Sample records for compounds silicates metal

  1. Hydrothermal Synthesis of Metal Silicates

    Institute of Scientific and Technical Information of China (English)

    Lii Kwang-Hwa


    Organically templated metal phosphates have been extensively studied because of interesting structural chemistry and potential applications in catalysis. However, in most cases the organic templates cannot be removed without collapse of the frameworks. This is in contrast to the high thermal stability and extensive applications of zeolites in refinery and petrochemical processes.Therefore, studies have been directed to the synthesis of transition metal silicates to produce more stable frameworks. Our synthetic methods are twofold, namely mild hydrothermal reactions in Teflon-lined autoclaves at 100-200 ℃ using organic amines as templates and high-temperature,high-pressure hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca. 550 ℃ and 150 Mpa using alkali metal cations as templates. In this presentation I will report the high-temperature, high-pressure hydrothermal synthesis, crystal structures, and solid-state NMR spectroscopy of a number of new silicates of indium, uranium, and transition metals.

  2. High Pressure/Temperature Metal Silicate Partitioning of Tungsten (United States)

    Shofner, G. A.; Danielson, L.; Righter, K.; Campbell, A. J.


    The behavior of chemical elements during metal/silicate segregation and their resulting distribution in Earth's mantle and core provide insight into core formation processes. Experimental determination of partition coefficients allows calculations of element distributions that can be compared to accepted values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Tungsten (W) is a moderately siderophile element and thus preferentially partitions into metal versus silicate under many planetary conditions. The partitioning behavior has been shown to vary with temperature, silicate composition, oxygen fugacity, and pressure. Most of the previous work on W partitioning has been conducted at 1-bar conditions or at relatively low pressures, i.e. <10 GPa, and in two cases at or near 20 GPa. According to those data, the stronger influences on the distribution coefficient of W are temperature, composition, and oxygen fugacity with a relatively slight influence in pressure. Predictions based on extrapolation of existing data and parameterizations suggest an increased pressured dependence on metal/ silicate partitioning of W at higher pressures 5. However, the dependence on pressure is not as well constrained as T, fO2, and silicate composition. This poses a problem because proposed equilibration pressures for core formation range from 27 to 50 GPa, falling well outside the experimental range, therefore requiring exptrapolation of a parametereized model. Higher pressure data are needed to improve our understanding of W partitioning at these more extreme conditions.

  3. Experiments on metal-silicate plumes and core formation. (United States)

    Olson, Peter; Weeraratne, Dayanthie


    Short-lived isotope systematics, mantle siderophile abundances and the power requirements of the geodynamo favour an early and high-temperature core-formation process, in which metals concentrate and partially equilibrate with silicates in a deep magma ocean before descending to the core. We report results of laboratory experiments on liquid metal dynamics in a two-layer stratified viscous fluid, using sucrose solutions to represent the magma ocean and the crystalline, more primitive mantle and liquid gallium to represent the core-forming metals. Single gallium drop experiments and experiments on Rayleigh-Taylor instabilities with gallium layers and gallium mixtures produce metal diapirs that entrain the less viscous upper layer fluid and produce trailing plume conduits in the high-viscosity lower layer. Calculations indicate that viscous dissipation in metal-silicate plumes in the early Earth would result in a large initial core superheat. Our experiments suggest that metal-silicate mantle plumes facilitate high-pressure metal-silicate interaction and may later evolve into buoyant thermal plumes, connecting core formation to ancient hotspot activity on the Earth and possibly on other terrestrial planets.

  4. Estimation of high temperature metal-silicate partition coefficients (United States)

    Jones, John H.; Capobianco, Christopher J.; Drake, Michael J.


    It has been known for some time that abundances of siderophile elements in the upper mantle of the Earth are far in excess of those expected from equilibrium between metal and silicate at low pressures and temperatures. Murthy (1991) has re-examined this excess of siderophile element problem by estimating liquid metal/liquid silicate partition coefficients reduces from their measured values at a lower temperature, implying that siderophile elements become much less siderophilic at high temperatures. Murthy then draws the important conclusion that metal/silicate equilibrium at high temperatures can account for the abundances of siderophile elements in the Earth's mantle. Of course, his conclusion is critically dependent on the small values of the partition coefficients he calculates. Because the numerical values of most experimentally-determined partition coefficients increase with increasing temperature at both constant oxygen fugacity and at constant redox buffer, we think it is important to try an alternative extrapolation for comparison. We have computed high temperature metal/silicate partition coefficients under a different set of assumptions and show that such long temperature extrapolations yield values which are critically dependent upon the presumed chemical behavior of the siderophile elements in the system.

  5. Light metal compound casting

    Institute of Scientific and Technical Information of China (English)

    Konrad; J.; M.; PAPIS; Joerg; F.; LOEFFLER; Peter; J.; UGGOWITZER


    Compound casting’simplifies joining processes by directly casting a metallic melt onto a solid metal substrate. A continuously metallurgic transition is very important for industrial applications, such as joint structures of spaceframe constructions in transport industry. In this project, ‘compound casting’ of light metals is investigated, aiming at weight-saving. The substrate used is a wrought aluminium alloy of type AA5xxx, containing magnesium as main alloying element. The melts are aluminium alloys, containing various alloying elements (Cu, Si, Zn), and magnesium. By replacing the natural oxygen layer with a zinc layer, the inherent wetting difficulties were avoided, and compounds with flawless interfaces were successfully produced (no contraction defects, cracks or oxides). Electron microscopy and EDX investigations as well as optical micrographs of the interfacial areas revealed their continu- ously metallic constitution. Diffusion of alloying elements leads to heat-treatable microstructures in the vicinity of the joining interfaces in Al-Al couples. This permits significant variability of mechanical properties. Without significantly cutting down on wettability, the formation of low-melting intermetallic phases (Al3Mg2 and Al12Mg17 IMPs) at the interface of Al-Mg couples was avoided by applying a protective coating to the substrate.

  6. Light metal compound casting

    Institute of Scientific and Technical Information of China (English)



    'Compound casting'simplifies joining processes by directly casting a metallic melt onto a solid metal substrate. A continuously metallurgic transition is very important for industrial applications, such as joint structures of spaceframe constructions in transport industry. In this project, 'compound casting' of light metals is investigated, aiming at weight-saving. The substrate used is a wrought aluminium alloy of type AA5xxx, containing magnesium as main alloying element. The melts are aluminium alloys, containing various alloying elements (Cu, Si, Zn), and magnesium. By replacing the natural oxygen layer with a zinc layer, the inherent wetting difficulties were avoided, and compounds with flawless interfaces were successfully produced (no contraction defects, cracks or oxides). Electron microscopy and EDX investigations as well as optical micrographs of the interfacial areas revealed their continu-ously metallic constitution. Diffusion of alloying elements leads to heat-treatable microstructures in the vicinity of the joining interfaces in Al-Al couples. This permits significant variability of mechanical properties. Without significantly cutting down on wettability, the formation of low-melting intermetallic phases (Al3Mg2 and AI12Mg17 IMPs) at the interface of Al-Mg couples was avoided by applying a protec-tive coating to the substrate.

  7. Core Formation Timescale, Silicate-Metal Equilibration, and W Diffusivity (United States)

    Yin, Q.; Jacobsen, B.; Tinker, D.; Lesher, C.


