cubic nature of the spinel nickel cobaltite with average crystallite size of 24 nm was determined from X-ray diffraction study. Functional groups present in the compound were determined from FTIR study and it further confirms the spinel formation. FESEM images reveal the porous nature of the prepared material and uniform size distribution of the particles. Electrochemical evaluation was performed using Cyclic Voltammetry (CV) technique, Chronopotentiometry (CP) and Electrochemical Impedance Spectroscopy (EIS). Results reveal the typical pseudocapacitive behaviour of the material. Maximum capacitance of 754 F/g was calculated at the scan rate of 5 mV/s, high capacitance was due to the unique porous morphology of the electrode. Nyquist plot depicts the low resistance and good electrical conductivity of nickel cobaltite. It has been found that nickel cobaltite prepared by this typical method will be a potential electrode material for supercapcitor application.

  10. Chemical vs. electrochemical extraction of lithium from the Li-excess Li(1.10)Mn(1.90)O4 spinel followed by NMR and DRX techniques.

    Science.gov (United States)

    Martinez, S; Sobrados, I; Tonti, D; Amarilla, J M; Sanz, J

    2014-02-21

    Lithium extraction from the Li-excess Li1.10Mn1.90O4 spinel has been performed by chemical and electrochemical methods in aqueous and in organic media, respectively. De-lithiated samples have been investigated by XRD, SEM, TG, (7)Li and (1)H MAS-NMR techniques. The comparative study has allowed demonstrating that the intermediate de-intercalated samples prepared during the chemical extraction by acid titration are similar to those prepared by the electrochemical way in a non-aqueous electrolyte. LiMn2O4 based spinel with a tailored de-lithiation degree can be prepared as a single phase by controlling the pH used in chemical extraction. (7)Li MAS-NMR spectroscopy has been used to follow the influence of the manganese oxidation state on tetra and octahedral Li-signals detected in Li-extracted samples. The oxidation of Mn(III) ions goes parallel to the partial dissolution of the spinel, following Hunter's mechanism. Based on this mechanism, a generalized chemical reaction has been proposed to explain the formation of intermediate Li(+) de-intercalated samples during acid treatment in aqueous media. By the (1)H MAS NMR study, no evidence of Li-H topotactic exchange in the bulk of the acid treated material was found.

  11. Defect kinetics in spinels: Long-time simulations of MgAl2O4, MgGa2O4, and MgIn2O4

    International Nuclear Information System (INIS)

    Uberuaga, B. P.; Voter, A. F.; Sickafus, K. E.; Bacorisen, D.; Smith, Roger; Ball, J. A.; Grimes, R. W.

    2007-01-01

    Building upon work in which we examined defect production and stability in spinels, we now turn to defect kinetics. Using temperature accelerated dynamics (TAD), we characterize the kinetics of defects in three spinel oxides: magnesium aluminate MgAl 2 O 4 , magnesium gallate MgGa 2 O 4 , and magnesium indate MgIn 2 O 4 . These materials have varying tendencies to disorder on the cation sublattices. In order to understand chemical composition effects, we first examine defect kinetics in perfectly ordered, or normal, spinels, focusing on point defects on each sublattice. We then examine the role that cation disorder has on defect mobility. Using TAD, we find that disorder creates local environments which strongly trap point defects, effectively reducing their mobility. We explore the consequences of this trapping via kinetic Monte Carlo (KMC) simulations on the oxygen vacancy (V O ) in MgGa 2 O 4 , finding that V O mobility is directly related to the degree of inversion in the system

  12. Detrital zircons from samples of five Neo proterozoic sandstone units deposited on Uruguay and Argentina: about evolution of paleographic Rio de la Plata craton

    International Nuclear Information System (INIS)

    Gaucher, C.; Poire, D.G.; Pamoukaghlian, K.; Gomez Peral, L.; Finney, S.; Valencia, V.; Blanco, G.

    2007-01-01

    We report U-Pb ages of detrital zircons from samples of five Neoproterozoic sandstone units deposited on the Rio de la Plata Craton (RPC) in Uruguay and Argentina. Quartz-arenites of the Piedras de Afilar Formation show typical Transamazonian ages, with peaks at 2.00-2.07, 1.87 and 1.78 Ga. However, the most important zircon population is Mesoproterozoic, showing maxima at 1.49, 1.35, 1.25 and 1.0 Ga. Zircons recovered from two sandstone levels in the Arroyo del Soldado Group (Yerbal and Cerros San Francisco formations) are mostly Archean in age, with maxima at 3.2 and 2.7 Ga. Palaeoproterozoic zircons are also prominent in this unit, with peaks at 2.45 and 2.18, with the latter a typical Transamazonian age. Two samples from the Sierras Bayas Group in Tandilia (Argentina) show different age spectra. Sandstones of the Villa Monica Formation show a unimodal zircon population of Transamazonian age (peak at 2.13 Ga). Sandstones of the Cerro Largo Formation are characterized by a dominant Transamazonian zircon population (peaks at 2.15, 2.0 and 1.79), but also important Archean-lowermost Palaeoproterozoic (3.33, 2.99, 2.7, 2.47 Ga) and Mesoproterozoic peaks (1.55, 1.23 and 1.06). The abundance of Mesoproterozoic detrital zircons is surprising. A proto-Andean, Mesoproterozoic belt is suggested as the source of the Mesoproterozoic detritus. Archean rocks of the RPC crop out only in the Nico Perez Terrane in Uruguay, suggesting that the Nico Perez Terrane was much closer to Tandilia than it is today. The sinistral reactivation of the Sarandi del Yi Shear Zone in the Cambrian, as a result of tangential collision of the Cuchilla Dionisio-Pelotas Terrane, may explain this observations. The absence of Neoproterozoic zircons shows that the studied units were deposited in a stable continental margin opening to the East and South. These Neoproterozoic basins had obviously no contribution whatsoever from Brasiliano-Pan African belts, supporting the idea of Cambrian terrane

  13. Integrated Laser Ablation U/Pb and (U-Th)/He Dating of Detrital Accessory Minerals from the Naryani River, Central Nepal

    Science.gov (United States)

    Horne, A.; Hodges, K. V.; Van Soest, M. C.

    2015-12-01

    The newly developed 'laser ablation double dating' (LADD) technique, an integrated laser microprobe U/Pb and (U-Th)/He dating method, could be an exceptionally valuable tool in detrital thermochronology for identifying sedimentary provenance and evaluating the exhumation history of a source region. A recent proof-of-concept study has used LADD to successfully date both zircon and titanite crystals from the well-characterized Fish Canyon tuff, but we also believe that another accessory mineral, rutile, could be amenable to dating via the LADD technique. To continue the development of the method, we present an application of LADD to detrital zircon, titanite, and rutile from a sample collected on the lower Naryani River of central Nepal. Preliminary analyses of the sample have yielded zircon U/Pb dates ranging from 31.4 to 2405 Ma; zircon (U-Th)/He from 1.8 to 15.4 Ma; titanite U/Pb between 18 and 110 Ma; titanite (U-Th)/He between 1 and 16 Ma; rutile U/Pb from 6 to 45 Ma; and rutile (U-Th)/He from 2 to 25 Ma. In addition to the initial data, we can use Ti-in-zircon, Zr-in-titanite, and Zr-in-rutile thermometers to determine the range of possible long-term cooling rates from grains with U/Pb ages younger than collision. Thus far our results from zircon analyses imply a cooling rate of approximately 15°C/Myr; titanite analyses imply between 10 and 67°C/Myr; and rutile between 9 and 267°C/Myr. This spread in potential cooling rates, especially in the order of magnitude differences of cooling rates calculated from the rutile grains, suggests that the hinterland source regions of the Naryani river experienced dramatically different exhumation histories during Himalayan orogenisis. Ongoing analyses will expand the dataset such that we can more adequately characterize the range of possibilities represented in the sample.

  14. Detrital Zircon Geo- and Thermochronologic Constraints on Late Mississippian-Early Pennsylvanian Sediment Transport and Tectonics, Southwestern Kansas and Northwestern Arkansas

    Science.gov (United States)

    Bidgoli, T. S.; Wang, W.; Moeller, A.; Stockli, D. F.; Watney, L.

    2017-12-01

    The Late Mississippian to Early Pennsylvanian is a critical time interval across the globe, with major changes in tectonics, climate, and eustacy. Transcontinental sediment transport in North America, from the Appalachians to Great Canyon, has been proposed to initiate at this time (Gehrels et al., 2011). In the midcontinent, clastic influx to the Hugoton Embayment and Arkoma Shelf, during widespread carbonate platform deposition, may record evidence for this model, but the limited number of provenance studies has hindered interpretations. To test this model and further constrain sediment dispersal and source-to-sink systems in the midcontinent, we evaluate the provenance of upper Mississippian to middle Pennsylvanian siliciclastic intervals, in two areas, using sandstone component analysis and detrital zircon U-Pb and (U-Th)/He double dating. (1) For the Hugoton Embayment in southwestern Kansas, we focus on sandstones deposited in two valley-filling intervals, the Chester and Morrow. A total of 1100 zircon U-Pb ages have been acquired from samples from 10 boreholes, 6 from Chester and 4 from Morrow. Preliminary analysis suggests that the Chester is characterized by two major zircon U-Pb age clusters of 900-1295 Ma (Grenville) and 390-475 Ma, consistent with sediment delivery from the Appalachian orogen. Morrow strata record a change in provenance, with the presence of two additional age groups, 1300-1500 Ma (24.5%) and 1600-1800 Ma (17.9%), that correspond well with the age of basement rocks in the Granite-Rhyolite and Yavapai-Maztzal provinces, respectively. We ascribe changes in the zircon age spectra and introduction of these grains to the development of local uplifts, like the Nemaha Ridge, in the early Pennsylvanian. Double dating of zircons from these peaks may reveal additional information about these basement sources and the timing of denudation of these uplifts. (2) For the Arkoma shelf, we are analyzing 11 samples, collected from outcrops in northwestern

  15. Timing of deformation and rapid subsidence in the northern Altiplano, Peru: Insights from detrital zircon geochronology of the Ayaviri hinterland basin

    Science.gov (United States)

    Horton, B. K.; Perez, N. D.; Saylor, J. E.

    2011-12-01

    Although age constraints on crustal deformation and sediment accumulation prove critical to testing hypotheses of orogenic plateau construction, a common lack of marine facies, volcanic tuffs, and suitable fossils hinders many attempts at chronological reconstructions. A series of elevated retroarc basins along the axis of the Andean orogenic belt provide opportunities to define the timing of deformation and transformation from foreland to hinterland basin configurations. In this study, we present new U-Pb ages of detrital zircons in the Ayaviri intermontane basin of southern Peru (~4 km elevation) in the northern part of the central Andean (Altiplano) plateau. Nearly all sandstone samples show strong unimodal U-Pb age peaks (generally defined by > 5-50 zircons), suggesting these age peaks represent syndepositional volcanism and can be regarded as accurate estimates of true depositional (stratigraphic) age. Integration of these ages with structural and stratigraphic relationships demonstrate the utility of zircon U-Pb geochronology in defining both (1) the timing of basin partitioning and (2) the pace of sediment accumulation. (1) U-Pb ages for several sandstone samples from growth-strata packages associated with two basin-bounding faults reveal structural partitioning of the Ayaviri basin from late Oligocene to Miocene time. In the north, displacement along the southwest-directed Ayaviri thrust fault commenced in late Oligocene time (~28-24 Ma), inducing initial structural partitioning of an upper Eocene-Oligocene, > 5 km thick succession potentially representing an early Andean retroarc foreland basin. In the south, the Ayaviri basin was further disrupted by initial displacement along the northeast-directed Pasani thrust fault in early to middle Miocene time (~18-15 Ma). (2) Additional U-Pb analyses from the Ayaviri basin fill help delimit the long-term rates of sedimentation, suggesting relatively short-lived (< 5 Myr) pulses of accelerated accumulation. Rapid

  16. U Pb and Lu Hf isotope record of detrital zircon grains from the Limpopo Belt Evidence for crustal recycling at the Hadean to early-Archean transition

    Science.gov (United States)

    Zeh, Armin; Gerdes, Axel; Klemd, Reiner; Barton, J. M., Jr.

    2008-11-01

    Detrital zircon grains from Beit Bridge Group quartzite from the Central Zone of the Limpopo Belt near Musina yield mostly ages of 3.35-3.15 Ga, minor 3.15-2.51 Ga components, and numerous older grains grouped at approximately 3.4, 3.5 and 3.6 Ga. Two grains yielded concordant Late Hadean U-Pb ages of 3881 ± 11 Ma and 3909 ± 26 Ma, which are the oldest zircon grains so far found in Africa. The combined U-Pb and Lu-Hf datasets and field relationships provide evidence that the sedimentary protolith of the Beit Bridge Group quartzite was deposited after the emplacement of the Sand River Gneisses (3.35-3.15 Ga), but prior to the Neoarchean magmatic-metamorphic events at 2.65-2.60 Ga. The finding of abundant magmatic zircon detritus with concordant U-Pb ages of 3.35-3.15 Ga, and 176Hf/ 177Hf of 0.28066 ± 0.00004 indicate that the Sand River Gneiss-type rocks were a predominant source. In contrast, detrital zircon grains older than approximately 3.35 Ga were derived from the hinterland of the Limpopo Belt; either from a so far unknown crustal source in southern Africa, possibly from the Zimbabwe Craton and/or a source, which was similar but not necessarily identical to the one that supplied the Hadean zircons to Jack Hills, Western Australia. The Beit Bridge Group zircon population at >3.35 Ga shows a general ɛHf t increase with decreasing age from ɛHf 3.9Ga = -6.3 to ɛHf 3.3-3.1Ga = -0.2, indicating that Hadean crust older than 4.0 Ga ( TDM = 4.45-4.36 Ga) was rejuvenated during magmatic events between >3.9 and 3.1 Ga, due to a successive mixing of crustal rocks with mantle derived magmas. The existence of a depleted mantle reservoir in the Limpopo's hinterland is reflected by the ˜3.6 Ga zircon population, which shows ɛHf 3.6Ga between -4.6 and +3.2. In a global context, our data suggest that a long-lived, mafic Hadean protocrust with some tonalite-trondhjemite-granodiorite constituents was destroyed and partly recycled at the Hadean/Archean transition, perhaps

  17. Ion microprobe (SHRIMP) dating of detrital zircon grains from quartzites of the Eckergneiss Complex, Harz Mountains (Germany): implications for the provenance and the geological history

    Science.gov (United States)

    Geisler, Thorsten; Vinx, Roland; Martin-Gombojav, Nergui; Pidgeon, Robert T.