    The extent to which material accreted to the proto-Earth and segregated to form the core was chemically and isotopically equilibrated with the silicate mantle is an outstanding problem in planetary science. This is particularly important when attempting to assign a meaningful age for planetary accretion and core formation based on Hf-W isotope systematics. The Earth and other terrestrial planets likely formed by accretion of previously differentiated planetesimals. For the planetesimals themselves the most important energy source for metal-silicate differentiation is the combined radioactive heating due to decay of 26Al (half-life 0.7 Ma) and 60Fe (half-life 1.5 Ma). It is expected that the fractionation of Hf and W during planetesimal core formation will lead to a divergence in the W isotopic compositions of the core and silicate portions of these bodies. This expectation is supported by the enormously radiogenic 182W signatures reported for basaltic eucrites. The observation that the W isotopic compositions of the silicate portions of Earth, Moon and Mars are similar and markedly less radiogenic than eucrites suggests that during planet accretion the pre-differentiated metallic core material containing low 182W must have equilibrated extensively with the more radiogenic (high 182W) silicate material to subdue the ingrowth of 182W in the silicate mantle of the planets. The standard theory of planet formation predicts that after runaway and oligarchic growth, the late stage of planet formation is characterized by impact and merging of Mars-sized objects. This is a tremendously energetic process estimated to raise the temperature of the proto-Earth to about 7000K (a temperature equivalent to a mass spectrometer's plasma source, which indiscriminately ionizes all incoming elements). After the giant impacts, the proto-Earth had a luminosity and surface temperature close to a low mass star for a brief period of time. Stevenson (1990) argued that emulsification caused

  8. Mathematical Viscosity Models for Ternary Metallic and Silicate Melts

    Institute of Scientific and Technical Information of China (English)

    FU Yuan-kun; MENG Xian-min; GUO Han-jie


    The mathematical viscosity models for metallic melts were discussed. The experimental data of Ag-Au-Cu systems were used to verify the models based on Chou's general geometric thermodynamic model and the calculated results are consistent with the reported experimental data. A new model predicting the viscosity of multi-component silicate melts was established. The CaO-MnO-SiO2, CaO-FeO-SiO2 and FeO-MnO-SiO2 silicate slag systems were used to verify the model.

  9. New Approach for Fractioning Metal Compounds Studies in Soils (United States)

    Minkina, Tatiana; Motuzova, Galina; Mandzhieva, Saglara; Bauer, Tatiana; Burachevskaya, Marina; Sushkova, Svetlana; Nevidomskaya, Dina; Kalinitchenko, Valeriy


    A combined approach for fractioning metal compounds in soils on the basis of sequential (Tessier, 1979) and parallel extractions (1 N NH4Ac, pH 8; 1% EDTA in NH4Ac; and 1N HCl) is proposed. Metal compounds in sequential and parallel extracts are grouped according to the strength of their bonds with soil components. A given group includes metal compounds with similar strengths of bonds and, hence, with similar migration capacities. The groups of firmly and loosely bound metal compounds can be distinguished. This approach has been used to assess the group composition of Zn, Cu, and Pb compounds in an ordinary chernozem and its changes upon the soil contamination with metals. Contamination of an ordinary chernozem from Rostov oblast with heavy metals caused a disturbance of the natural ratios between the metal compounds. In the natural soil, firmly bound metals predominate (88-95%of the total content), which is mainly caused by the fixation of metals in lattices of silicate minerals (56-83%of the total content). The mobility of the metals in the natural soil is low (5-12%) and is mainly related to metal compounds loosely bound with the soil carbonates. Upon the soil contamination with metals (application rates of 100-300 mg/kg), the content of all the metal compounds increases, but the ratio between them shifts towards a higher portion of the potentially mobile metal compounds (up to 30-40% of the bulk contents of the metals). Organic substances and non-silicate Fe, Al, and Mn minerals become the main carriers of the firmly and loosely bound metals. The strengths of their bonds with Cu, Pb, and Zn differ. Lead in the studied chernozems is mainly fixed in a loosely bound form with organic matter, whereas copper and zinc are fixed both by the organic matter and by the non-silicate Fe, Al, and Mn compounds. Firm fixation of the applied Cu and Pb is mainly ensured by the soil organic matter and non-silicate minerals, whereas firm fixation of Zn is mainly due to non-silicate

  10. Electron stimulated hydroxylation of a metal supported silicate film. (United States)

    Yu, Xin; Emmez, Emre; Pan, Qiushi; Yang, Bing; Pomp, Sascha; Kaden, William E; Sterrer, Martin; Shaikhutdinov, Shamil; Freund, Hans-Joachim; Goikoetxea, Itziar; Wlodarczyk, Radoslaw; Sauer, Joachim


    Water adsorption on a double-layer silicate film was studied by using infrared reflection-absorption spectroscopy, thermal desorption spectroscopy and scanning tunneling microscopy. Under vacuum conditions, small amounts of silanols (Si-OH) could only be formed upon deposition of an ice-like (amorphous solid water, ASW) film and subsequent heating to room temperature. Silanol coverage is considerably enhanced by low-energy electron irradiation of an ASW pre-covered silicate film. The degree of hydroxylation can be tuned by the irradiation parameters (beam energy, exposure) and the ASW film thickness. The results are consistent with a generally accepted picture that hydroxylation occurs through hydrolysis of siloxane (Si-O-Si) bonds in the silica network. Calculations using density functional theory show that this may happen on Si-O-Si bonds, which are either parallel (i.e., in the topmost silicate layer) or vertical to the film surface (i.e., connecting two silicate layers). In the latter case, the mechanism may additionally involve the reaction with a metal support underneath. The observed vibrational spectra are dominated by terminal silanol groups (ν(OD) band at 2763 cm(-1)) formed by hydrolysis of vertical Si-O-Si linkages. Film dehydroxylation fully occurs only upon heating to very high temperatures (∼ 1200 K) and is accompanied by substantial film restructuring, and even film dewetting upon cycling hydroxylation/dehydroxylation treatment.

  11. 40 CFR 721.3100 - Oligomeric silicic acid ester compound with a hy-droxyl-al-kyla-mine. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Oligomeric silicic acid ester compound... Significant New Uses for Specific Chemical Substances § 721.3100 Oligomeric silicic acid ester compound with a... chemical substance identified generically as oligomeric silicic acid ester compound with...

  12. Carbonation of metal silicates for long-term CO.sub.2 sequestration

    Energy Technology Data Exchange (ETDEWEB)

    Blencoe, James G.; Palmer, Donald A.; Anovitz, Lawrence M.; Beard, James S.


    In a preferred embodiment, the invention relates to a process of sequestering carbon dioxide. The process comprises the steps of: (a) reacting a metal silicate with a caustic alkali-metal hydroxide to produce a hydroxide of the metal formerly contained in the silicate; (b) reacting carbon dioxide with at least one of a caustic alkali-metal hydroxide and an alkali-metal silicate to produce at least one of an alkali-metal carbonate and an alkali-metal bicarbonate; and (c) reacting the metal hydroxide product of step (a) with at least one of the alkali-metal carbonate and the alkali-metal bicarbonate produced in step (b) to produce a carbonate of the metal formerly contained in the metal silicate of step (a).

  13. Transition Metal Compounds Towards Holography

    Directory of Open Access Journals (Sweden)

    Volker Dieckmann


    Full Text Available We have successfully proposed the application of transition metal compounds in holographic recording media. Such compounds feature an ultra-fast light-induced linkage isomerization of the transition-metal–ligand bond with switching times in the sub-picosecond regime and lifetimes from microseconds up to hours at room temperature. This article highlights the photofunctionality of two of the most promising transition metal compounds and the photophysical mechanisms that are underlying the hologram recording. We present the latest progress with respect to the key measures of holographic media assembled from transition metal compounds, the molecular embedding in a dielectric matrix and their impressive potential for modern holographic applications.

  14. Biological and therapeutic effects of ortho-silicic acid and some ortho-silicic acid-releasing compounds: New perspectives for therapy

    Directory of Open Access Journals (Sweden)

    Jurkić Lela Munjas


    Full Text Available Abstract Silicon (Si is the most abundant element present in the Earth's crust besides oxygen. However, the exact biological roles of silicon remain unknown. Moreover, the ortho-silicic acid (H4SiO4, as a major form of bioavailable silicon for both humans and animals, has not been given adequate attention so far. Silicon has already been associated with bone mineralization, collagen synthesis, skin, hair and nails health atherosclerosis, Alzheimer disease, immune system enhancement, and with some other disorders or pharmacological effects. Beside the ortho-silicic acid and its stabilized formulations such as choline chloride-stabilized ortho-silicic acid and sodium or potassium silicates (e.g. M2SiO3; M= Na,K, the most important sources that release ortho-silicic acid as a bioavailable form of silicon are: colloidal silicic acid (hydrated silica gel, silica gel (amorphous silicon dioxide, and zeolites. Although all these compounds are characterized by substantial water insolubility, they release small, but significant, equilibrium concentration of ortho-silicic acid (H4SiO4 in contact with water and physiological fluids. Even though certain pharmacological effects of these compounds might be attributed to specific structural characteristics that result in profound adsorption and absorption properties, they all exhibit similar pharmacological profiles readily comparable to ortho-silicic acid effects. The most unusual ortho-silicic acid-releasing agents are certain types of zeolites, a class of aluminosilicates with well described ion(cation-exchange properties. Numerous biological activities of some types of zeolites documented so far might probably be attributable to the ortho-silicic acid-releasing property. In this review, we therefore discuss biological and potential therapeutic effects of ortho-silicic acid and ortho-silicic acid -releasing silicon compounds as its major natural sources.

  15. Metals and metal compounds in cancer treatment. (United States)

    Desoize, Bernard


    Metals and metal compounds have been used in medicine for several thousands of years. In this review we summarized the anti-cancer activities of the ten most active metals: arsenic, antimony, bismuth, gold, vanadium, iron, rhodium, titanium, gallium and platinum. The first reviewed metal, arsenic, presents the anomaly of displaying anti-cancer and oncogenic properties simultaneously. Some antimony derivatives, such as Sb2O3, salt (tartrate) and organic compounds, show interesting results. Bismuth directly affects Helicobacter pylori and gastric lymphoma; the effects of bismuth complexes of 6-mercaptopurine are promising. Gold(I) and (III) compounds show anti-tumour activities, although toxicity remains high. Research into the potential use of gold derivatives is still ongoing. Several derivatives of vanadium show anti-proliferative activity, but their toxicity must be overcome. Several pieces of evidence indicate that iron deprivation could be an excellent therapeutic approach; furthermore, it is synergistic with classic anti-cancer drugs. Rhodium belongs to the same group as platinum and it also presents interesting activity, but with the same nephrotoxicity. Several rhodium compounds have entered phase I clinical trials. In contrast to the platinum complexes, titanium derivatives showed no evidence of nephrotoxicity or myelotoxicity; titanocene dichloride is undergoing clinical trial. The anti-proliferative effect of gallium could be related to its competition with the iron atom; in addition a derivative appears to reverse the multidrug resistance. The last metal reviewed, platinum, has given some of the very best anti-cancer drugs. Four derivatives are used today in the clinic; their mechanism of action and of resistance are described.

  16. Alkoxy-Siloxide Metal Complexes: Precursors to Metal Silica, Metal Oxide Silica, and Metal Silicate Materials. (United States)

    Terry, Karl William

    The alkoxy-siloxide complexes M (OSi(O ^{rm t}Bu)_3 ]_4 (M = Ti(1), Zr(2), Hf(3)), were prepared by reaction with their respective metal diethylamides. These compounds readily undergo low-temperature decomposition to their respective metal oxide silica materials rm(MO_2{cdot}4SiO_2). The volatile products of the thermolysis of 2 (ca. 200 ^circC) were isobutylene (11.7 equiv) and water (5.4 equiv). The rm ZrO _2{cdot}4SiO_2 material from the decomposition of 2 at 400^circ C was amorphous until ca. 1100^ circC where crystallization of t-ZrO _2 occurred. After thermolysis to 1500 ^circC, t-ZrO_2 and cristobalite were the major products with minor amounts of m-ZrO_2. The rm HfO_2{cdot}4SiO_2 material from the decomposition of 3 at 400^ circC was amorphous until ca. 1000 ^circC where crystallization of c/t -HfO_2 was observed. Thermolysis to 1460^circC yielded c/t -HfO_2, m-HfO_2, and minor amounts of cristobalite. The crystallization of anatase in the rm TiO_2{cdot }4SiO_2 material from decomposed 1 at 400^circC was apparent after thermolysis to 1000^circC. Thermolysis to 1400^circC gave a mixture of anatase, rutile, and cristobalite. Compound 2 was decomposed in xylenes and yielded a transparent gel which was isolated as a white powder upon drying in vacuuo. The compounds [ Me _2AlOSi(O^{t}Bu)_3] _2 (4) and [( ^{t}BuO)MeAlOSi(O^{t}Bu) _3]_2 (5) were structurally characterized and contain bent and planar rm Al_2O_2 four membered rings, respectively. Both 4 and 5 yield isobutylene upon thermolysis (ca. 200 ^circC) and the crystallization of mullite occurs at 1034^circC and 1017^circC, respectively (by DTA). The solution thermolysis of 4 in refluxing toluene yields an opaque white gel. The crystallization of mullite occurs at 1029^circC (by DTA). The compounds [ CuOSi(O ^{t}Bu)_3]_{n } (6) and [ CuOSi(O ^{t}Bu)_2Ph]_4 (7) were prepared by reaction with [ CuO^{t}Bu]_4. The thermolysis of 6 at 1000^circ C under argon gave Cu^circ and amorphous silica and thermolysis under

  17. Turbulent metal-silicate mixing, fragmentation, and equilibration in magma oceans

    CERN Document Server

    Deguen, Renaud; Olson, Peter


    Much of the Earth was built by high-energy impacts of planetesimals and embryos, many of these impactors already differentiated, with metallic cores of their own. Geochemical data provide critical information on the timing of accretion and the prevailing physical conditions, but their interpretation depends critically on the degree of metal-silicate chemical equilibration during core-mantle differentiation, which is poorly constrained. Efficient equilibration requires that the large volumes of iron derived from impactor cores mix with molten silicates down to scales small enough to allow fast metal-silicate mass transfer. Here we use fluid dynamics experiments to show that large metal blobs falling in a magma ocean mix with the molten silicate through turbulent entrainment, with fragmentation into droplets eventually resulting from the entrainment process. In our experiments, fragmentation of the dense fluid occurs after falling a distance equal to 3-4 times its initial diameter, at which point a sizable volu...