    2005-07-01

    The Eckergneiss Complex (EGC) is a geologically unique medium- to high-grade metamorphic unit within the Rhenohercynian domain of the Mid-European Variscides. A previously, poorly defined conventional lower U Pb intercept age of about 560 Ma from detrital zircons of metasedimentary rocks has led to speculations about an East Avalonian affinity of the EGC. In order to unravel the provenance and to constrain the age of the sediment protolith, we carried out sensitive high-resolution ion microprobe U Pb analyses on detrital zircons from five different EGC quartzite occurrences. The obtained age spectrum indicates a SW Baltica provenance of the detritus. Sveconorwegian ages between 0.9 1.2 Ga are particularly well represented by analyses from metamorphic recrystallization/alteration zones penetrating into igneous zircon. Cadomian (Pan-African) ages, which might reflect a metamorphic event, could not be substantiated. Instead, zircons of igneous origin yielded concordant Lower Devonian and Silurian ages of 410±10, 419±10, and 436±6 Ma (1σ), implying that sedimentation of the EG protolith must have taken place after 410±10 Ma. The lower age limit of the EGC metamorphism is constrained by 295 Ma intrusion ages of the adjacent, nonmetamorphosed Harzburg Gabbronorite and Brocken Granite. Sedimentation and metamorphism must thus have taken place between about 410 Ma and 295 Ma. Given that this time span coincides with most of the sedimentation within the virtually nonmetamorphosed (lowest grade) Rhenohercynian in the Harz Mountains, including the direct vicinity of the EGC, along with the high-grade metamorphism, the EGC can hardly be seen as uplifted local basement. A possible candidate for the root region is an easterly, concealed marginal segment of the Rhenohercynian domain of the Variscides, which is tectonically overridden and suppressed by the Mid-German Crystalline Rise during continent collision. However, based on the concept of strike-slip movement of Variscan

  18. Sulfur isotope composition of orogenic spinel lherzolite massifs from Ariege (north-eastern pyrenees, France): An ion microprobe study

    Energy Technology Data Exchange (ETDEWEB)

    Chaussidon, M. (Centre de Recherches Petrographiques et Geochimiques, Vandoeuvre-les-Nancy (France)); Lorand, J. (Unite associee au CNRS, Paris (France))

    1990-10-01

    The orogenic spinel lherzolite massifs from Ariege, which represent tectonically emplaced fragments of the sub-continental upper mantle, are composed mainly of variously depleted peridotites. These rocks are crosscut by two generations of pyroxenites. The first is made up of layered pyroxenites, which are interpreted either as crystal segregates from Triassic continental tholeiites or as subducted parts of the oceanic crust re-injected within the upper mantle. The second consists of amphibole-rich dikes separated from Cretaceous alkali basalts. Forty sulfide grains, occurring either as inclusions within silicates or as interstitial grains, were investigated by ion microprobe for their sulfur isotopic compositions. Comparison between sulfide inclusions in silicates and interstitial sulfide grains strongly suggests that serpentinization and pyrenean metamorphism had no significant effect don the {delta}{sup 34}S values. Likewise, these values are broadly independent of the degree of partial melting. The negative {delta}{sup 34}S values of the massive peridotites could represent an ancient depletion event in the upper mantle. By contrast, the positive {delta}{sup 34}S values observed in the layered pryoxenites and the amphibole-rich dikes indicate that the two parent magmas had in common a mantle source variously enriched in {sup 34}S. Therefore, the present study reveals two extreme reservoirs characterized by different {delta}{sup 34}S values in the upper mantle. This range of variations can explain most {delta}{sup 34}S values found in MORB, continental tholeiites, and alkali basalts.

  19. Nanoporous LiMn2O4 spinel prepared at low temperature as cathode material for aqueous supercapacitors

    Science.gov (United States)

    Wang, F. X.; Xiao, S. Y.; Gao, X. W.; Zhu, Y. S.; Zhang, H. P.; Wu, Y. P.; Holze, R.

    2013-11-01

    LiMn2O4 spinel was prepared by a hydrothermal method using α-MnO2 nanotubes as precursor at 180 °C, a temperature much lower than that in previously reported methods. It is nanoporous with a pore size of about 40-50 nm and a BET surface area of 9.76 m2 g-1. It exhibits a high specific capacitance of 189 F g-1 at 0.3 A g-1 as a cathode for an aqueous supercapacitor. Even at 12 A g-1, it still has a capacitance of 166 F g-1. After 1500 cycles, there is no evident capacity fading. The LiMn2O4 cathode can deliver an energy density of 31.9 Wh kg-1 at 3480 W kg-1 and even maintain 19.4 Wh kg-1 at about 5100 W kg-1 based on the mass of LiMn2O4.

  20. Monitoring non-pseudomorphic epitaxial growth of spinel/perovskite oxide heterostructures by reflection high-energy electron diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Schütz, P.; Pfaff, F.; Scheiderer, P.; Sing, M.; Claessen, R. [Physikalisches Institut and Röntgen Center for Complex Material Systems (RCCM), Universität Würzburg, Am Hubland, D-97074 Würzburg (Germany)

    2015-02-09

    Pulsed laser deposition of spinel γ-Al{sub 2}O{sub 3} thin films on bulk perovskite SrTiO{sub 3} is monitored by high-pressure reflection high-energy electron diffraction (RHEED). The heteroepitaxial combination of two materials with different crystal structures is found to be inherently accompanied by a strong intensity modulation of bulk diffraction patterns from inelastically scattered electrons, which impedes the observation of RHEED intensity oscillations. Avoiding such electron surface-wave resonance enhancement by de-tuning the RHEED geometry allows for the separate observation of the surface-diffracted specular RHEED signal and thus the real-time monitoring of sub-unit cell two-dimensional layer-by-layer growth. Since these challenges are essentially rooted in the difference between film and substrate crystal structure, our findings are of relevance for the growth of any heterostructure combining oxides with different crystal symmetry and may thus facilitate the search for novel oxide heterointerfaces.

  1. MnCo{sub 2}O{sub 4} spinel chromium barrier coatings for SOFC interconnect by HVOF

    Energy Technology Data Exchange (ETDEWEB)

    Lagerbom, J.; Varis, T.; Pihlatie, M.; Himanen, O.; Saarinen, V.; Kiviaho, J.; Turunen, E. [VTT Technical Research Centre of Finland, Espoo (Finland); Puranen, J. [Tampere Univ. of Technology (Finland). Inst. of Materials Science

    2010-07-01

    Chromia released from steel parts used for interconnect plates by evaporation and condensation can quickly degrade the cell (cathode) performance in solid oxide fuel cell SOFC. Coatings on top of the IC plate can work as a chromium evaporation barrier. The coating material should have good electrical conductivity, high temperature stability and nearly the same coefficient of thermal expansion as the cell materials. One candidate for the coating material is MnCo{sub 2}O{sub 4} spinel because of its suitable properties. High velocity oxy fuel (HVOF) spraying was used for the coating application on Crofer 22 APU steel samples. Using commercial and self made spray dried powders together with an HV2000 spray gun it was possible to successfully manufacture, well adhering, dense and reasonably uniform coatings. The samples were tested in oxidation exposure tests in air followed by post analysis in SEM. Powders and coatings microstructures are presented here, both before and after exposure. It was found out that together with spraying parameters the powder characteristics used influence clearly to the coating quality. Especially as very thin coatings was aimed with dense structure fine powders was found to be essential. (orig.)

  2. YSZ-based sensor using Cr-Fe-based spinel-oxide electrodes for selective detection of CO.

    Science.gov (United States)

    Anggraini, Sri Ayu; Fujio, Yuki; Ikeda, Hiroshi; Miura, Norio

    2017-08-22

    A selective carbon monoxide (CO) sensor was developed by the use of both of CuCrFeO 4 and CoCrFeO 4 as the sensing electrode (SE) for yttria-stabilized zirconia (YSZ)-based potentiometric sensor. The sensing-characteristic examinations of the YSZ-based sensors using each of spinel oxides as the single-SE sensor showed that CuCrFeO 4 -SE had the ability to detect CO, hydrocarbons and NO x gases, while CoCrFeO 4 -SE was sensitive to hydrocarbons and NO x gases. Thus, when both SEs were paired as a combined-SEs sensor, the resulting sensor could generate a selective response to CO at 450 °C under humid conditions. The sensor was also capable of detecting CO in the concentration range of 20-700 ppm. Its sensing mechanism that was examined via polarization-curve measurements was confirmed to be based on mixed-potential model. The CO response generated by the combined-SEs sensor was unaffected by the change of water vapor concentration in the range of 1.3-11.5 vol% H 2 O. Additionally, the sensing performance was stable during 13 days tested. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Synthesis, characterization and photocatalytic properties of spinel CuAl2O4 nanoparticles by a sonochemical method

    International Nuclear Information System (INIS)

    Lv Weizhong; Liu Bo; Qiu Qi; Wang Fang; Luo Zhongkuan; Zhang Peixin; Wei Shaohui

    2009-01-01

    Spinel copper aluminate (CuAl 2 O 4 ) nanoparticles were synthesized with the aid of sonication by a precursor approach. The precursors were prepared by sonicating an aqueous solution of copper nitrate, aluminium nitrate, and urea. Upon heating at 900 deg. C for 6 h, the precursor formed nanosized CuAl 2 O 4 particles with an average size of 17 nm and with a surface area of about 110 m 2 g -1 . The nanosized copper aluminate particles as well as the precursors were characterized by elemental analysis, powder X-ray diffraction, transmission electron microscopy (TEM) image with electron diffraction pattern, thermogravimetric analysis, differential scanning calorimeter (DSC), Fourier transform of infrared spectroscopy (FT-IR), and Brunauer-Emmett-Teller (BET) surface area measurements. The photocatalytic degradation was investigated using methyl orange under the irradiation of Hg lamp (λ > 400 nm). The resulting degradation rates of the methyl orange were measured to be as high as 98% in 2 h.

  4. Influence of the preparation method on the morphology of templated NiCo{sub 2}O{sub 4} spinel

    Energy Technology Data Exchange (ETDEWEB)

    Cabo, Moises; Pellicer, Eva, E-mail: eva.pellicer.icn@uab.cat; Rossinyol, Emma; Solsona, Pau [Universitat Autonoma de Barcelona, Departament de Fisica, Facultat de Ciencies (Spain); Castell, Onofre [Universitat Autonoma de Barcelona, Servei de Microscopia, Facultat de Ciencies (Spain); Surinach, Santiago; Baro, Maria Dolors [Universitat Autonoma de Barcelona, Departament de Fisica, Facultat de Ciencies (Spain)

    2011-09-15

    The synthesis of NiCo{sub 2}O{sub 4} spinel by several nanocasting strategies (i.e., multi-step nanocasting, one-step nanocasting and soft-templating), in which nickel and cobalt nitrates are used as precursors and Pluronic P123 as surfactant, is explored. First, in the multi-step nanocasting, the effect of the impregnation method (evaporation, solid-liquid and two-solvent) of the SBA-15 silica template on the morphology of NiCo{sub 2}O{sub 4} replica is investigated. The evaporation method seems to be the best choice to obtain mesoporous NiCo{sub 2}O{sub 4} powder which, after calcination at 375 Degree-Sign C and subsequent template removal, displays the highest surface area (93.1 m{sup 2}/g). We have also checked the feasibility of the one-step nanoscating approach for the synthesis of ordered NiCo{sub 2}O{sub 4} arrays, though this methodology entails severe difficulties, mainly related to the different decomposition temperature of the nitrate precursors and the P123 surfactant. Finally, randomly oriented, aggregated NiCo{sub 2}O{sub 4} nanoparticles are obtained by means of P123 surfactant-assisted soft-templating approach.

  5. A Critical Review of Spinel Structured Iron Cobalt Oxides Based Materials for Electrochemical Energy Storage and Conversion

    Directory of Open Access Journals (Sweden)

    Hongyan Gao

    2017-11-01

    Full Text Available Iron cobalt oxides, such as typical FeCo2O4 and CoFe2O4, are two spinel structured transitional metal oxide materials with excellent electrochemical performance. As the electrodes, they have been widely applied in the current energy storage and conversion processes such as supercapacitors, Lithium-ion batteries and fuel cells. Based on synthesis approaches and controlled conditions, these two materials exhibited broad morphologies and nanostructures and thus distinct electrochemical performance. Some of them have shown promising applications as electrodes in energy storage and conversion. The incorporation with other materials to form composites further improved their performance. This review briefly summarized the recent applications of FeCo2O4 and CoFe2O4 in energy storage and conversion, current understandings on mechanisms and especially the relevance of morphologies and structures and composites to electrochemical performance. Some recommendations were finally put forward addressing current issues and future prospects on electrodes of FeCo2O4 and CoFe2O4 based materials in energy storage and conversion, implying there was still space to further optimize their performance.

  6. Delithiation/relithiation process of LiCoMnO4 spinel as 5 V electrode material

    Science.gov (United States)

    Dräger, Christoph; Sigel, Florian; Indris, Sylvio; Mikhailova, Daria; Pfaffmann, Lukas; Knapp, Michael; Ehrenberg, Helmut

    2017-12-01

    In this work, the LiCoMnO4 spinel has been synthesized by a two-step sol-gel based method, followed by sintering at temperatures up to 750 °C in oxygen. After structural characterization of the pristine material via synchrotron and neutron diffraction, the material was characterized via SEM and 6Li-MAS-NMR spectroscopy. 6Li-MAS-NMR spectroscopy in different states of charge revealed, that manganese and cobalt are distributed homogenously throughout the material and the delithiation primary occurs from the manganese environments. It was also shown, that it is not possible to fully delithiate the material in a practical voltage range of an electrolyte. Electrochemical cycling results reveal that about 70% of the lithium can be extracted and reinserted electrochemically in the voltage window from 4.5 to 5.4 V against lithium from/into LiCoMnO4. In situ synchrotron powder diffraction results show that lithium extraction/insertion occurs via a single-phase mechanism over the whole range of lithium contents and that the discharge capacity is mainly restricted by the voltage-window of the electrolyte. Furthermore it was shown, that the delithiation occurs up to a potential of 5.6 V.