  18. Sorption properties of finely dispersed metal-containing polymer-silicate materials

    Directory of Open Access Journals (Sweden)

    Андрій Сергійович Масюк


    Full Text Available Sorption properties of metal-containing polymer-silicate materials on regarding to different acid-base indicators have been investigated. The effect of the nature of metal and polymer modifier (polyvinyl alcohol and polyvinylpyrrolidone on the amount of active centers and specific active surface area of such material was determined. Moisture absorption of modified and not modified silicate fillers was founded. The effect of Ni-containing polymer-silicate fillers on the speed of curing of polyester compositions was determined

  19. Metal-Silicate Differentiation from a Metal Pond Emulsion during Core Formation (United States)

    Fleck, J.; Weeraratne, D. S.


    The terrestrial planets demonstrate a heavy bombardment of impacts in their early formation history. Impacts are violent, energetic collisions that may melt the surface and/or cause segregation of impactor material including silicates and liquid metal iron. Although theoretical studies have been done with conceptual models for metal diapir descent to form terrestrial planetary cores, physical or computer modeling studies are scarce due to the strong variations in physical properties between liquid metals and solid silicates. We use laboratory fluid experiments to study core formation processes using liquid metal gallium and high viscosity glucose syrup which provide the buoyancy ratios expected for planetary interiors and low Reynolds number flow dynamics. Preliminary results indicate that the physical process of sinking metal diapirs form trailing conduits that may drag low density surface magmatic material to the base of the mantle. The low density material collects, grows at the base of the box, and rises back to the surface. We compare two cases of a pond made of 1) liquid metal emulsion and 2) a smooth coalesced metal pond. We find that emulsion experiments entrain greater amounts of low density fluid to the base of the box. Once the metal diapir reaches the base, conduit material exhibits flow reversal to return buoyantly to the surface. In the case of coalesced liquid metal diapirs, low density conduit material returns to the surface through the pre-established conduit. In the emulsion diapir case, we observe the formation of a new thermo-chemical buoyant plume that grows, exits the conduit, and travels along a new pathway to the surface. Metal plume descent and chemical plume rise velocities are consistent with Stokes velocity. Estimates of metal-silicate plume sinking time and thermo-chemical plume rise time for terrestrial planetary interiors are provided. We suggest the observation of a thermo-chemical plume as a source for orogeny at the surface of

  20. Determining the Metal/Silicate Partition Coefficient of Germanium: Implications for Core and Mantle Differentiation. (United States)

    King, C.; Righter, K.; Danielson, L.; Pando, K.; Lee, C.


    Currently there are several hypotheses for the thermal state of the early Earth. Some hypothesize a shallow magma ocean, or deep magma ocean, or heterogeneous accretion which requires no magma ocean at all. Previous models are unable to account for Ge depletion in Earth's mantle relative to CI chondrites. In this study, the element Ge is used to observe the way siderophile elements partition into the metallic core. The purpose of this research is to provide new data for Ge and to further test these models for Earth's early stages. The partition coefficients (D(sub Ge) = c(sub metal)/c(sub silicate), where D = partition coefficient of Ge and c = concentration of Ge in the metal and silicate, respectively) of siderophile elements were studied by performing series of high pressure, high temperature experiments. They are also dependent on oxygen fugacity, and metal and silicate composition. Ge is a moderately siderophile element found in both the mantle and core, and has yet to be studied systematically at high temperatures. Moreover, previous work has been limited by the low solubility of Ge in silicate melts (less than 100 ppm and close to detection limits for electron microprobe analysis). Reported here are results from 14 experiments studying the partitioning of Ge between silicate and metallic liquids. The Ge concentrations were then analyzed using Laser Ablation Inductively Coupled Mass Spectrometry (LA-ICP-MS) which is sensitive enough to detect ppm levels of Ge in the silicate melt.

  1. Depletion of Vandium in Planetary Mantles: Controlled by Metal, Oxide, or Silicate? (United States)

    Righter, Kevin


    Vanadium concentrations in planetary mantles can provide information about the conditions during early accretion and differentiation. Because V is a slightly siderophile element, it is usually assumed that any depletion would be due to core formation and metal-silicate equilibrium. However, V is typically more compatible in phases such as spinel, magnesiowuestite and garnet. Fractionation of all of these phases would cause depletions more marked than those from metal. In this paper consideration of depletions due to metal, oxide and silicate are critically evaluated.

  2. Pt, Au, Pd and Ru Partitioning Between Mineral and Silicate Melts: The Role of Metal Nanonuggets (United States)

    Malavergne, V.; Charon, E.; Jones, J.; Agranier, A.; Campbell, A.


    The partition coefficients of Pt and other Pt Group Elements (PGE) between metal and silicate D(sub Metal-Silicate) and also between silicate minerals and silicate melts D(sub Metal-Silicate) are among the most challenging coefficients to obtain precisely. The PGE are highly siderophile elements (HSE) with D(sub Metal-Silicate) >10(exp 3) due to the fact that their concentrations in silicates are very low (ppb to ppt range). Therefore, the analytical difficulty is increased by the possible presence of HSE-rich-nuggets in reduced silicate melts during experiments). These tiny HSE nuggets complicate the interpretation of measured HSE concentrations. If the HSE micro-nuggets are just sample artifacts, then their contributions should be removed before calculations of the final concentration. On the other hand, if they are produced during the quench, then they should be included in the analysis. We still don't understand the mechanism of nugget formation well. Are they formed during the quench by precipitation from precursor species dissolved homogeneously in the melts, or are they precipitated in situ at high temperature due to oversaturation? As these elements are important tracers of early planetary processes such as core formation, it is important to take up this analytical and experimental challenge. In the case of the Earth for example, chondritic relative abundances of the HSE in some mantle xenoliths have led to the concept of the "late veneer" as a source of volatiles (such as water) and siderophiles in the silicate Earth. Silicate crystal/liquid fractionation is responsible for most, if not all, the HSE variation in the martian meteorite suites (SNC) and Pt is the element least affected by these fractionations. Therefore, in terms of reconstructing mantle HSE abundances for Mars, Pt becomes a very important player. In the present study, we have performed high temperature experiments under various redox conditions in order to determine the abundances of Pt, Au

  3. Metal-Silicate Partitioning of Tungsten from 10 to 50 GPa (United States)

    Shofner, G. A.; Campbell, A. J.; Danielson, L.; Rahman, Z.; Righter, K.


    Geochemical models of core formation are commonly based on core and mantle abundances of siderophile elements that partitioned between silicate and metal in a magma ocean in the early Earth. Tungsten is a moderately siderophile element that may provide constraints on the pressure, temperature, composition, and oxygen fugacity conditions, and on the timing of core formation in the Earth. Previous experimental studies suggest that pressure exerts little to no influence over W metal-silicate partitioning up to 24 GPa, and indicate that the stronger influences are temperature, composition, and oxygen fugacity. However, core formation models based in part on W, predict metal-silicate equilibration pressures outside the available experimental pressure range, requiring extrapolation of parameterized models. Therefore, higher pressure experimental data on W were needed to constrain this important parameter.

  4. Chromatographic separation studies of penicillins, cephalosporins and carbapenems on transition-metal silicate modified silica layers. (United States)

    Singh, Dhruv K; Maheshwari, Gunjan


    The chromatographic behavior of penicillins, cephalosporins and carbapenems has been studied on the thin layers of transition-metal ion (viz. Ni(2+)/Zn(2+)/Cu(2+)/Co(2+)) silicate modified silica. Transition-metal silicate (3.92%) and silica (96.08%) were found to be optimum and resulted in spherical-compact spots and improved resolution of the analytes. The effect of various mobile phases was also investigated. The chromatograms were visualized as yellow spots by placing in an I(2)-chamber. The method has been found to be reproducible and convenient for routine analysis.

  5. Nano porous alkaline earth metal silicates as free fatty acid adsorbents from Crude Palm Oil (CPO) (United States)

    Masmur, Indra; Sembiring, Seri Bima; Bangun, Nimpan; Kaban, Jamaran; Putri, Nabila Karina


    Free fatty acids(FFA) from Crude Palm Oil (CPO) have been adsorbed by alkaline earth metal silicate (M-silicate : M = Mg, Ca, Sr and Ba) adsorbents in ethanol using batch method. The adsorbents were prepared from the chloride salts of alkaline metals and Na2SiO3. The resulting white solid of the alkaline earth metal silicates were then heated at 800°C for 3 hours to enlarge their porosities. All adsorbents were characterized by SEM-EDX, XRD and BET. The EDX spectrum of SEM-EDX showed the appearance of all elements in the adsorbents, and the XRD spectrum of all adsorbents showed that they have crystobalite structure. The porosity of the adsorbents calculated by BET method showed that the porosities of the adsorbents range from 2.0884 - 2.0969 nm. All the adsorbents were used to adsorb the FFA from CPO containing 4.79%, 7.3%, 10.37% and 13.34% of FFA. The ratio of adsorbent to CPO to be used in adsorption of FFA from CPO were made 1:1, 1:2 and 1:3, with adsorption time of 1 hour. We found that the maximum adsorption of FFA from CPO was given by Ca-Silicate adsorbent which was between 69.86 - 94.78%, while the lowest adsorption was shown by Mg-silicate adsorbent which was 49.32 -74.53%.

  6. Nanotubes within transition metal silicate hollow spheres: Facile preparation and superior lithium storage performances

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Fan; An, Yongling; Zhai, Wei; Gao, Xueping [Key Laboratory for Liquid–Solid Structural Evolution & Processing of Materials (Ministry of Education), Jinan 250100 (China); Feng, Jinkui, E-mail: [Key Laboratory for Liquid–Solid Structural Evolution & Processing of Materials (Ministry of Education), Jinan 250100 (China); Ci, Lijie [Key Laboratory for Liquid–Solid Structural Evolution & Processing of Materials (Ministry of Education), Jinan 250100 (China); Xiong, Shenglin [School of Materials Science and Engineering, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100 (China)


    Highlights: • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} were successfully prepared by a facile hydrothermal method using SiO{sub 2} nanosphere. • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} were tested as anode materials for lithium batteries. • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} delivered superior electrochemical performance. • The lithium storage mechanism is probe via cyclic voltammetry and XPS. - Abstract: A series of transition metal silicate hollow spheres, including cobalt silicate (Co{sub 2}SiO{sub 4}), manganese silicate (MnSiO{sub 3}) and copper silicate (CuSiO{sub 3}.2H{sub 2}O, CuSiO{sub 3} as abbreviation in the text) were prepared via a simple and economic hydrothermal method by using silica spheres as chemical template. Time-dependent experiments confirmed that the resultants formed a novel type of hierarchical structure, hollow spheres assembled by numerous one-dimensional (1D) nanotubes building blocks. For the first time, the transition metal silicate hollow spheres were characterized as novel anode materials of Li-ion battery, which presented superior lithium storage capacities, cycle performance and rate performance. The 1D nanotubes assembly and hollow interior endow this kind of material facilitate fast lithium ion and electron transport and accommodate the big volume change during the conversion reactions. Our study shows that low-cost transition metal silicate with rationally designed nanostructures can be promising anode materials for high capacity lithium-ion battery.

  7. Thermometry of the magma ocean: Controls on the metal-silicate partitioning of gold (United States)

    Bennett, N. R.; Brenan, J. M.; Fei, Y.


    We have performed experiments to investigate the solubility and metal-silicate partitioning of gold as a function of metal sulphur content (XS), silicate melt polymerization (NBO/T) and pressure (P). These experiments show that Au becomes less siderophile both with increasing pressure and as the metal phase becomes more sulphur-rich. For the studied range of compositions, melt polymerization has no effect on the solubility of Au. The reduction in the siderophile tendency of gold with increasing metal sulphur content is greater than expected on the basis of activity-composition relationships in the metal phase. This suggests a significant role for complexing between Au and S in the silicate melt. Our new experimental results are combined with literature data to yield a parameterisation for the exchange coefficient of Au (KdAuMet/Sil) as a function of P, T and XS: Using this relationship, alongside similar parameterisations for Ni and Co selected from the literature, we performed continuous accretion models to delineate regions of parameter space in which Au and moderately siderophile element (MSE) abundances in the primitive upper mantle (PUM) could be reproduced. These models suggest that for metal-silicate equilibrium at very high pressures, Au will be overabundant in the PUM if equilibrium also occurs at extreme temperatures. Instead, most successful models are found when equilibrium occurs at high pressure but sub-liquidus temperatures. This result is in keeping with the physical conditions expected for a scenario where core-forming metal ponds and equilibrates at the rheological base of a magma ocean (e.g. Wade and Wood, 2005).

  8. XANES spectra of transition metal compounds

    NARCIS (Netherlands)

    de Groot, F.M.F.|info:eu-repo/dai/nl/08747610X


    An overview is given of the interactions that determine the XANES spectral shapes of transition metal compounds. The interactions are divided into ground state effects, final state effects and transition effects. The metal L edges, metal K edges and ligand K edges are analysed with respect to these

  9. Self consistent model of core formation and the effective metal-silicate partitioning (United States)

    Ichikawa, H.; Labrosse, S.; Kameyama, M.


    It has been long known that the formation of the core transforms gravitational energy into heat and is able to heat up the whole Earth by about 2000 K. However, the distribution of this energy within the Earth is still debated and depends on the core formation process considered. Iron rain in the surface magma ocean is supposed to be the first mechanism of separation for large planets, iron then coalesces to form a pond at the base of the magma ocean [Stevenson 1990]. The time scale of the separation can be estimated from falling velocity of the iron phase, which is estimated by numerical simulation [Ichikawa et al., 2010] as ˜ 10cm/s with iron droplet of centimeter-scale. A simple estimate of the metal-silicate partition from the P-T condition of the base of the magma ocean, which must coincide with between peridotite liquidus and solidus by a single-stage model, is inconsistent with Earth's core-mantle partition. P-T conditions where silicate equilibrated with metal are far beyond the liquidus or solidus temperature for about ˜ 700K. For example, estimated P-T conditions are: 40GPa at 3750K for Wade and Wood, 2005, T ≧ 3600K for Chabot and Agee, 2003 and 35GPa at T ≧ 3300K for Gessmann and Rubie, 2000. Meanwhile, Rubie et al., 2003 shown that metal couldn't equilibrate with silicate on the base of the magma ocean before crystallization of silicate. On the other hand, metal-silicate equilibration is achieved only ˜ 5 s in the state of iron rain. Therefore metal and silicate simultaneously separate and equilibrate each other at the P-T condition during the course to the iron pond. Taking into account the release of gravitational energy, temperature of the middle of the magma ocean would be higher than the liquidus. Estimation of the thermal structure during the iron-silicate separation requires the development of a planetary-sized calculation model. However, because of the huge disparity of scales between the cm-sized drops and the magma ocean, a direct