  7. Elucidation of structural, vibrational and dielectric properties of transition metal (Co2+) doped spinel Mg-Zn chromites

    Science.gov (United States)

    Choudhary, Pankaj; Varshney, Dinesh

    2018-05-01

    Co2+ doped Mg-Zn spinel chromite compositions Mg0.5Zn0.5-xCoxCr2O4 (0.0 ≤ x ≤ 0.5) have been synthesized by the high-temperature solid state method. Synchrotron and X-ray diffraction (XRD) studies show single-phase crystalline nature. The structural analysis is validated by Rietveld refinement confirms the cubic structure with space group Fd3m. Crystallite size is estimated from Synchrotron XRD which was found to be 30-34 nm. Energy dispersive analysis confirms stoichiometric Mg0.5Zn0.5-xCoxCr2O4 composition. Average crystallite size distribution is estimated from imaging software (Image - J) of SEM is in the range of 100-250 nm. Raman spectroscopy reveals four active phonon modes, and a pronounced red shift is due to enhanced Co2+ concentration. Increased Co2+ concentration in Mg-Zn chromites shows a prominent narrowing of band gap from 3.46 to 2.97 eV. The dielectric response is attributed to the interfacial polarization, and the electrical modulus study supports non-Debye type of dielectric relaxation. Ohmic junctions (minimum potential drop) at electrode interface are active at lower levels of doping (x transformer applications at high frequencies.

  8. Dielectric studies of Co3-xMnxO4 (x=0.1-1.0) cubic spinel multiferroic

    Science.gov (United States)

    Meena, P. L.; Kumar, Ravi; Prajapat, C. L.; Sreenivas, K.; Gupta, Vinay

    2009-07-01

    A series of Co3-xMnxO4 (x =0.1-1.0) multiferroic cubic spinel ceramics were prepared to study the effect of Mn substitution at Co site on the crystal structures and dielectric properties. No significant change in the structural symmetry was observed with increasing x up to 1.0. A linear increase in lattice parameter with x is attributed to the substitution of Co3+ by Mn3+ (large ionic radii) at the octahedral sites. An antiferromagnetic-type ordering of Co3O4 changes to ferrimagnetic-type order after incorporation of Mn. The effect of Mn substitution on the dielectric constant and loss tangent was studied over a wide range of frequency (75 kHz-5 MHz) and temperature of 150-450 K. The measured value of room temperature ac conductivity at 1.0 MHz was found to increase from 2.0×10-6 to 4.4×10-4 Ω-1 cm-1 and follows power law (σac=Aωs) behavior. The dielectric constant ɛ'(ω) shows a weak frequency dispersion and small temperature dependence below 250 K for all ceramic samples. However, a strong temperature and frequency dependence on ɛ'(ω) was observed at higher temperature (>250 K). The temperature dependent ɛ'(ω) data show the existence of room temperature ferroelectricity in all prepared samples.

  9. Structural, magnetic and electrical properties of nickel doped Mn-Zn spinel ferrite synthesized by sol-gel method

    Energy Technology Data Exchange (ETDEWEB)

    Jalaiah, K., E-mail: kjalu4u@gmail.com [Department of Physics, Andhra University, Visakhapatnam 530003 (India); Vijaya Babu, K. [Advanced Analytical Laboratory, Andhra University, Visakhapatnam 530003 (India)

    2017-02-01

    Manganese ferrites (MnFe{sub 2}O{sub 4}) have been of great interest for their remarkable and soft-magnetic properties (low coercivity, moderate saturation magnetization) accompanied by good chemical stability and mechanical hardness. X-ray diffraction analysis confirmed the presence of single phase cubic spinel ferrite with space group Fm3m for all prepared samples. Structural parameters such as lattice constant, crystallite size were calculated from the studies of X-ray diffraction. The morphological analysis of all the compounds is studied using scanning electron microscope. The magnetic properties were measured using electron spin resonance (ESR) and vibrating sample magnetometer (VSM). The results obtained showed the formation of manganese ferrites with an average particle size are in good agreement with previous results and displayed good magnetic properties. The dielectric and impedance properties are studied over a frequency range 20 Hz–1 MHz at room temperature. - Highlights: • We prepared Mn{sub 0.85}Zn{sub 0.15}Ni{sub x}Fe{sub 2}O{sub 4} (x=0.03, 0.06, 0.09, 0.12 and 0.15) nano-ferrite materials by using sol-gel method. • All the compounds characterized by XRD, SEM, VSM, ESR and dielectric studies. • We get lower coercivity values. • We get good results from ESR spectra.

  10. An infrared study of the surface chemistry of lithium titanate spinel (Li4Ti5O12)

    International Nuclear Information System (INIS)

    Snyder, Mark Q.; DeSisto, William J.; Tripp, Carl P.

    2007-01-01

    While there are numerous studies examining the performance of lithium titanate spinel (LTS) as a lithium-ion battery, little is known about the surface chemistry of this material. In this paper, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy spectroscopy was used to study the type of surface groups present on LTS as a function of temperature. The surface was found to contain isolated and hydrogen-bonded TiOH groups and the dehydroxylation behavior with thermal treatment was similar to that of TiO 2 . In addition, hexamethyldisilazane (HMDZ) and pyridine were used to probe the reactivity of surface hydroxyl groups and the presence of Lewis acid sites, respectively. The reaction of HMDZ occurred with both LiOH and TiOH groups to form Li-O-Si and Ti-O-Si. In addition, the reaction of gaseous CO 2 with the Li + ions resulted in the formation of surface carbonate ions. The carbonate ions are removed by heating at 400 deg. C in air

  11. A prolonged Cenozoic erosional period in East Kunlun (Western China): Constraints of detrital apatite (U-Th)/He ages on the onset of mountain building along the northern margin of the Tibetan Plateau

    Science.gov (United States)

    Shi, Wenbei; Wang, Fei; Wu, Lin; Yang, Liekun; Zhang, Weibin; Wang, Yinzhi

    2018-01-01

    The timing of the development of the highland topography along the northern margin of the Tibetan Plateau is the key to understanding the manner of Tibetan growth and the far-field effects of the collision between India and Eurasia. Although various studies have investigated the exhumation and uplift of the basement rocks, thermochronological studies on the detritus from a continuous depositional sequence inan intermontane basin are lacking but might shed light on this issue. In this study, a set of detrital apatites from an upper Eocene to Pliocene depositional sequence in the Kumukol Basin, the largest intermontane basin in the East Kunlun, were dated by using the (U-Th)/He technique. The detrital apatites had consistent ages of ∼40 Ma for all deposit formations from bottom to top, which were older than the depositional ages. The ages and their consistency suggested that these detrital apatites were not reset and that the ages represented the original ages in the provenance region. These detrital apatite ages from the upper Eocene to Pliocene formations strongly suggested that the high mountains surrounding the Kumukol Basin formed at or before ∼40 Ma and have remained high since then. The process of mountain building resulted in a prolonged period of erosion from ∼40 to 2.6 Ma. The coupling of mountain and basin at ∼40 Ma was widespread along the East Kunlun. Our present results constrain the time of onset of the mountain building along the northern margin of the Tibetan Plateau, which may represent a rapid response to the India-Eurasian collision.

  12. South China provenance of the lower-grade Penglai Group north of the Sulu UHP orogenic belt, eastern China. Evidence from detrital zircon ages and Nd-Hf isotopic composition

    International Nuclear Information System (INIS)

    Li Xianghui; Chen Fukun; Guo Jinghui; Xie Liewen; Siebel, Wolfgang

    2007-01-01

    The Dabie-Sulu ultrahigh-pressure orogenic belt resulted from the early Mesozoic collision of the North China block and South China block (comprising the Yangtze and the Cathaysia) and subsequent exhumation of the subducted South China continental slabs. This belt consists of tectonically juxtaposed rock units of different metamorphic grade. Provenance of the low-grade metamorphic terranes exposed along the northern part of the belt can offer useful information about the location of the boundary between these two continental blocks. This study reports detrital zircon ages and Nd-Hf isotopic composition of sedimentary rocks of the low-grade Penglai Group, situated north of the Sulu UHP terrane. Results show that detrital zircon grains mostly crystallized during Mesoproterozoic time, clustering at 1.7 Ga to 1.6 Ga and 1.2 Ga. Nd isotopic composition (T DM value) of the Penglai Group suggests that sedimentary sources are similar to average crustal material of the Yangtze block and mostly formed in Paleo- to Mesoproterozoic. Late Mesoproterozoic detrital zircons probably demonstrate the sedimentary material was derived from the boundary of the Yangtze and Cathaysia blocks, which was formed by the late Mesoproterozoic convergence. Absence of Neoproterozoic detrital zircons from the Penglai sediments probably suggests a late Mesoproterozoic to early Neoproterozoic deposition age (about 1.1 Ga to 0.8 Ga). The age and isotopic evidence implies that the Penglai Group originated from the South China block and probably was thrust onto the basement of the North China block during the early Mesozoic continental collision. (author)

  13. A comparative study of detrital zircon ages from river sediment and rocks of the Karoo Supergroup (Late Carboniferous to Jurassic), Eastern Cape Province, South Africa : implications for the tectono-sedimentary evolution of Gondwanaland’s southern continental margin

    OpenAIRE

    2014-01-01

    M.Sc. (Geology) The Mzimvubu River, situated in the Eastern Cape Province of South Africa, drains essentially strata of the Late Carboniferous to Jurassic Karoo Supergroup with minor intersection of the underlying Devonian Msikaba Formation near the mouth of the river at Port St. Johns. Rock- and river sediment samples were collected at specific points from within the Mzimvubu River drainage basin, based on changes in the geology through which the rivers flow. Detrital zircon age populatio...

  14. Synthesis and characterization of advanced high capacity cathode active nanomaterials with three integrated spinel-layered phases for Li-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Bulut, Emrah, E-mail: ebulut@sakarya.edu.tr [Department of Chemistry, Sakarya University, 54187 Serdivan, Sakarya (Turkey); Can, Mustafa, E-mail: mstfacan@gmail.com [Vocational School of Arifiye, Sakarya University, 54580 Arifiye, Sakarya (Turkey); Özacar, Mahmut, E-mail: nmozacart@hotmail.com [Department of Chemistry, Sakarya University, 54187 Serdivan, Sakarya (Turkey); Akbulut, Hatem, E-mail: akbulut@Sakarya.edu.tr [Department of Metallurgical and Materials Engineering, Sakarya University, 54187 Serdivan, Sakarya (Turkey)

    2016-06-15

    Mesoporous cathode active materials that included undoped and separated Cu{sup 2+} and Co{sup 3+} doped spinels were prepared. The “doped spinel-Layered-Li-rich spinel” composite nanoparticles within the three integrated phased (LiM{sub 0,02}Mn{sub 1,98}O{sub 4}–Li{sub 2}MnO{sub 3}–Li{sub 1,27}Mn{sub 1,73}O{sub 4}; where M is Cu{sup 2+} and Co{sup 3+}) were synthesized by a microwave assisted hydrothermal synthesis. These materials were investigated with X-Ray powder Diffraction spectroscopy (XRD), Scanning Electron Microscopy (SEM and FE-SEM), High Resolution Transmission Electron Microscopy (HR-TEM), galvanostatic cycling at 0.1C and 0.5C rates, Cyclic Voltammetry (CV), and Electrochemical Impedance Spectroscopy (EIS). The effects of the calcination temperature and the partial substitution of Mn{sup 3+} in the spinel by Cu{sup 2+} and Co{sup 3+}, and onto the spinel structure were investigated with XRD. The lattice parameters of the spinel structured compounds were calculated from the XRD data using the Williamson-Hall equation. However, the morphological changes, which depended on the calcination temperature, were examined by SEM, FE-SEM and HRTEM. Furthermore, the two other phases which were different from LiM{sub 0,02}Mn{sub 1,98}O{sub 4} had a great impact on the electrochemical performance over the potential range of the 3–5 V. At the 0.1C rate, the first discharge capacities of undoped and Cu{sup 2+}, Co{sup 3+} doped materials were 577, 285, 560 mAh/g respectively. After 50 cycles at 0.5C rate, we achieved 96.2%; 52.5%; 95.4% capacity retention for the undoped and Cu{sup 2+}, Co{sup 3+} doped materials respectively. - Highlights: • Mesoporous cathode active nanomaterials with three integrated phase were synthesized. • The materials were characterized structurally by XRD, FE-SEM, HR-TEM. • Integrated phases provide an additional 400 mAh/g discharge capacity at low rate. • Higher specific capacities than literature values were achieved at 0

  15. X-ray diffraction at high pressure and high/low temperatures using synchrotron radiation. Applications in the study of spinel structures

    International Nuclear Information System (INIS)

    Gerward, L.; Jiang, J.Z.; Olsen, J.S.; Recio, J.M.; Wakowska, A.

    2004-01-01

    High-pressure x-ray diffraction made a quantum leap in the 1960's with the advent of the diamond-anvil cell. This ingenious device, where two opposing diamond faces apply pressure to a tiny sample, made it possible to replicate the pressure near the core of the Earth by turning a thumbscrew. Multianvil cells, such as the Japanese MAX80 press, were developed for combined high-pressure and high-temperature studies. The availability n at about the same time n of dedicated synchrotron radiation sources of hard x-rays was another big step forward. Since then, the white-beam energy-dispersive method has been the workhorse for high pressure, high-temperature x-ray diffraction, although it is now gradually being replaced by high-resolution monochromatic methods based on the image plate, the CCD camera or other electronic area detectors. The first part of the paper is a review of high-pressure x-ray diffraction (HPXRD), covering roughly the last three decades. Physical parameters, such as the bulk modulus, the compressibility and the equation of state, are defined. The diamond-anvil cell, the multianvil press and other high-pressure devices are described, as well as synchrotron radiation sources and recording techniques. Examples are drawn from current experimental and theoretical research on crystal structures of the spinel type. Accurate structural parameters have been determined at ambient conditions and at low temperatures using single-crystal diffraction and four-circle diffractometers. The uniform high-pressure behavior of the oxide spinels has been investigated in detail and compared with the corresponding behavior of selenium-based spinels. The synthesis of advanced novel materials is exemplified in the case of the cubic spinel Si 3 N 4 . This and other nitrogen spinels, which have a bulk modulus of about 300 GPa modulated by the actual cation, are opening a road towards superhard materials. The paper finishes off with an outlook into the future, where new

  16. Detrital zircon typology and U/Pb geochronology for the Miocene Ladrilleros-Juanchaco sedimentary sequence, Equatorial Pacific (Colombia): New constraints on provenance and paleogeography in northwestern South America

    Energy Technology Data Exchange (ETDEWEB)

    Osorio-Granada, E.; RESTREPO-MORENO, S.A.; MUÑOZ-VALENCIA, J.A.; TREJOS-TAMAYO, R.A.; PARDO-TRUJILLO, A.; BARBOSA-ESPITIA, A.A.

    2017-11-01

    Typology and internal texture analyses were performed on detrital zircons obtained from the Miocene sandstones of the Ladrilleros-Juanchaco sedimentary sequence (Colombia, Equatorial Pacific). This analysis was complemented with zircon U/Pb dating to identify typology-age associations as indicators of sediment provenance. Our results show that zircons with S and P dominant typologies have internal structures/zoning indicative of igneous, and potentially also metamorphic, origins. Morphometric results suggest limited transport from source areas. Both typology and U/Pb data point to the western Cordillera as the principal source of detrital materials for this sedimentary sequence. A paleogeographic reconstruction shows that, during the Late Miocene, significant portions of the western Cordillera were uplifted and actively eroding, thereby forming a fluvio-topographic barrier that prevented sediments from the central Cordillera reaching the Pacific basins. Exhumed Miocene plutons located along the axis of the western Cordillera may also have played a role as geomorphologically active massifs. This study demonstrates that typologic analysis on detrital zircon grains is a useful tool for establishing provenance and paleogeography in complex litho-tectonic areas where overlapping U/Pb signatures can lead to contradictory results.

  17. Pan-Gondwanaland post-collisional extension marked by 650 500 Ma alkaline rocks and carbonatites and related detrital zircons: A review

    Science.gov (United States)

    Veevers, J. J.

    2007-07-01

    Pan-Gondwanaland (650-500 Ma) tectonics is dominated by transcurrent motions driven by post-collisional oblique stresses. Extension is commonly marked by the intrusion of alkaline rocks, in particular A-type granite, nepheline syenite, and carbonatites (ARCs), during or after collision, as well as by field studies. ARCs of this age are common in Africa, South America, India, Antarctica, and Australia, and are indicated by related detrital zircons of 650-500 Ma age in Permian-Triassic and younger sediments from Australia, Antarctica, southern Africa, and India. Structural studies suggest that ARCs fill openings at releasing bends along transcurrent fractures and during reversal of the sense of motion as well as during relaxation of stress after collision. On the Paleo-Pacific margin, 550-500 Ma ARCs of the Koettlitz Glacier Alkaline Province were emplaced syn-tectonically within the Ross orogen during oblique subduction. The concentration of ARC magmas emplaced during the amalgamation of Gondwanaland is correlated with the transtension generated by the 650-570 Ma oblique subduction between Avalonia-Cadomia and the West African craton, and the 550-490 Ma oblique subduction of the Paleo-Pacific underneath Antarctica. In the Eastern Ghats and the Prince Charles Mountains of East Antarctica, ARCs and related zircons were generated 1000-900 Ma during an earlier continental collision.

  18. Detrital Zircon Geochronology of Sedimentary Rocks of the 3.6 - 3.2 Ga Barberton Greenstone Belt: No Evidence for Older Continental Crust

    Science.gov (United States)

    Drabon, N.; Lowe, D. R.; Byerly, G. R.; Harrington, J.

    2017-12-01

    The crustal setting of early Archean greenstone belts and whether they formed on or associated with blocks of older continental crust or in more oceanic settings remains a major issue in Archean geology. We report detrital zircon U-Pb age data from sandstones of the 3.26-3.20 Ga Fig Tree and Moodies Groups and from 3.47 to 3.23 Ga meteorite impact-related deposits in the 3.55-3.20 Ga Barberton greenstone belt (BGB), South Africa. The provenance signatures of these sediments are characterized by zircon age peaks at 3.54, 3.46, 3.40, 3.30, and 3.25 Ga. These clusters are coincident either with the ages of major episodes of felsic to intermediate igneous activity within and around the belt or with the ages of thin felsic tuffs reflecting distant volcanic activity. Only 15 of the reported 3410 grains (old zircons could represent felsic rocks in older, unexposed parts of the BGB sequence, but are too few to provide evidence for a continental source. This finding offers further evidence that the large, thick, high-standing, highly evolved blocks of continental crust with an andesitic bulk composition that characterize the Earth during younger geologic times were scarce in the early Archean.

  19. Sediment provenance in contractional orogens: The detrital zircon record from modern rivers in the Andean fold-thrust belt and foreland basin of western Argentina

    Science.gov (United States)

    Capaldi, Tomas N.; Horton, Brian K.; McKenzie, N. Ryan; Stockli, Daniel F.; Odlum, Margaret L.

    2017-12-01

    This study analyzes detrital zircon U-Pb age populations from Andean rivers to assess whether active synorogenic sedimentation accurately records proportional contributions from varied bedrock source units across different drainage areas. Samples of modern river sand were collected from west-central Argentina (28-33°S), where the Andes are characterized by active uplift and deposition in diverse contractional provinces, including (1) hinterland, (2) wedge-top, (3) proximal foreland, and (4) distal broken foreland basin settings. Potential controls on sediment provenance were evaluated by comparing river U-Pb age distributions with predicted age spectra generated by a sediment mixing model weighted by relative catchment exposure (outcrop) areas for different source units. Several statistical measures (similarity, likeness, and cross-correlation) are employed to compare how well the area-weighted model predicts modern river age populations. (1) Hinterland basin provenance is influenced by local relief generated along thrust-bounded ranges and high zircon fertility of exposed crystalline basement. (2) Wedge-top (piggyback) basin provenance is controlled by variable lithologic durability among thrust-belt bedrock sources and recycled basin sediments. (3) Proximal foreland (foredeep) basin provenance of rivers and fluvial megafans accurately reflect regional bedrock distributions, with limited effects of zircon fertility and lithologic durability in large (>20,000 km2) second-order drainage systems. (4) In distal broken segments of the foreland basin, regional provenance signatures from thrust-belt and hinterland areas are diluted by local contributions from foreland basement-cored uplifts.

  20. Multiband PSInSAR and long-period monitoring of land subsidence in a strategic detrital aquifer (Vega de Granada, SE Spain): An approach to support management decisions

    Science.gov (United States)

    Mateos, Rosa María; Ezquerro, Pablo; Luque-Espinar, Juan Antonio; Béjar-Pizarro, Marta; Notti, Davide; Azañón, Jose Miguel; Montserrat, Oriol; Herrera, Gerardo; Fernández-Chacón, Francisca; Peinado, Tomás; Galve, Jorge Pedro; Pérez-Peña, Vicente; Fernández-Merodo, Jose A.; Jiménez, Jorge

    2017-10-01

    This work integrates detailed geological and hydrogeological information with PSI data to obtain a better understanding of subsidence processes detected in the detrital aquifer of the Vega de Granada (SE Spain) during the past 13 years. Ground motion was monitored by exploiting SAR images from the ENVISAT (2003-2009), Cosmo-SkyMed (2011-2014) and Sentinel-1A (2015-2016) satellites. PSInSAR results show an inelastic deformation in the aquifer and small land surface displacements (up to -55 mm). The most widespread land subsidence is detected during the ENVISAT period (2003-2009), which coincided with a long, dry period in the region. The highest displacement rates recorded during this period (up to 10 mm/yr) were detected in the central part of the aquifer, where many villages are located. For this period, there is a good correlation between groundwater level depletion and the augmentation of the average subsidence velocity and slight hydraulic head changes (account critical levels of groundwater depletion to avoid land subsidence in the areas identified as vulnerable. The European Space Agency satellite Sentinel-1A could be an effective decision-making tool in the near future.

  1. Synthesis and electrochemical study of Mg{sub 1.5}MnO{sub 3}: A defect spinel cathode for rechargeable magnesium battery

    Energy Technology Data Exchange (ETDEWEB)

    Saha, Partha [Department of Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); US Department of Energy, National Energy Technology Laboratory, Morgantown, WV 26507 (United States); Jampani, Prashanth H., E-mail: pjampani@pitt.edu [Department of Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Hong, DaeHo [Department of Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Gattu, Bharat [Mechanical Engineering and Materials Science, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Poston, James A.; Manivannan, Ayyakkannu [US Department of Energy, National Energy Technology Laboratory, Morgantown, WV 26507 (United States); Datta, Moni Kanchan [Department of Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); US Department of Energy, National Energy Technology Laboratory, Morgantown, WV 26507 (United States); Kumta, Prashant N., E-mail: pkumta@pitt.edu [Department of Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); US Department of Energy, National Energy Technology Laboratory, Morgantown, WV 26507 (United States); Mechanical Engineering and Materials Science, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); School of Dental Medicine, University of Pittsburgh, PA 15261 (United States); Center for Complex Engineered Multifunctional Materials, University of Pittsburgh, Pittsburgh, PA 15261 (United States)

    2015-12-15

    Graphical abstract: Mg{sub 1.5}MnO{sub 3}, a defect oxide spinel derived by the Pechini route, was tested as cathode for rechargeable magnesium battery. TEM and XRD analyses of Mg{sub 1.5}MnO{sub 3} shows the formation of ∼100 nm sized nano particles in the cubic defect spinel structure (space group: Fd3m; unit cell: 0.833294 nm). Cyclic voltammetry illustrates a reversible reaction occurring between 0.3 and 1.5 V versus magnesium. Galvanostatic cycling of the Mg{sub 1.5}MnO{sub 3} cathode exhibits a low capacity of ∼12.4 mAh/g up to 20 cycle with ∼99.9% Coulombic efficiency when cycled at a current rate of ∼C/27. XPS (X-ray photoelectron spectroscopy) surface probe of magnesiated/de-magnesiated electrodes confirm a change in the redox center of Mn-ions during intercalation/de-intercalation of Mg-ion from the Mg{sub 1.5}MnO{sub 3} electrode. The low capacity of Mg{sub 1.5}MnO{sub 3} electrode mainly stem from the kinetic limitation of Mg-ion removal from the defect oxide spinel as the electrochemical impedance spectroscopy results of electrodes after 1st and 2nd cycle show that charge transfer resistance, R{sub e}, increases post charge state whereas interfacial resistance, R{sub i}, increases after discharge state, respectively. - Highlights: • Pechini process yields 100 nm sized particles of the defect cubic spinel Mg{sub 1.5}MnO{sub 3}. • Stable capacity of ∼12.4 mAh/g obtained at C/27 rate and 99.9% Coulombic efficiency. • XPS shows change in valence state of Mn{sup 3+}/Mn{sup 4+} center with cycling. • Low capacity stems from increase in charge-transfer and interfacial resistances with cycling. - Abstract: Mg{sub 1.5}MnO{sub 3}, a defect oxide spinel (space group: Fd3m; unit cell: 0.833294 nm) of particle size ∼100 nm derived by the Pechini route was tested as a cathode for rechargeable magnesium battery. Cyclic voltammetry illustrates a reversible reaction occurring in the 0.3–2.0 V potential window versus magnesium. The spinel however

  2. Surface modification of spinel λ-MnO2 and its lithium adsorption properties from spent lithium ion batteries

    International Nuclear Information System (INIS)

    Li, Li; Qu, Wenjie; Liu, Fang; Zhao, Taolin; Zhang, Xiaoxiao; Chen, Renjie; Wu, Feng

    2014-01-01

    Highlights: • A method is designed to synthesize a λ-MnO 2 ion-sieve for lithium ions adsorption. • Ultrasonic treatment with acid is highly efficient for lithium ions extraction. • Surface modification by CeO 2 is used to improve the adsorption capacity. • A 0.5 wt.% CeO 2 -coated ion-sieve shows the best adsorption properties. • λ-MnO 2 ion-sieves are promising for recovering scarce lithium resources. - Abstract: Spinel λ-MnO 2 ion-sieves are promising materials because of their high selectivity toward lithium ions, and this can be applied to the recovery of lithium from spent lithium ion batteries. However, manganese dissolution loss during the delithiation of LiMn 2 O 4 causes a decrease in adsorption capacity and poor cycling stability for these ion-sieves. To improve the lithium adsorption properties of λ-MnO 2 ion-sieves, surface modification with a CeO 2 coating was studied using hydrothermal-heterogeneous nucleation. The structure, morphology and composition of the synthesized materials were determined by XRD, SEM, TEM and EDS. The effect of hydrothermal synthesis conditions and the amount of CeO 2 coating on the adsorption performance of λ-MnO 2 were also investigated. A 0.5 wt.% CeO 2 -coated ion-sieve was synthesized by heating at 120 °C for 3 h and it had better adsorption properties than the bare samples. The effect of ultrasonic treatment on the lithium extraction ratio from LiMn 2 O 4 upon acid treatment at various temperatures was studied and the results were compared with conventional mechanical stirring. We found that ultrasonic treatment at lower temperature gave almost the same maximum lithium extraction ratio and was more efficient and economic

  3. Provenance of detrital zircons from the Ribeira and Dom Feliciano Belts, comparison with African equivalents and implications on western Gondwana amalgamation. Geological Society of London-2008

    International Nuclear Information System (INIS)

    Basei, M.; Frimmel, H.E.; Nutman, A.P.; Preciozzi, F.

    2005-01-01

    The geologic make-up of southern Brazil has been defined by processes related to the Brasiliano orogenic cycle and, in particular, to con tractional tectonic events that led to the amalgamation of different terranes, which culminated in the formation of Western Gondwana (Campos Neto and Figueiredo, 1995; Brito Neves and Cordani,1991; Brito Neves et al, 1999, Campos Neto, 2000). Polycyclic deformation and metamorphism that masked the characteristics, including the age records, of the protoliths were associated with the juxtaposition of these different terranes. Ophiolitic remains and magmatic arc roots signal the existence of fossil subduction and collision zones, whereas intense post-tectonic to an orogenic granitic magmatism marks the end of the orogenic cycle towards the end of the Neoproterozoic Era. U-Pb dating of domains within single zircon grains has proven to be a very powerful tool for the unraveling of the complex tecto no-thermal evolution as well as in characterizing the provenance of the original sediments. This is due to the high resistance to weathering and to high closure temperatures with respect to the U-Pb isotope system in zircon. Over the past decade, the standard technique for this analytical approach has become the analyses of U-Pb isotope ratios by SHRIMP,preceded by cathodoluminescence analysis (McClaren et al 1994). In this study, a set of 11 new SHRIMP analyses on detrital zircon grains from the major metasedimentary units of the Ribeira and Dom Feliciano Belts of the southeastern portion of South America is presented and the data are compared with available analyses for the Gariep Belt (Basei et al. 2005) and a new analysis for the Damara Belt. Combined with available Sm-Nd bulk rock isotope data, the results will form the basis for a revised tectonic model for the formation of Western Gondwana

  4. Provenance of detrital zircons from the Ribeira and Dom Feliciano Belts, comparison with African equivalents and implications on Western Gondwana amalgamation

    International Nuclear Information System (INIS)

    Basei, M.; Frimmel, H.E.; Nutman, A.P.; Preciozzi, F.