    Energy Technology Data Exchange (ETDEWEB)

    Wurm, Gerhard [Fakultaet fuer Physik, Universitaet Duisburg-Essen, Lotharstr. 1, D-47057 Duisburg (Germany); Trieloff, Mario [Institut fuer Geowissenschaften, Universitaet Heidelberg, Im Neuenheimer Feld 234-236, D-69120 Heidelberg (Germany); Rauer, Heike, E-mail: [Institut fuer Planetenforschung, Extrasolare Planeten und Atmosphaeren, Deutsches Zentrum fuer Luft- und Raumfahrt (DLR), Rutherfordstrasse 2, D-12489 Berlin (Germany)


    Mercury's high uncompressed mass density suggests that the planet is largely composed of iron, either bound within metal (mainly Fe-Ni) or iron sulfide. Recent results from the MESSENGER mission to Mercury imply a low temperature history of the planet which questions the standard formation models of impact mantle stripping or evaporation to explain the high metal content. Like Mercury, the two smallest extrasolar rocky planets with mass and size determination, CoRoT-7b and Kepler-10b, were found to be of high density. As they orbit close to their host stars, this indicates that iron-rich inner planets might not be a nuisance of the solar system but be part of a general scheme of planet formation. From undifferentiated chondrites, it is also known that the metal to silicate ratio is highly variable, which must be ascribed to preplanetary fractionation processes. Due to this fractionation, most chondritic parent bodies-most of them originated in the asteroid belt-are depleted in iron relative to average solar system abundances. The astrophysical processes leading to metal silicate fractionation in the solar nebula are essentially unknown. Here, we consider photophoretic forces. As these forces particularly act on irradiated solids, they might play a significant role in the composition of planetesimals forming at the inner edge of protoplanetary disks. Photophoresis can separate high thermal conductivity materials (iron) from lower thermal conductivity solids (silicate). We suggest that the silicates are preferentially pushed into the optically thick disk. Subsequent planetesimal formation at the edge moving outward leads to metal-rich planetesimals close to the star and metal depleted planetesimals farther out in the nebula.

  11. Turbulent Mixing of Metal and Silicate during Planet Accretion – and interpretation of the Hf-W chronometer

    DEFF Research Database (Denmark)

    Dahl, Tais Wittchen; Stevenson, David


    to the last major metal–silicate re-equilibration, believed to coincide with time of the Moon-forming impact. However, we show that large cores have limited ability to reset the Hf–W systemin the silicate Earth. Excess 182W in bulk silicate Earth is more sensitive to early core formation processes than......In the current view of planet formation, the final assembly of the Earth involved giant collisions between protoplanets (N1000 kmradius), with theMoon formed as a result of one such impact.At this stage the colliding bodies had likely differentiated into a metallic core surrounded by a silicate...... mantle. During the Moon-forming impact, nearly all metal sank into the Earth's core. Weinvestigate towhat extent large self-gravitating iron cores can mix with surrounding silicate and howthis influences the short-lived chronometer, Hf–W, used to infer the age of the Moon. We present fluid dynamical...

  12. Experimental partitioning of Zr, Ti, and Nb between silicate liquid and a complex noble metal alloy and the partitioning of Ti between perovskite and platinum metal (United States)

    Jurewicz, Stephen R.; Jones, John H.


    El Goresy et al.'s observation of Nb, Zr, and Ta in refractory platinum metal nuggets (RPMN's) from Ca-Al-rich inclusions (CAI's) in the Allende meteorite led them to propose that these lithophile elements alloyed in the metallic state with noble metals in the early solar nebula. However, Grossman pointed out that the thermodynamic stability of Zr in the oxide phase is vastly greater than metallic Zr at estimated solar nebula conditions. Jones and Burnett suggested this discrepancy may be explained by the very non-ideal behavior of some lithophile transition elements in noble metal solutions and/or intermetallic compounds. Subsequently, Fegley and Kornacki used thermodynamic data taken from the literature to predict the stability of several of these intermetallic compounds at estimated solar nebula conditions. Palme and Schmitt and Treiman et al. conducted experiments to quantify the partitioning behavior of certain lithophile elements between silicate liquid and Pt-metal. Although their results were somewhat variable, they did suggest that Zr partition coefficients were too small to explain the observed 'percent' levels in some RPMN's. Palme and Schmitt also observed large partition coefficients for Nb and Ta. No intermetallic phases were identified. Following the work of Treiman et al., Jurewicz and Jones performed experiments to examine Zr, Nb, and Ti partitioning near solar nebula conditions. Their results showed that Zr, Nb, and Ti all have an affinity for the platinum metal, with Nb and Ti having a very strong preference for the metal. The intermetallic phases (Zr,Fe)Pt3, (Nb,Fe)Pt3, and (Ti,Fe)Pt3 were identified. Curiously, although both experiments and calculations indicate that Ti should partition strongly into Pt-metal (possibly as TiPt3), no Ti has ever been observed in any RPMN's. Fegley and Kornacki also noticed this discrepancy and hypothesized that the Ti was stabilized in perovskite which is a common phase in Allende CAI's.

  13. Environmentally stable flexible metal-insulator-metal capacitors using zirconium-silicate and hafnium-silicate thin film composite materials as gate dielectrics. (United States)

    Meena, Jagan Singh; Chu, Min-Ching; Wu, Chung-Shu; Ravipati, Srikanth; Ko, Fu-Hsiang


    Fully flexible metal-insulator-metal (MIM) capacitors fabricated on 25 microm thin polyimide (PI) substrates via the surface sol-gel process using 10-nm-thick zirconium-silicate (ZrSixOy) and hafnium-silicate (HfSimOn) films as gate dielectrics. The surface morphology of the ZrSixOy and HfSimOn films were investigated using atomic force microscopy and scanning electron microscopy, which confirmed that continuous and crack-free surface growth had occurred on the PI. Both the films treated with oxygen (O2) plasma and annealing (ca. 250 degrees C) consisted of amorphous phase; confirmed by X-ray diffraction. We employed X-ray photoelectron spectroscopy (XPS) at high resolution to examine the chemical composition of the films subjected to various treatment conditions. The shift of the XPS peaks towards higher binding energy revealed the O2 plasma-pretreatment followed by annealing was the most effective process to the surface oxidation at relatively low-temperature, for further passivate the grease traps and making dielectric films thermally stable. The ZrSixOy and HfSimOn films in sandwich-like MIM configuration on the PI substrates exhibited the low leakage current densities of 7.1 x 10(-9) and 8.4 x 10(-9) A/cm2 at applied electric field of 10 MV/cm and maximum capacitance densities of 7.5 and 5.3 fF/microm2 at 1 MHz, respectively. In addition, the ZrSixOy and HfSimOn films in MIM capacitors showed the estimated dielectric constants of 8.2 and 6.0, respectively. Prior to use of flexible MIM capacitors in advanced flexible electronic devices; the reliability test was studied by applying day-dependent leakage current density measurements up to 30 days. These films of silicate-surfactant mesostructured materials have special interest to be used as gate dielectrics in future for flexible metal-oxide-semiconductor devices.