    2008-01-01

    The geologic make-up of southern Brazil has been defined by processes related to the Brasiliano orogenic cycle and, in particular, to con tractional tectonic events that led to the amalgamation of different terranes, which culminated in the formation of Western Gondwana (Campos Neto and Figueiredo, 1995; Brito Neves and Cordani, 1991; Brito Neves et al, 1999, Campos Neto, 2000). Polycyclic deformation and metamorphism that masked the characteristics, including the age records, of the protoliths were associated with the juxtaposition of these different terranes. Ophiolitic remains and magmatic arc roots signal the existence of fossil subduction and collision zones, whereas intense post-tectonic to an orogenic granitic magmatism marks the end of the orogenic cycle towards the end of the Neoproterozoic Era. U-Pb dating of domains within single zircon grains has proven to be a very powerful tool for the unraveling of the complex tecto no-thermal evolution as well as in characterizing the provenance of the original sediments. This is due to the high resistance to weathering and to high closure temperatures with respect to the U-Pb isotope system in zircon. Over the past decade, the standard technique for this analytical approach has become the analyses of U-Pb isotope ratios by SHRIMP, preceded by cathodoluminescence analysis (McClaren et al 1994). In this study, a set of 11 new SHRIMP analyses on detrital zircon grains from the major metasedimentary units of the Ribeira and Dom Feliciano Belts of the southeastern portion of South America is presented and the data are compared with available analyses for the Gariep Belt (Basei et al. 2005) and a new analysis for the Damara Belt. Combined with available Sm-Nd bulk rock isotope data, the results will form the basis for a revised tectonic model for the formation of Western Gondwana

  5. SAR interferometry monitoring of subsidence in a detritic basin related to water depletion in the underlying confined carbonate aquifer (Torremolinos, southern Spain).

    Science.gov (United States)

    Ruiz-Constán, A; Ruiz-Armenteros, A M; Martos-Rosillo, S; Galindo-Zaldívar, J; Lazecky, M; García, M; Sousa, J J; Sanz de Galdeano, C; Delgado-Blasco, J M; Jiménez-Gavilán, P; Caro-Cuenca, M; Luque-Espinar, J A

    2018-04-30

    This research underlines the need to improve water management policies for areas linked to confined karstic aquifers subjected to intensive exploitation, and to develop additional efforts towards monitoring their subsidence evolution. We analyze subsidence related to intensive use of groundwater in a confined karstic aquifer, through the use of the InSAR technique, by the southern coast of Spain (Costa del Sol). Carbonates are overlain by an unconfined detritic aquifer with interlayered high transmissivity rocks, in connection with the Mediterranean Sea, where the water level is rather stable. Despite this, an accumulated deformation in the line-of-sight (LOS) direction greater than -100 mm was observed by means of the ERS-1/2 (1992-2000) and Envisat (2003-2009) satellite SAR sensors. During this period, the Costa del Sol experienced a major population increase due to the expansion of the tourism industry, with the consequent increase in groundwater exploitation. The maximum LOS displacement rates recorded during both time spans are respectively -6 mm/yr and -11 mm/yr, respectively. During the entire period, there was an accumulated descent of the confined water level of 140 m, and several fluctuations of more than 80 m correlating with the subsidence trend observed for the whole area. Main sedimentary depocenters (up to 800 m), revealed by gravity prospecting, partly coincide with areas of subsidence maxima; yet ground deformation is also influenced by other factors, the main ones being the fine-grained facies distribution and rapid urbanization due to high touristic pressure. Copyright © 2018 Elsevier B.V. All rights reserved.

  6. A new parameterization for surface ocean light attenuation in Earth System Models: assessing the impact of light absorption by colored detrital material

    Science.gov (United States)

    Kim, G. E.; Pradal, M.-A.; Gnanadesikan, A.

    2015-03-01

    Light limitation can affect the distribution of biota and nutrients in the ocean. Light absorption by colored detrital material (CDM) was included in a fully coupled Earth System Model using a new parameterization for shortwave attenuation. Two model runs were conducted, with and without light attenuation by CDM. In a global average sense, greater light limitation associated with CDM increased surface chlorophyll, biomass and nutrients together. These changes can be attributed to the movement of biological productivity higher up the water column, which increased surface chlorophyll and biomass while simultaneously decreasing total biomass. Meanwhile, the reduction in biomass resulted in greater nutrient availability throughout the water column. Similar results were found on a regional scale in an analysis of the oceans by biome. In coastal regions, surface chlorophyll increased by 35% while total integrated phytoplankton biomass diminished by 18%. The largest relative increases in modeled surface chlorophyll and biomass in the open ocean were found in the equatorial biomes, while largest decreases in depth-integrated biomass and chlorophyll were found in the subpolar and polar biomes. This mismatch of surface and subsurface trends and their regional dependence was analyzed by comparing the competing factors of diminished light availability and increased nutrient availability on phytoplankton growth in the upper 200 m. Overall, increases in surface biomass were expected to accompany greater nutrient uptake and therefore diminish surface nutrients, but changes in light limitation decoupled trends between these two variables. Understanding changes in biological productivity requires both surface and depth-resolved information. Surface trends may be minimal or of the opposite sign to depth-integrated amounts, depending on the vertical structure of phytoplankton abundance.

  7. Detrital Zircon Provenance Record of Pre-Andean to Modern Tectonics in the Northern Andes: Examples from Peru, Ecuador, and Colombia

    Science.gov (United States)

    George, S. W. M.; Jackson, L. J.; Horton, B. K.

    2015-12-01

    Detrital zircon U-Pb age distributions from modern rivers and Mesozoic-Cenozoic basin fill in the northern Andes provide insights into pre-Andean, Andean, and active uplift and exhumation of distinctive sediment source regions. Diagnostic age signatures enable straightforward discrimination of competing sediment sources within the Andean magmatic arc (Western Cordillera-Central Cordillera), retroarc fold-thrust belt (Eastern Cordillera-Subandean Zone), and Amazonian craton (composed of several basement provinces). More complex, however, are the mid/late Cenozoic provenance records generated by recycling of basin fill originally deposited during early/mid Mesozoic extension, late Mesozoic thermal subsidence, and early Cenozoic shortening. Although subject to time-transgressive trends, regionally significant provenance patterns in Peru, Ecuador, and Colombia reveal: (1) Triassic-Jurassic growth of extensional subbasins fed by local block uplifts (with commonly unimodal 300­-150 Ma age peaks); (2) Cretaceous deposition in an extensive postrift setting fed by principally cratonic sources (with common 1800-900 Ma ages); and (3) Cenozoic growth of a broad flexural basin fed initially fed by magmatic-arc rocks (100-0 Ma), then later dominance by thrust-belt sedimentary rocks with progressively greater degrees of basin recycling (yielding diverse and variable age populations from the aforementioned source regions). U-Pb results from modern rivers and smaller subbasins prove useful in evaluating source-to-sink relationships, downstream mixing relationships, hinterland-foreland basin connectivity, paleodrainage integration, and tectonic/paleotopographic reconstructions. Most but not all of the elevated intermontane basins in the modern hinterland of the northern Andes contain provenance records consistent with genesis in a broader foreland basin developed at low elevation. Downstream variations within modern axial rivers and Cenozoic axial basins inform predictive models of

  8. Evidence of early Archean crust in northwest Gondwana, from U-Pb and Hf isotope analysis of detrital zircon, in Ediacaran surpacrustal rocks of northern Spain

    Science.gov (United States)

    Naidoo, Thanusha; Zimmermann, Udo; Vervoort, Jeff; Tait, Jenny

    2018-03-01

    The Mora Formation (Narcea Group) is one of the oldest Precambrian supracrustal successions in northern Spain. Here, we use U-Pb and in situ Hf isotope analysis on detrital zircon to determine its age and provenance. The youngest U-Pb dates constrain the maximum depositional age of the Mora Formation at 565 ± 11 Ma. Results indicate: (1) a dominant Ediacaran zircon population (33%; 565-633 Ma, Cadomian) within a spectrum of Neoproterozoic ages (40%; 636-996 Ma); and (2) smaller Mesoproterozoic (5%; 1004-1240 Ma), Palaeoproterozoic (11%; 1890-2476 Ma) and Archean (11%; 2519-3550 Ma) populations. Results here do not point to one specific cratonic source area; instead, detritus may have been derived from the West African craton and Amazonia, or even the concealed Iberian basement. The lack of 1.3-1.8 Ga grains suggests exclusion of the Sahara Craton as a major source, but this is not certain. This mixed composition favours a complex source history with reworking of detritus across terrane/craton boundaries. Hafnium isotope compositions indicate a range of crustal and juvenile sources, with initial ɛHf values between -15.8 and 11.1, and Hf model ages from 0.8 to 3.7 Ga. For Neoproterozoic zircons (80%), juvenile components (ɛHf(i) +10) may be related to Rodinia fragmentation and the onset of an active margin setting leading to the Cadomian orogeny. Palaeoproterozoic to Paleoarchean grains (20%) all have negative ɛHf values and Meso- to Eoarchean Hf model ages. This indicates an early (Archean) sialic crustal component for northwestern Gondwana.

  9. Interactive effects of an insecticide and a fungicide on different organism groups and ecosystem functioning in a stream detrital food web.

    Science.gov (United States)

    Dawoud, Mohab; Bundschuh, Mirco; Goedkoop, Willem; McKie, Brendan G

    2017-05-01

    Freshwater ecosystems are often affected by cocktails of multiple pesticides targeting different organism groups. Prediction and evaluation of the ecosystem-level effects of these mixtures is complicated by the potential not only for interactions among the pesticides themselves, but also for the pesticides to alter biotic interactions across trophic levels. In a stream microcosm experiment, we investigated the effects of two pesticides targeting two organism groups (the insecticide lindane and fungicide azoxystrobin) on the functioning of a model stream detrital food web consisting of a detritivore (Ispoda: Asellus aquaticus) and microbes (an assemblage of fungal hyphomycetes) consuming leaf litter. We assessed how these pesticides interacted with the presence and absence of the detritivore to affect three indicators of ecosystem functioning - leaf decomposition, fungal biomass, fungal sporulation - as well as detritivore mortality. Leaf decomposition rates were more strongly impacted by the fungicide than the insecticide, reflecting especially negative effects on leaf processing by detritivores. This result most like reflects reduced fungal biomass and increased detritivore mortality under the fungicide treatment. Fungal sporulation was elevated by exposure to both the insecticide and fungicide, possibly representing a stress-induced increase in investment in propagule dispersal. Stressor interactions were apparent in the impacts of the combined pesticide treatment on fungal sporulation and detritivore mortality, which were reduced and elevated relative to the single stressor treatments, respectively. These results demonstrate the potential of trophic and multiple stressor interactions to modulate the ecosystem-level impacts of chemicals, highlighting important challenges in predicting, understanding and evaluating the impacts of multiple chemical stressors on more complex food webs in situ. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Stratigraphy, tectonics and detrital zircon U-Pb (LA-ICP-MS) geochronology of the Rio Preto Belt and northern Paramirim corridor, NE, Brazil

    Energy Technology Data Exchange (ETDEWEB)

    Alcantara, Davi da Costa Bezerra Gobira de; Uhlein, Alexandre; Caxito, Fabricio de Andrade; Pedrosa-Soares, Antonio Carlos, E-mail: davibgobira@hotmail.com, E-mail: auhlein@gmail.com, E-mail: facaxito@yahoo.com.br, E-mail: pedrosasoares@gmail.com [Universidade Federal de Minas Gerais (CPMTC/UFMG), Belo Horizonte, MG (Brazil). Instituto de Geociencias. Centro de Pesquisa Professor Manoel Teixeira da Costa; Dussin, Ivo, E-mail: ivodusin@yahoo.com.br [Universidade Estadual do Rio de Janeiro (UERJ), Rio de Janeiro, RJ (Brazil). Faculdade de Geologia

    2017-04-15

    Two important Proterozoic metasedimentary sequences, the Rio Preto and Santo Onofre Groups, crop out along the northwestern margin of the Sao Francisco craton and in northern Paramirim corridor, respectively. The Rio Preto Group, involved in the eponymous fold-thrust belt along the northwestern cratonic boundary, comprises the Formosa (garnet schist, quartz schist, quartzite, chlorite-sericite schist and ferriferrous quartz schist) and Canabravinha (quartzite, micaceous quartzite, metarhytmite, phylite, schist and metaturbidite) formations. The Santo Onofre Group occurs exclusively in the Paramirim corridor, and is composed of quartzite and minor carbonaceous or Mn-rich phylite. These units record sedimentation in shallow to deep-water marine settings related to rift basins, and were deformed and metamorphosed under green schist facies conditions during the Brasiliano orogeny. Here we present 427 new detrital zircon U-Pb ages, which constrain the maximum depositional ages of ca. 971 Ma for the Santo Onofre Group, ca. 912 Ma for the Canabravinha Formation, and ca. 65 Ma for the Formosa Formation of the Rio Preto Group. Our data suggests that the Santo Onofre and the Rio Preto Groups accumulated in two distinct basin settings. The latter, composed mostly of sandy rocks, would represent a relatively stable, shallow-marine shelf environment. The Rio Preto Group, with metadiamictite, quartzite, pelitic and rhythmitic rocks, represents a shallow to deep marine environment influenced by gravity flows. Both groups were probably deposited in the Late Tonian, and are potential correlatives of the lower (pre-glacial) units of the Macaubas Group of the Aracuai belt. (author)

  11. Detrital zircon dating and tracing the provenance of dinosaur bone beds from the Late Cretaceous Wangshi Group in Zhucheng, Shandong, East China

    Directory of Open Access Journals (Sweden)

    Wei An

    2016-01-01

    Full Text Available The mass burial of dinosaur bone fossils in the Late Cretaceous Wangshi Group in Zhucheng, Shandong Province has been a research focus in recent years. However, the provenance of the dinosaur bone fossils and the accurate depositional age of the bone beds remain ambiguous. Through U–Pb dating of detrital zircons collected from six conglomerate samples from the dinosaur bone beds, we found that the youngest single grain age (YSG of sample 090414-24-D was 77.3 Ma, representing the maximum depositional age of the dinosaur fossil beds and sediments. This also indicates that the Hongtuya Formation was deposited during the Campanian. Dating results revealed an age peak of 120–110 Ma, which corresponds with the peak age of volcanic rocks of the Lower Cretaceous Qingshan Group. The volcanic rocks of the Qingshan Group are mainly exposed in Laiyang, to the north of Zhucheng, although a few also appear to the south and northwest. Through analysis of conglomerate composition and palaeocurrents in the sediments containing the bone beds, we found that the three different data sets of gravel compositions of the conglomerates were mainly composed of volcanic or pyroclastic rocks. Three different data sets of palaeocurrents suggested that the main sediment source of the Wangshi Group dinosaur bone beds was from the north−northwest of the Basin. Only one data set had a provenance south of the basin. This study revealed that the areas of Laiyang and the Yishu Fault Zone were the main provenance areas of both the dinosaur bone fossils and the sediments of the Wangshi Group in Zhucheng. The southern margin of the Zhucheng Basin may be a secondary source area. This research provides an important basis for judging the deposition time and the sediment source of fossil layers in the Wangshi Group, as well as reconstructing the palaeogeography of the Wangshi Group in the Jiaolai Basin.

  12. Assessing the role of detrital zircon sorting on provenance interpretations in an ancient fluvial system using paleohydraulics - Permian Cutler Group, Paradox Basin, Utah and Colorado

    Science.gov (United States)

    Findlay, C. P., III; Ewing, R. C.; Perez, N. D.

    2017-12-01

    Detrital zircon age signatures used in provenance studies are assumed to be representative of entire catchments from which the sediment was derived, but the extent to which hydraulic sorting can bias provenance interpretations is poorly constrained. Sediment and mineral sorting occurs with changes in hydraulic conditions driven by both allogenic and autogenic processes. Zircon is sorted from less dense minerals due to the difference in density, and any age dependence on zircon size could potentially bias provenance interpretations. In this study, a coupled paleohydraulic and geochemical provenance approach is used to identify changes in paleohydraulic conditions and relate them to spatial variations in provenance signatures from samples collected along an approximately time-correlative source-to-sink pathway in the Permian Cutler Group of the Paradox Basin. Samples proximal to the uplift have a paleoflow direction to the southwest. In the medial basin, paleocurrent direction indicates salt movement caused fluvial pathways divert to the north and northwest on the flanks of anticlines. Channel depth, flow velocity, and discharge calculations were derived from field measurements of grain size and dune and bar cross-stratification indicate that competency of the fluvial system decreased from proximal to the medial basin by up to a factor of 12. Based upon the paleohydraulic calculations, zircon size fractionation would occur along the transect such that the larger zircons are removed from the system prior to reaching the medial basin. Analysis of the size and age distribution of zircons from the proximal and distal fluvial system of the Cutler Group tests if this hydraulic sorting affects the expected Uncompahgre Uplift age distribution.

  13. Enhancement of Electrochemical Performance of LiMn2O4 Spinel Cathode Material by Synergetic Substitution with Ni and S

    Directory of Open Access Journals (Sweden)

    Monika Bakierska

    2016-05-01

    Full Text Available 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.

  14. Molecular dynamics simulations of spinels: LiMn2O4 and Li4Mn5O12 at high temperatures

    International Nuclear Information System (INIS)

    Ledwaba, R S; Matshaba, M G; Ngoepe, P E

    2015-01-01

    Energy storage technologies are critical in addressing the global challenge of clean sustainable energy. Spinel lithium manganates have attracted attention due to their electrochemical properties and also as promising cathode materials for lithium-ion batteries. The current study focused on the effects of high temperatures on the materials, in order to understand the sustainability in cases where the battery heats up to high temperature and analysis of lithium diffusion aids in terms of intercalation host compatibility. It is also essential to understand the high temperature behaviour and lithium ion host capability of these materials in order to perform the armorphization and recrystalization of spinel nano-architectures. Molecular dynamics simulations carried out to predict high temperature behaviour of the spinel systems. The NVE ensemble was employed, in the range 300 - 3000K. The melting temperature, lithium-ion diffusion and structural behaviour were monitored in both supercell systems. LiMn 2 O 4 indicated a diffusion rate that increased rapidly above 1500K, just before melting (∼1700K) and reached its maximum diffusion at 2.756 × 10 -7 cm 2 s -1 before it decreased. Li 4 Mn 5 O 12 indicated an exponential increase above 700K reaching 8.303 × 10 −7 cm 2 s −1 at 2000K and allowing lithium intercalation even above its melting point of around 1300K. This indicated better structural stability of Li 4 Mn 5 O 12 and capability to host lithium ions at very high temperatures (up to 3000 K) compared to LiMn 2 O 4 . (paper)

  15. Structural Changes and Material Transport in Al2O3-Supported Cu/Fe Spinel Particles in a Simulated Chemical Looping Combustion Environment

    Science.gov (United States)

    Nealley, W. H. Harrison; Nakano, Anna; Nakano, Jinichiro; Bennett, James P.

    2018-05-01

    Alumina-supported Cu/Fe spinel particles were exposed to oxidation/reduction atmospheres at 800°C. Structural changes of the particles subjected to gas cycles between air and 10 vol.% CO-90 vol.% Ar were studied from physical data and real-time images collected using a confocal scanning laser microscope equipped with a heating chamber. Overall particle volume slowly expanded with cycles while surface roughness decreased. Cross-sections of the exposed particles showed segregation of Cu and Fe to the edges of inner grains, which may have acted as oxygen carriers during the exposures. The particles remained whole during the cyclic exposures without any noticeable structural breakdown.

  16. Petrological, Geochemical and Sr–Nd–O Isotopic Constraints on the Origin of Garnet and Spinel Pyroxenites from the Moldanubian Zone of the Bohemian Massif

    Czech Academy of Sciences Publication Activity Database

    Svojtka, Martin; Ackerman, Lukáš; Medaris Jr., G.; Hegner, E.; Valley, J. W.; Hirajima, T.; Jelínek, E.; Hrstka, Tomáš

    2016-01-01

    Roč. 57, č. 5 (2016), s. 897-920 ISSN 0022-3530 Grant - others:Rada Programu interní podpory projektů mezinárodní spolupráce AV ČR(CZ) M100131203 Program:Program interní podpory projektů mezinárodní spolupráce AV ČR Institutional support: RVO:67985831 Keywords : garnet and spinel pyroxenites * Bohemian Massif * Sr, Nd, and oxygen isotopes * trace elements * subduction Subject RIV: DD - Geochemistry Impact factor: 3.280, year: 2016

  17. Nanocrystalline spinel ferrite (MFe2O4, M = Ni, Co, Mn, Mg, Zn) powders prepared by a simple aloe vera plant-extracted solution hydrothermal route

    International Nuclear Information System (INIS)

    Phumying, Santi; Labuayai, Sarawuth; Swatsitang, Ekaphan; Amornkitbamrung, Vittaya; Maensiri, Santi

    2013-01-01

    Graphical abstract: This figure shows the specific magnetization curves of the as-prepared MFe 2 O 4 (M = Ni, Co, Mn, Mg, Zn) powders obtained from room temperature VSM measurement. These curves are typical for a soft magnetic material and indicate hysteresis ferromagnetism in the field ranges of ±500 Oe, ±1000 Oe, and ±2000 Oe for the CoFe 2 O 4 , MgFe 2 O 4 and MnFe 2 O 4 respectively, whereas the samples of NiFe 2 O 4 and ZnFe 2 O 4 show a superparamagnetic behavior. Highlights: ► Nanocrystalline MFe 2 O 4 powders were synthesized by a novel hydrothermal method. ► Metal acetylacetonates and aloe vera plant-extracted solution are used. ► This biosynthetic route is very simple and provides high-yield oxide nanomaterials. ► XRD and TEM results indicate that the prepared samples have only spinel structure. ► The maximum M s of 68.9 emu/g at 10 kOe were observed for the samples of MnFe 2 O 4 . - Abstract: Nanocrystalline spinel ferrite MFe 2 O 4 (M = Ni, Co, Mn, Mg, Zn) powders were synthesized by a novel hydrothermal method using Fe(acac) 3 , M(acac) 3 (M = Ni, Co, Mn, Mg, Zn) and aloe vera plant extracted solution. The X-ray diffraction and selected-area electron diffraction results indicate that the synthesized nanocrystalline have only spinel structure without the presence of other phase impurities. The crystal structure and morphology of the spinel ferrite powders, as revealed by TEM, show that the NiFe 2 O 4 and CoFe 2 O 4 samples contain nanoparticles, whereas the MnFe 2 O 4 and MgFe 2 O 4 samples consist of many nanoplatelets and nanoparticles. Interestingly, the ZnFe 2 O 4 sample contains plate-like structure of networked nanocrystalline particles. Room temperature magnetization results show a ferromagnetic behavior of the CoFe 2 O 4 , MnFe 2 O 4 and MgFe 2 O 4 samples, whereas the samples of NiFe 2 O 4 and ZnFe 2 O 4 exhibit a superparamagnetic behavior

  18. In Situ Measurements of the Post-Spinel and Post-Garnet Phase Boundaries in Pyrolite at 17-32 GPa and 1500-2400 K

    Science.gov (United States)

    Ye, Y.; Gu, C.; Shim, S. H.; Prakapenka, V.; Meng, Y.

    2014-12-01

    Recent seismic studies have revealed complex structures near 660-km depth. In order to understand the effects of composition and temperature, we measured the depth and Clapeyron slope of the post-spinel and post-garnet boundaries at the pressure-temperature conditions of 600-700 km depths in pyrolitic compositions: (1) MgO-Al2O3-SiO2 (MAS) and (2) CaO-MgO-Al2O3-SiO2-FeO (CMASF). Glass starting materials were mixed with either gold or platinum powder (10 wt%) for laser coupling and internal pressure scale. Cold compressed foils of the mixtures were loaded in the diamond-anvil cell together with Ar or KCl for thermal insulation and pressure transmission. X-ray diffraction patterns were measured for the samples in the diamond-anvil cell at in situ high pressure and high temperature combined with double side laser heating at beamlines 13-IDD (GSECARS) and 16-IDB (HPCAT) in the Advanced Photon Source. Within 5 to 8 minutes of heating, stable crystalline phase assemblages were formed and persisted with further heating for 20 to 30 minutes. A total of 160 heating cycles were conducted at different pressures and temperatures, providing tight constrains on the phase boundaries. Our data show that the post-spinel transition occurs at 23.6-24.5 GPa and 1850 K with a Clapeyron slope of -2.5(4) MPa/K if the Pt pressure scales are used, consistent with the seismic observation of the 660 discontinuity. The post-garnet boundary occurs at 24.2-27.5 GPa and 1900 - 2450 K. We found that the Clapeyron slope of the post-garnet transition increases with Fe: from 2.4 MPa/K for MAS to 6.2 MPa/K for CMASF. Below 1900 K, garnet disappears near the post-spinel boundary within the resolution of our measurements. Our new data supports the notion that the 660 discontinuity is dominated by the post-spinel phase transition below 1900 K while dominated by the post-garnet phase transition above 1900 K. However, our data indicate much larger Clapeyron slope of the post-garnet transition, suggesting

  19. Improvement of catalytic activity in selective oxidation of styrene with H{sub 2}O{sub 2} over spinel Mg–Cu ferrite hollow spheres in water

    Energy Technology Data Exchange (ETDEWEB)

    Tong, Jinhui, E-mail: jinhuitong@126.com [Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education, Lanzhou 730070 (China); Key Laboratory of Gansu Polymer Materials, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070 (China); Cai, Xiaodong; Wang, Haiyan; Zhang, Qianping [Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education, Lanzhou 730070 (China); Key Laboratory of Gansu Polymer Materials, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070 (China)

    2014-07-01

    Graphical abstract: Uniform spinel Mg–Cu ferrite hollow spheres were prepared using carbon spheres as templates. Solid spinel Mg{sub 0.5}Cu{sub 0.5}Fe{sub 2}O{sub 4} ferrite nanocrystals were also prepared by sol–gel auto-combustion, hydrothermal and coprecipitation methods for comparison. The samples were found to be efficient catalysts for oxidation of styrene using hydrogen peroxide as oxidant. Especially, in the case of Mg{sub 0.5}Cu{sub 0.5}Fe{sub 2}O{sub 4} hollow spheres, obvious improvement on catalytic activity was observed and 21.2% of styrene conversion and 75.2% of selectivity for benzaldehyde were obtained at 80 °C for 6 h reaction in water. The catalyst can be magnetically separated easily for reuse and no obvious loss of activity was observed when reused in six consecutive runs. - Highlights: • Uniform spinel ferrite hollow spheres were prepared by a simple method. • The catalyst has been proved much more efficient for styrene oxidation than the reported analogues. • The catalyst can be easily separated by external magnetic field and has exhibited excellent reusability. • The catalytic system is environmentally friendly. - Abstract: Uniform spinel Mg–Cu ferrite hollow spheres were prepared using carbon spheres as templates. For comparison, solid Mg–Cu ferrite nanocrystals were also prepared by sol–gel auto-combustion, hydrothermal and coprecipitation methods. All the samples were characterized by Fourier transform infrared spectrophotometry (FT-IR), X-ray diffractometry (XRD), transmission electron microscopy (TEM) and N{sub 2} physisorption. The samples were found to be efficient catalysts for oxidation of styrene using hydrogen peroxide as oxidant. Especially, in the case of Mg{sub 0.5}Cu{sub 0.5}Fe{sub 2}O{sub 4} hollow spheres, obvious improvement on catalytic activity was observed, and 21.2% of styrene conversion and 75.2% of selectivity for benzaldehyde were obtained at 80 °C for 6 h reaction in water. The catalyst can be

  20. Characterization and evaluation of employment of nanostructured spinel MA on oxidation resistance of graffiti; Caracterizacao e avaliacao do emprego de espinelio MA nanoestruturado na resistencia a oxidacao de grafites

    Energy Technology Data Exchange (ETDEWEB)

    Vitor, P.A.M.; Guaglianoni, W.C.; Braganca, S.R.; Bergmann, C.P., E-mail: pedroaugusto89@hotmail.com [Universidade Federal do Rio Grande do Sul (LACER/UFRS), Porto Alegre, RS (Brazil). Laboratorio de Materiais Ceramicos

    2016-07-01

    This study aimed to investigate the obtaining of nanostructured powders of spinel MA (MgAl2O4) via synthesis of combustion in solution (SCS), and the influence of its incorporation in oxidation resistance in natural graphites. The crystalline phase only was obtained after a heat treatment at 900 ° C of the powder as-synthesized. The powders were characterized by differential thermal analysis (DTA) and thermogravimetric (ATG) and crystallographic analysis by X-ray diffraction (XRD) and Raman spectroscopy. The results, using thermogravimetric dynamic and isothermal analysis showed a relationship between embedded content of spinel (as-synthesized and calcined) and the raising of the temperature to start the oxidation process (onset temperature) of the samples. The rate of oxidation is reduced at temperatures from 700 ° C, retarding the oxidation of graphite with increasing level of spinel, but this effect ceases at temperatures above 1000 ° C. (author)

  1. Enhanced nonlinear optical absorption and optical limiting properties of superparamagnetic spinel zinc ferrite decorated reduced graphene oxide nanostructures

    International Nuclear Information System (INIS)

    Saravanan, M.; Sabari Girisun, T.C.