  15. Spectroscopic Properties and Judd-Ofelt Theory Analysis of Er3+-Doped Heavy Metal Oxyfluoride Silicate Glass

    Institute of Scientific and Technical Information of China (English)

    徐时清; 杨中民; 戴世勋; 张军杰; 胡丽丽; 姜中宏


    Er3+-doped heavy metal oxyfluoride silicate glass was fabricated and characterized, and the absorption spectrum and fluorescence spectrum of the glass were studied. The Judd-Ofelt intensity parameters Ωt (t=2, 4, 6), spontaneous transition probability, fluorescence branching ratio and radiative lifetime of each energy levels for Er3+ were calculated by Judd-Ofelt theory, and stimulated emission cross-section of 4I13/2→4I15/2 transition was calculated by McCumber theory. The results show that fluorescence full width at half maximum and stimulated emission cross-section of Er3+-doped heavy metal oxyfluoride silicate glass are broad and large, respectively. Compared with other host glasses, the gain bandwidth property of Er3+-doped heavy metal oxyfluoride silicate glass is close to those of tellurite and bismuth glasses, and has advantage over those of silicate, phosphate and germante glasses.

  16. Metal-silicate Partitioning and Its Role in Core Formation and Composition on Super-Earths (United States)

    Schaefer, Laura; Jacobsen, Stein B.; Remo, John L.; Petaev, M. I.; Sasselov, Dimitar D.


    We use a thermodynamic framework for silicate-metal partitioning to determine the possible compositions of metallic cores on super-Earths. We compare results using literature values of the partition coefficients of Si and Ni, as well as new partition coefficients calculated using results from laser shock-induced melting of powdered metal-dunite targets at pressures up to 276 GPa, which approaches those found within the deep mantles of super-Earths. We find that larger planets may have little to no light elements in their cores because the Si partition coefficient decreases at high pressures. The planet mass at which this occurs will depend on the metal-silicate equilibration depth. We also extrapolate the equations of state (EOS) of FeO and FeSi alloys to high pressures, and present mass–radius diagrams using self-consistent planet compositions assuming equilibrated mantles and cores. We confirm the results of previous studies that the distribution of elements between mantle and core will not be detectable from mass and radius measurements alone. While observations may be insensitive to interior structure, further modeling is sensitive to compositionally dependent properties, such as mantle viscosity and core freeze-out properties. We therefore emphasize the need for additional high pressure measurements of partitioning as well as EOSs, and highlight the utility of the Sandia Z-facilities for this type of work.

  17. Extent of metal-silicate disequilibrium during accretion and early differentiation of the Earth (United States)

    Rubie, D. C.; Nimmo, F.; Morbidelli, A.; Frost, D. J.


    Earth, Mars, Venus and Mercury accreted on a timescale of 10-100 My through a series of violent collisions with planetesimals and embryos. The high energy of such impacts was sufficient to cause deep magma ocean formation which facilitated the segregation of metal and silicate liquids. Planetary cores thus formed as a multistage process that was inseparable from the accretion process. In order to better understand the formation and early differentiation of the terrestrial planets, we are integrating a multistage core-formation model with N-body accretion simulations. Constraints on model parameters are the compositions of the Earth's primitive mantle and, to a lesser extent, the mantles of Mars and Mercury which may be FeO rich and FeO-poor respectively. We use a least-squares minimization to optimise 4 model parameters. Elements currently considered include Si, O, Ni, Co, W, Nb, Cr, Ta and V. We concentrate on recent N-body simulations that result in an approximately Earth-mass planet at ~1 AU. In order to satisfy the model constraints, accretion has to be heterogeneous, with embryos and planetesimals originating in the inner part of the solar system (e.g. emulsify and equilibrate in a magma ocean and (2) the fraction of magma oceans that are involved in the equilibration process for both impacting planetesimals and embryos. Both estimates are crucial for interpreting Hf-W age determinations. Best results are obtained when the fraction of silicate mantle/magma ocean that interacts chemically with the metallic cores of impactors is limited and lies in the range 0.003 to 0.1, depending on the size of the impactor and magma ocean depth. The degree of incomplete metal equilibration depends on the extent to which the impactor's mantle participates in the metal-silicate equilibration process.

  18. Argon Partitioning Between Metal and Silicate Liquids in the Laser-Heated DAC to 25 GPa (United States)

    Bouhifd, M. A.; Jephcoat, A. P.


    The accretion of the Earth from primordial material and its subsequent segregation into core and mantle are fundamental problems in terrestrial and solar system science. Many of the questions about the process, although well developed as model scenarios over the last few decades, are still open and much debated, and include, for example, whether the core is, or was, a reservoir for the noble (rare) gases. In the present study we use for the first time the laser-heated diamond-anvil cell (LHDAC) to study the Ar partitioning at high-pressure and temperature between metal and silicate liquids. Little work has been reported on noble gas partitioning at pressure since a single multi-anvil experiment to 10 GPa (Matsuda et al., 1993). We used either compacted glass powders simulating that of a model C1 chondrite and iron metal, or pure metal alloys (pure Fe, FeNiCo alloy, FeSi). Thermal insulation from the diamonds was achieved with solid argon as pressure medium. The samples were heated by a multimode YAG laser for an average of 15 minutes and temperatures were determined spectro-radiometrically with a fit to a grey-body Planck function. Samples recovered after the runs were analysed by electron microprobe with spatial resolution near 1 μ m. The argon melts by conductive heating from the molten sample dissolving into the metal/silicate melt. Preliminary results on Ar solubility at lower pressures show good agreement with data reported by White et al. (1986) for Ar solubility in sanidine (KAlSi3O8). With sanidine melt, Ar solubility increases up to around 5-6 GPa where it reaches about 2.5 wt%, and remains roughly constant to higher pressures, suggesting that a threshold concentration is reached. Similar behavior is observed for a mix of C1-chondrite composition and iron and the results imply that the solubility of Ar is intimately related to liquid structure at high pressure. We also present results on Ar solubility into pure silicate liquids of varying composition in

  19. Structural study and crystallography of the major compound of anhydrous cement: tri-calcium silicate; Etude structurale et cristallographie du compose majoritaire du ciment anhydre: le silicate tricalcique

    Energy Technology Data Exchange (ETDEWEB)

    Noirfontaine, M.N. de


    Anhydrous (Portland) cement is mainly composed of a synthetic material, the clinker, whose major compound is tri-calcium silicate (Ca{sub 3}SiO{sub 5}), often referred as C{sub 3}S with the compact oxides notations, C = CaO et S = SiO{sub 2}. The polymorphism of C{sub 3}S, still not well known, is the main subject of the thesis. Various crystal structures (rhombohedral R, monoclinic M1, M2, M3 and triclinic T1, T2, T3) can be found, depending on temperature and impurities. The only known structures are T1, M1 and M3, involving large unit cells with an orientational disorder of silicate tetrahedra. The single crystal studies exhibit no clear relation between the various polymorphs. Starting from known results from literature single crystal experiments, we establish the metric and structural relations between the different structures. Averaged structures for the T1, M1 and M3 polymorphs are proposed, together with all the matrices of transformation between the unit cells. We also introduce new 1-D, 2-D, and 3-D structural units, which make easier the understanding of the structures of C{sub 3}S, with the result of a better description of the orientational disorder. The effects of impurities on the structure are discussed. In industrial clinkers, impurities stabilize mainly M1 and M3 monoclinic forms. We propose a space group (Pc) and two structural models (a superstructure and an approximate averaged structure) for the M1 form. All the models are validated on synthetic compounds (M3, M2, M1 et T1) and industrial clinkers analysed by X-Ray powder diffraction with Rietveld analysis. (author)

  20. Distribution of Sb, As, Ge, and In between metal and silicate during accretion and core formation in the Earth (United States)

    Righter, K.; Nickodem, K.; Pando, K.; Danielson, L.; Boujibar, A.; Righter, M.; Lapen, T. J.