    2017-01-01

    Highlights: • Nanospindle and nanosphere ZnFe_2O_4 were decorated upon GO by hydrothermal method. • All the samples show superparamagnetism with almost zero coercivity and remanence. • The observed nonlinearity arises due to effective two photon absorption process. • Tuning of NLO behavior with variation in amount of ZnFe_2O_4 upon GO were achieved. • ZnFe_2O_4-(15 wt%)GO show higher NLO coefficients and superior limiting actions. - Abstract: Nonlinear absorption and optical limiting properties of ZnFe_2O_4-rGO magnetic nanostructures was investigated by the Z-scan technique using Q-switched Nd:YAG laser (5 ns, 532 nm, 10 Hz) as an excitation source. Excited state absorption was the dominant process responsible for the observed nonlinearity in ZnFe_2O_4 decorated rGO which arises due to photo-generated charge carriers in the conduction band of zinc ferrite and increases in defects at the surface of rGO due to the incorporation of ZnFe_2O_4. The magnitude of the nonlinear absorption co-efficient was found to be in the order of 10"−"1"0 m/W. A noteworthy enhancement in the third-order NLO properties in ZnFe_2O_4-(15 wt%) rGO with those of individual counter parts and well known graphene composites was reported. Role of induced defects states (sp"3) arising from the functionalization of rGO in the enhancement of NLO response was explained through Raman studies. Earlier incorporation and distribution of ZnFe_2O_4 upon GO through one-step hydrothermal method was analyzed by XRD and FTIR. Formation of (nanospheres/nanospindles) ZnFe_2O_4 along with reduction of graphene oxide was confirmed through TEM analysis. VSM studies showed zinc ferrite decorated rGO posseses superparamagnetic behavior. The tuning of nonlinear optical and magnetic behavior with variation in the content of spinel ferrites upon reduced graphene oxide provides an easy way to attain tunable properties which are exceedingly required in both optoelectronics and photothermal therapy

  2. Enhanced nonlinear optical absorption and optical limiting properties of superparamagnetic spinel zinc ferrite decorated reduced graphene oxide nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Saravanan, M.; Sabari Girisun, T.C., E-mail: sabarigirisun@bdu.ac.in

    2017-01-15

    Highlights: • Nanospindle and nanosphere ZnFe{sub 2}O{sub 4} were decorated upon GO by hydrothermal method. • All the samples show superparamagnetism with almost zero coercivity and remanence. • The observed nonlinearity arises due to effective two photon absorption process. • Tuning of NLO behavior with variation in amount of ZnFe{sub 2}O{sub 4} upon GO were achieved. • ZnFe{sub 2}O{sub 4}-(15 wt%)GO show higher NLO coefficients and superior limiting actions. - Abstract: Nonlinear absorption and optical limiting properties of ZnFe{sub 2}O{sub 4}-rGO magnetic nanostructures was investigated by the Z-scan technique using Q-switched Nd:YAG laser (5 ns, 532 nm, 10 Hz) as an excitation source. Excited state absorption was the dominant process responsible for the observed nonlinearity in ZnFe{sub 2}O{sub 4} decorated rGO which arises due to photo-generated charge carriers in the conduction band of zinc ferrite and increases in defects at the surface of rGO due to the incorporation of ZnFe{sub 2}O{sub 4}. The magnitude of the nonlinear absorption co-efficient was found to be in the order of 10{sup −10} m/W. A noteworthy enhancement in the third-order NLO properties in ZnFe{sub 2}O{sub 4}-(15 wt%) rGO with those of individual counter parts and well known graphene composites was reported. Role of induced defects states (sp{sup 3}) arising from the functionalization of rGO in the enhancement of NLO response was explained through Raman studies. Earlier incorporation and distribution of ZnFe{sub 2}O{sub 4} upon GO through one-step hydrothermal method was analyzed by XRD and FTIR. Formation of (nanospheres/nanospindles) ZnFe{sub 2}O{sub 4} along with reduction of graphene oxide was confirmed through TEM analysis. VSM studies showed zinc ferrite decorated rGO posseses superparamagnetic behavior. The tuning of nonlinear optical and magnetic behavior with variation in the content of spinel ferrites upon reduced graphene oxide provides an easy way to attain tunable

  3. Liquid flow deposited spinel (Ni,Mn){sub 3}O{sub 4} thin films for microbolometer applications

    Energy Technology Data Exchange (ETDEWEB)

    Le, Duc Thang, E-mail: ducthang36@skku.edu [Intelligent Electronic Component Team, Electronic Materials Convergence Division, Korea Institute of Ceramic Engineering and Technology, Seoul 153-801 (Korea, Republic of); School of Advanced Materials Science & Engineering, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Jeon, Chang Jun; Lee, Kui Woong; Jeong, Young Hun; Yun, Ji Sun [Intelligent Electronic Component Team, Electronic Materials Convergence Division, Korea Institute of Ceramic Engineering and Technology, Seoul 153-801 (Korea, Republic of); Yoon, Dae Ho, E-mail: dhyoon@skku.edu [School of Advanced Materials Science & Engineering, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Cho, Jeong Ho, E-mail: goedc@kicet.re.kr [Intelligent Electronic Component Team, Electronic Materials Convergence Division, Korea Institute of Ceramic Engineering and Technology, Seoul 153-801 (Korea, Republic of)

    2015-03-01

    Highlights: • Highly quality (Ni,Mn){sub 3}O{sub 4} thin films were grown using liquid flow deposited (LFD) technique. • It is possible to deposit multi–component manganite–oxide thin films by LFD at low temperatures. • Nickel–manganite films showed a good negative temperature coefficient (NTC) characteristic. • Liquid flow deposited (Ni,Mn){sub 3}O{sub 4} thin films are very potential for microbolometer applications. - Abstract: A liquid flow deposition (LFD) technique was initially used for the fabrication of single-component Mn{sub 3}O{sub 4} thin films onto Si wafer substrates at a range of substrate temperatures of 30–80 °C, with the introduction of an oxidizing reagent (H{sub 2}O{sub 2}). As a result, solid thin films were well formed from an aqueous solution. An X-ray diffraction (XRD) analysis showed typical characteristics of hausmannite Mn{sub 3}O{sub 4} with a spinel tetragonal phase. Field-emission scanning electron microscopy (FE-SEM) observations revealed nano-sized grains arranged uniformly on a dense and smooth surface for all of the as-deposited films. On the other hand, the LFD method was then extended to prepare two-component nickel–manganite films according to the binary chemical composition of Ni{sub x}Mn{sub 3−x}O{sub 4} with x = 0.02–0.2. The as-grown nickel–manganite films showed a surface with a good quality with a spherical bead-like architecture when x ≤ 0.10, while a conversion from spherical grains into highly porous nanowalls in the microstructure was noted in films when x ≥ 0.12. These results signify that it is possible to fabricate various multi-component manganite-oxide thin films at a low temperature. In addition, the dependences of the room-temperature electrical resistivity (ρ) and the temperature coefficient of resistance (TCR) on the Ni substitution level (x) were investigated on films annealed at 400 °C.

  4. Electronic, optical and transport properties of {alpha}-, {beta}- and {gamma}-phases of spinel indium sulphide: An ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Yamini, E-mail: sharma.yamini62@gmail.com [Department of Physics, Feroze Gandhi College, Rae Bareli 229001, U.P. (India); Srivastava, Pankaj [Department of Physics, Feroze Gandhi College, Rae Bareli 229001, U.P. (India)

    2012-08-15

    Spinel indium sulphide exists in three phases. The tetragonal {beta}-phase transforms to the cubic {alpha}-phase at 420 Degree-Sign C which further transforms to the trigonal {gamma}-phase at 754 Degree-Sign C. Due to wide energy bandgap, the phases of indium sulphide have possibilities of applications in photo-electrochemical solar cell devices as a replacement of toxic CdS. The electronic, optical and transport properties of the three phases have therefore been investigated using full potential linear augmented plane wave (FP-LAPW) + local orbitals (lo) scheme, in the framework of density functional theory (DFT) with generalized gradient approximation (GGA) for the purpose of exchange-correlation energy functional. We present the structure, energy bands and density of states (DOS) for {alpha}-, {beta}- and {gamma}-phases. The partial density of states (PDOS) of {beta}-In{sub 2}S{sub 3} is in good agreement with experiment and earlier ab initio calculations. To obtain the fundamental characteristics of these phases we have analysed their linear optical properties such as the dynamic dielectric function in the energy range of 0-15 eV. From the dynamic dielectric function it is seen that there is no directional anisotropy for {alpha}-phase since the longitudinal and transverse components are almost identical, however the {beta} and {gamma}-phases show birefringence. The optical absorption profiles clearly indicate that {beta}-phase has possibility of greater multiple direct and indirect interband transitions in the visible regions compared to the other phases. To study the existence of interesting thermoelectric properties, transport properties like electrical and thermal conductivities, Seebeck and Hall coefficients etc. are also calculated. Good agreements are found with the available experimental results. -- Highlights: Black-Right-Pointing-Pointer The electronic properties of phases of In{sub 2}S{sub 3} have been investigated. Black-Right-Pointing-Pointer The

  5. A new indicator mineral methodology based on a generic Bi-Pb-Te-S mineral inclusion signature in detrital gold from porphyry and low/intermediate sulfidation epithermal environments in Yukon Territory, Canada

    Science.gov (United States)

    Chapman, R. J.; Allan, M. M.; Mortensen, J. K.; Wrighton, T. M.; Grimshaw, M. R.

    2017-12-01

    Porphyry-epithermal and orogenic gold are two of the most important styles of gold-bearing mineralization within orogenic belts. Populations of detrital gold resulting from bulk erosion of such regions may exhibit a compositional continuum wherein Ag, Cu, and Hg in the gold alloy may vary across the full range exhibited by natural gold. This paper describes a new methodology whereby orogenic and porphyry-epithermal gold may be distinguished according to the mineralogy of microscopic inclusions observed within detrital gold particles. A total of 1459 gold grains from hypogene, eluvial, and placer environments around calc-alkaline porphyry deposits in Yukon (Nucleus-Revenue, Casino, Sonora Gulch, and Cyprus-Klaza) have been characterized in terms of their alloy compositions (Au, Ag, Cu, and Hg) and their inclusion mineralogy. Despite differences in the evolution of the different magmatic hydrothermal systems, the gold exhibits a clear Bi-Pb-Te-S mineralogy in the inclusion suite, a signature which is either extremely weak or (most commonly) absent in both Yukon orogenic gold and gold from orogenic settings worldwide. Generic systematic compositional changes in ore mineralogy previously identified across the porphyry-epithermal transition have been identified in the corresponding inclusion suites observed in samples from Yukon. However, the Bi-Te association repeatedly observed in gold from the porphyry mineralization persists into the epithermal environment. Ranges of P-T-X conditions are replicated in the geological environments which define generic styles of mineralization. These parameters influence both gold alloy composition and ore mineralogy, of which inclusion suites are a manifestation. Consequently, we propose that this methodology approach can underpin a widely applicable indicator methodology based on detrital gold.

  6. High-voltage LiNi0.5Mn1.5O4-d spinel material synthesized by microwave-assisted thermo-polymerization: some insights into the microwave-enhancing physico-chemistry

    CSIR Research Space (South Africa)

    Kebede, Mesfin A

    2017-10-01

    Full Text Available candidates as cathode materials29 for rechargeable lithium-ion batteries due to its ability to provide a30 high operating voltage (∼4.7 V) and 3-D channels for diffusion of31 lithium ions in its spinel structure.1–11 The advantageous properties32 of the LMNO... capability and long-term58 cycling) of nanostructured LMNO by virtue of tuning its Mn3+ con-59 centration.60 Aside from controlling the concentration of the Mn3+ in the61 spinel structure,11 it is known that the electrochemical performance62 of lithium-ion...

  7. Nitrogen-doped graphene aerogel-supported spinel CoMn2O4 nanoparticles as an efficient catalyst for oxygen reduction reaction

    Science.gov (United States)

    Liu, Yisi; Li, Jie; Li, Wenzhang; Li, Yaomin; Chen, Qiyuan; Zhan, Faqi

    2015-12-01

    Spinel CoMn2O4 (CMO) nanoparticles grown on three-dimensional (3D) nitrogen-doped graphene areogel (NGA) is prepared by a facile two-step hydrothermal method. The NGA not only possesses the intrinsic property of graphene, but also has abundant pore conformations for supporting spinel metal oxide nanoparticles, thus would be suitable as a good electrocatalysts' support for oxygen reduction reaction (ORR). The structure, morphology, porous properties, and chemical composition of CMO/NGA are investigated by X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, nitrogen adsorption-desorption measurements, and X-ray photoelectron spectroscopy (XPS). The electrocatalytic activity of catalysts is discussed by cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS), and rotating disk electrode (RDE) measurements in O2-saturated 0.1 M KOH electrolyte. The CMO/NGA hybrid exhibits more positive onset potential and half-wave potential, faster charge transfer than that of CMO and NGA, and its electrocatalytic performance is comparable with the commercial 20 wt.% Pt/C. Furthermore, it mainly favors a direct 4e- reaction pathway, and has excellent ethanol tolerance and high durability, which is attributed to the unique 3D crumpled porous nanostructure of NGA with large specific area and fast electron transport, and the synergic covalent coupling between the CoMn2O4 nanoparticles and NGA.

  8. Versatile electronic behavior of the Li{sub x}Mn{sub 3−x−y}Fe{sub y}O{sub 4} spinels

    Energy Technology Data Exchange (ETDEWEB)

    Alonso-Domínguez, D. [Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid (Spain); CEI Moncloa, UCM-UPM, Madrid (Spain); Álvarez-Serrano, I., E-mail: ias@quim.ucm.es [Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid (Spain); López, M.L.; Veiga, M.L.; Pico, C. [Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid (Spain); Mompeán, F.; García-Hernández, M. [Instituto de Ciencia de Materiales, CSIC, Cantoblanco, 28049 Madrid (Spain); Cuello, G.J. [Institut Laue-Langevin, 6 rue Jules Horowitz, F-38042 Grenoble (France)

    2013-11-15

    Highlights: •The Li{sub x}Mn{sub 3−x−y}Fe{sub y}O{sub 4} spinels show a versatile electronic behavior. •Optimal compositional ranges for different application fields are proposed. •Frustrated ferromagnetic response is compositionally driven. •High ε′ values are obtained when B sites are occupied by both Mn and Fe cations. •High lithium contents are linked to the electrochemical behavior. -- Abstract: The detailed structural and electronic characterization of microcrystalline powders of new spinels Li{sub x}Mn{sub 3−x−y}Fe{sub y}O{sub 4} (0.4 ⩽ x ⩽ 1.33; 0 ⩽ y ⩽ 1.30), obtained by the “liquid mix” method, is reported. Compositional characterization was carried out by means of thermogravimetric analysis, energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy, and their structure was refined from neutron and X-ray diffraction showing a cubic symmetry between 5 and 550 K, Space Group Fd3{sup ¯}m. However, at temperatures above ca. 950 K, a reversible transformation, probably implying the formation of an ordered vacant phase, has been detected. The magnetic behavior, analyzed from neutron diffraction data and magnetization measurements, is interpreted considering an “incomplete” ferrimagnetic response, due to magnetic frustration in the B sites. Potential applications have been evaluated from the magnetocaloric, electrochemical and dielectric behavior in selected compositional ranges.

  9. Oxygen vacancies at the spinel/perovskite γ-Al{sub 2}O{sub 3}/SrTiO{sub 3} heterointerface probed by resonant photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Schuetz, Philipp; Pfaff, Florian; Zapf, Michael; Gabel, Judith; Dudy, Lenart; Berner, Goetz; Sing, Michael; Claessen, Ralph [Physikalisches Institut and Roentgen Center for Complex Material Systems (RCCM), Universitaet Wuerzburg (Germany); Chen, Yunzhong; Pryds, Nini [Department of Energy Conversion and Storage, Technical University of Denmark, Risoe (Denmark); Schlueter, Christoph; Lee, Tien-Lin [Diamond Light Source Ltd., Harwell Science and Innovation Campus, Didcot (United Kingdom)

    2016-07-01

    The spinel/perovskite heterointerface between the band insulators γ-Al{sub 2}O{sub 3} and SrTiO{sub 3} hosts a two-dimensional electron system (2DES) with exceptionally high electron mobility. Soft x-ray resonant photoelectron spectroscopy at the Ti L absorption edge is used to probe the Ti 3d derived interface states. Marked differences in the resonance behavior are found for the SrTiO{sub 3} valence band and the different interface states, which are observed in the band gap of SrTiO{sub 3}. A comparison to X-ray absorption spectra of Ti 3d{sup 0} and Ti 3d{sup 1} systems reveals the presence of different types of electronic states with Ti 3d character, i.e., oxygen vacancy induced, trapped in-gap states and itinerant states contributing to the 2DES. Exposure to low doses of oxygen during irradiation allows for the reversible manipulation of the oxygen stoichiometry, thus revealing the presence of an oxygen vacancy-induced state, which is characteristic for this spinel/perovskite interface.

  10. Epitaxial Fe{sub 3-x}Ti{sub x}O{sub 4} films from magnetite to ulvöspinel by pulsed laser deposition

    Energy Technology Data Exchange (ETDEWEB)

    Droubay, T.C.; Pearce, C.I.; Ilton, E.S.; Engelhard, M.H.; Engelhard, M.H.; Heald, S.M.; Arenholz, E.; Rosso, K.M.

    2011-07-21

    Epitaxial films along the Fe{sub 3-x}Ti{sub x}O{sub 4} (titanomagnetite) compositional series from pure end-members magnetite (Fe{sub 3}O{sub 4}) to ulvöspinel (Fe{sub 2}TiO{sub 4}) were successfully grown by pulsed laser deposition on MgO(100) substrates. Spectroscopic characterization including high resolution x-ray diffraction, x-ray photoelectron spectroscopy, and synchrotron-based x-ray absorption and magnetic circular dichroism consistently shows that Ti(IV) substitutes for Fe(III) in the inverse spinel lattice with a proportional increase in lattice Fe(II) concentration. No evidence of Ti interstitials, spinodal decomposition, or secondary phases was found in the bulk of the grown films. At the uppermost few nanometers of the Ti-bearing film surfaces, evidence suggests that Fe(II) is susceptible to facile oxidation, and that an associated lower Fe/Ti ratio in this region is consistent with surface compositional incompleteness or alteration to a titanomaghemite-like composition and structure. The surface of these films nonetheless appear to remain highly ordered and commensurate with the underlying structure despite facile oxidation, a surface condition that is found to be reversible to some extent by heating in low oxygen environments.

  11. Electrochemical and Electronic Charge Transport Properties of Ni-Doped LiMn2O4 Spinel Obtained from Polyol-Mediated Synthesis

    Directory of Open Access Journals (Sweden)

    Shuo Yang

    2018-05-01

    Full Text Available LiNi0.5Mn1.5O4 (LNMO spinel has been extensively investigated as one of the most promising high-voltage cathode candidates for lithium-ion batteries. The electrochemical performance of LNMO, especially its rate performance, seems to be governed by its crystallographic structure, which is strongly influenced by the preparation methods. Conventionally, LNMO materials are prepared via solid-state reactions, which typically lead to microscaled particles with only limited control over the particle size and morphology. In this work, we prepared Ni-doped LiMn2O4 (LMO spinel via the polyol method. The cycling stability and rate capability of the synthesized material are found to be comparable to the ones reported in literature. Furthermore, its electronic charge transport properties were investigated by local electrical transport measurements on individual particles by means of a nanorobotics setup in a scanning electron microscope, as well as by performing DFT calculations. We found that the scarcity of Mn3+ in the LNMO leads to a significant decrease in electronic conductivity as compared to undoped LMO, which had no obvious effect on the rate capability of the two materials. Our results suggest that the rate capability of LNMO and LMO materials is not limited by the electronic conductivity of the fully lithiated materials.

  12. Crystallographic origin of cycle decay of the high-voltage LiNi0.5Mn1.5O4 spinel lithium-ion battery electrode.

    Science.gov (United States)

    Pang, Wei Kong; Lu, Cheng-Zhang; Liu, Chia-Erh; Peterson, Vanessa K; Lin, Hsiu-Fen; Liao, Shih-Chieh; Chen, Jin-Ming

    2016-06-29

    High-voltage spinel LiNi0.5Mn1.5O4 (LNMO) is considered a potential high-power-density positive electrode for lithium-ion batteries, however, it suffers from capacity decay after extended charge-discharge cycling, severely hindering commercial application. Capacity fade is thought to occur through the significant volume change of the LNMO electrode occurring on cycling, and in this work we use operando neutron powder diffraction to compare the structural evolution of the LNMO electrode in an as-assembled 18650-type battery containing a Li4Ti5O12 negative electrode with that in an identical battery following 1000 cycles at high-current. We reveal that the capacity reduction in the battery post cycling is directly proportional to the reduction in the maximum change of the LNMO lattice parameter during its evolution. This is correlated to a corresponding reduction in the MnO6 octahedral distortion in the spinel structure in the cycled battery. Further, we find that the rate of lattice evolution, which reflects the rate of lithium insertion and removal, is ∼9 and ∼10% slower in the cycled than in the as-assembled battery during the Ni(2+)/Ni(3+) and Ni(3+)/Ni(4+) transitions, respectively.

  13. Magnetic phase diagrams of the spinels AB2xGa2-2xO4 (A = Zn, Co; B = Al, Cr) systems

    International Nuclear Information System (INIS)

    Hamedoun, M.; Masrour, R.; Bouslykhane, K.; Hourmatallah, A.; Benzakour, N.

    2008-01-01

    The magnetic properties of the spinels CoAl 2x Ga 2-2x O 4 and ZnCr 2x Ga 2-2x O 4 systems in the range 0 ≤ x ≤ 1 have been studied by mean field theory and high-temperature series expansions. By using the first theory, we have evaluated the nearest neighbour and the next-neighbour super-exchange interaction J 1 (x) and J 2 (x), respectively, for the first systems in the range 0 ≤ x ≤ 1 and J 1 (x = 1), J 2 (x = 1) for the second system. The intra-planar and the inter-planar interactions are deduced. The corresponding classical exchange energy for magnetic structure is obtained for the first system. The second theory have been applied in the spinels CoAl 2x Ga 2-2x O 4 and ZnCr 2x Ga 2-2x O 4 systems, combined with the Pade approximants method, we have obtained the magnetic phase diagrams (T N versus dilution x) in the range 0 ≤ x ≤ 1. The obtained theoretical results are in agreement with experimental ones obtained by magnetic measurements and Moessbauer spectroscopy. The threshold percolation in the second system is x p ∼ 0.4. The critical exponents associated with the magnetic susceptibility (γ) and the correlation lengths (ν) are deduced in the range 0 ≤ x ≤ 1

  14. The performance of spinel bulk-like oxygen-deficient CoGa2O4 as an air-cathode catalyst in microbial fuel cell

    Science.gov (United States)

    Liu, Di; Mo, Xiaoping; Li, Kexun; Liu, Yi; Wang, Junjie; Yang, Tingting

    2017-08-01

    Nano spinel bulk-like CoGa2O4 prepared via a facile hydrothermal method is used as a high efficient electrochemical catalyst in activated carbon (AC) air-cathode microbial fuel cell (MFC). The maximum power density of the modified MFC is 1911 ± 49 mW m-2, 147% higher than the MFC of untreated AC cathode. Transmission electron microscope (TEM) and X-ray diffraction (XRD) exhibit the morphology and crystal structure of CoGa2O4. Rotating disk electrode (RDE) confirms the four-electron pathway at the cathode during the oxygen reduction reaction (ORR). Thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) illustrate that the high rate oxygen vacancy exist in the CoGa2O4. The oxygen vacancy of CoGa2O4 plays an important role in catalytic activity. In a word, the prepared nano spinel bulk-like CoGa2O4 provides an alternative to the costly Pt in air-cathode for power output.

  15. 3D CNT macrostructure synthesis catalyzed by MgFe2O4 nanoparticles-A study of surface area and spinel inversion influence

    Science.gov (United States)

    Zampiva, Rúbia Young Sun; Kaufmann Junior, Claudir Gabriel; Pinto, Juliano Schorne; Panta, Priscila Chaves; Alves, Annelise Kopp; Bergmann, Carlos Pérez

    2017-11-01

    The MgFe2O4 spinel exhibits remarkable magnetic properties that open up numerous applications in biomedicine, the environment and catalysis. MgFe2O4 nanoparticles are excellent catalyst for carbon nanotube (CNT) production. In this work, we proposed to use MgFe2O4 nanopowder as a catalyst in the production of 3D macroscopic structures based on CNTs. The creation of these nanoengineered 3D architectures remains one of the most important challenges in nanotechnology. These systems have high potential as supercapacitors, catalytic electrodes, artificial muscles and in environmental applications. 3D macrostructures are formed due to an elevated density of CNTs. The quantity and quality of the CNTs are directly related to the catalyst properties. A heat treatment study was performed to produce the most effective catalyst. Factors such as superficial area, spinel inversion, crystallite size, degree of agglomeration and its correlation with van der Waals forces were examined. As result, the ideal catalyst properties for CNT production were determined and high-density 3D CNT macrostructures were produced successfully.

  16. Structural Rietveld refinement and vibrational study of MgCr{sub x}Fe{sub 2−x}O{sub 4} spinel ferrites

    Energy Technology Data Exchange (ETDEWEB)

    Sabri, K. [Laboratoire des Sciences et technique de l’Environnement et de la Valorisation, département de Génie des Procédés, Université de Mostaganem, Mostaganem (Algeria); Rais, A., E-mail: amrais@yahoo.com [Laboratoire des Sciences et technique de l’Environnement et de la Valorisation, département de Génie des Procédés, Université de Mostaganem, Mostaganem (Algeria); Taibi, K. [Laboratoire de Science et Génie des Matériaux, USTHB, Alger, Algéria (Algeria); Moreau, M.; Ouddane, B. [Laboratory of LASIR Spectrochemistry, University of Science and Technology, 59650 Villeneuve d’Ascq (France); Addou, A. [Laboratoire des Sciences et technique de l’Environnement et de la Valorisation, département de Génie des Procédés, Université de Mostaganem, Mostaganem (Algeria)

    2016-11-15

    Spinel ferrites with the general formula MgCr{sub x}Fe{sub 2−x}O{sub 4} (0≤x≤1) were synthesized by the standard ceramic technique and characterized by X-ray diffraction. The XRD patterns confirmed that the mixed ferrite samples are in the cubic spinel structure which is further validated by Rietveld refinement in the space group Fd3m. The crystal structure and cell parameters were refined by Rietveld analysis. The vibrational study was achieved using Fourier Transform-InfraRed (FT-IR) and Raman spectroscopy. From FT-IR band frequencies, the force constants K{sub t} and K{sub o} , for tetrahedra