    A large number of siderophile (iron-loving) elements are also volatile, thus offering constraints on the origin of volatile elements in differentiated bodies such as Earth, Moon, Mars and Vesta. Metal-silicate partitioning data for many of these elements is lacking, making their overall mantle concentrations in these bodies difficult to model and origin difficult to distinguish between core formation and volatile depletion. To address this gap in understanding, we have undertaken systematic studies of four volatile siderophile elements - Sb, As, Ge and In - at variable temperature and variable Si content of metal. Several series were carried out at 1 GPa, and between 1500 and 1900 °C, for both C saturated and C-free conditions. The results show that temperature causes a decrease in the metal/silicate partition coefficient for all four elements. In addition, activity coefficients for each element have been determined and show a very strong dependence on Si content of Fe alloy. Si dissolved in metal significantly decreases the metal/silicate partition coefficients, at both 1600 and 1800 °C. The combination of temperature and Si content of the metal causes reduction of the metal-silicate partition coefficient to values that are close to those required for an origin of mantle As, Sb, Ge, and In concentrations by metal-silicate equilibrium processes. Combining these new results with previous studies on As, Sb, Ge, and In, allowed derivation of predictive expressions for metal/silicate partition coefficients for these elements which can then be applied to Earth. The expressions are applied to two scenarios for continuous accretion of Earth; specifically for constant and increasing fO2 during accretion. The results indicate that mantle concentrations of As, Sb, Ge, and In can be explained by metal-silicate equilibrium during an accretion scenario. The modeling is not especially sensitive to either scenario, although all element concentrations are explained better by a

  1. Turbulent mixing of metal and silicate during planet accretion — And interpretation of the Hf–W chronometer


    Dahl, Tais W.; Stevenson, David J.


    In the current view of planet formation, the final assembly of the Earth involved giant collisions between proto-planets (> 1000 km radius), with the Moon formed as a result of one such impact. At this stage the colliding bodies had likely differentiated into a metallic core surrounded by a silicate mantle. During the Moon-forming impact, nearly all metal sank into the Earth's core. We investigate to what extent large self-gravitating iron cores can mix with surrounding silicate and how this ...

  2. Metal and silicate particles including nanoparticles are present in electronic cigarette cartomizer fluid and aerosol.

    Directory of Open Access Journals (Sweden)

    Monique Williams

    Full Text Available Electronic cigarettes (EC deliver aerosol by heating fluid containing nicotine. Cartomizer EC combine the fluid chamber and heating element in a single unit. Because EC do not burn tobacco, they may be safer than conventional cigarettes. Their use is rapidly increasing worldwide with little prior testing of their aerosol.We tested the hypothesis that EC aerosol contains metals derived from various components in EC.Cartomizer contents and aerosols were analyzed using light and electron microscopy, cytotoxicity testing, x-ray microanalysis, particle counting, and inductively coupled plasma optical emission spectrometry.The filament, a nickel-chromium wire, was coupled to a thicker copper wire coated with silver. The silver coating was sometimes missing. Four tin solder joints attached the wires to each other and coupled the copper/silver wire to the air tube and mouthpiece. All cartomizers had evidence of use before packaging (burn spots on the fibers and electrophoretic movement of fluid in the fibers. Fibers in two cartomizers had green deposits that contained copper. Centrifugation of the fibers produced large pellets containing tin. Tin particles and tin whiskers were identified in cartridge fluid and outer fibers. Cartomizer fluid with tin particles was cytotoxic in assays using human pulmonary fibroblasts. The aerosol contained particles >1 µm comprised of tin, silver, iron, nickel, aluminum, and silicate and nanoparticles (<100 nm of tin, chromium and nickel. The concentrations of nine of eleven elements in EC aerosol were higher than or equal to the corresponding concentrations in conventional cigarette smoke. Many of the elements identified in EC aerosol are known to cause respiratory distress and disease.The presence of metal and silicate particles in cartomizer aerosol demonstrates the need for improved quality control in EC design and manufacture and studies on how EC aerosol impacts the health of users and bystanders.

  3. Turbulent Mixing of Metal and Silicate during Planet Accretion – and interpretation of the Hf-W chronometer

    DEFF Research Database (Denmark)

    Dahl, Tais Wittchen; Stevenson, David


    In the current view of planet formation, the final assembly of the Earth involved giant collisions between protoplanets (N1000 kmradius), with theMoon formed as a result of one such impact.At this stage the colliding bodies had likely differentiated into a metallic core surrounded by a silicate m...

  4. Turbulent mixing of metal and silicate during planet accretion — And interpretation of the Hf-W chronometer (United States)

    Dahl, Tais W.; Stevenson, David J.


    In the current view of planet formation, the final assembly of the Earth involved giant collisions between proto-planets (> 1000 km radius), with the Moon formed as a result of one such impact. At this stage the colliding bodies had likely differentiated into a metallic core surrounded by a silicate mantle. During the Moon-forming impact, nearly all metal sank into the Earth's core. We investigate to what extent large self-gravitating iron cores can mix with surrounding silicate and how this influences the short-lived chronometer, Hf-W, used to infer the age of the Moon. We present fluid dynamical models of turbulent mixing in fully liquid systems, attempting to place constraints on the degree of mixing. Erosion of sinking cores driven by Rayleigh-Taylor instability does lead to intimate mixing and equilibration, but large blobs (> 10 km diameter) do not emulsify entirely. Emulsification is enhanced if most of the accreting metal cores deform into thin structures during descent through the Earth's mantle. Yet, only 1-20% of Earth's core would equilibrate with silicate during Earth's accretion. The initial speed of the impactor is of little importance. We proceed to evaluate the mixing potential for shear instabilities where silicate entrainment across vertical walls causes mixing. The turbulent structure indicates that vortices remain at the largest scale and do not mix to centimeter length scale, where diffusion operates and isotopes can equilibrate. Thus, incomplete emulsification and equilibration of accreting iron cores is likely to occur. The extent of metal-silicate equilibration provides key information for interpretation of siderophile budgets and the timing of core formation using the Hf-W chronometer. The time scale of core formation derived from the Hf-W chronometer is usually tied to the last major metal-silicate re-equilibration, believed to coincide with time of the Moon-forming impact. However, we show that large cores have limited ability to reset

  5. Heavy metal screening in compounds feeds

    Directory of Open Access Journals (Sweden)

    Tomas Toth


    Full Text Available Heavy metals are generally classified as basic groups of pollutants that are now a days found in different environmental compartments. This is quite a large group of contaminants, which have different characteristics, effects on the environment and sources of origin. For environment pose the greatest risks, especially heavy metals produced by anthropogenic activities that adversely affect the health and vitality of organisms and natural environmental conditions. Livestock nutrition is among the main factors which affect not only the deficiency of livestock production and quality of food of animal origin, but they are also a factor affecting the safety and wholesomeness and the animal health. Compound feeds is characterized as a mixture of two or more feed grain. Containing organic, inorganic nutrients and specifically active compound feed meet the nutritional requirements of a given kind and age category of animals. They are used mainly in the diet of pigs, poultry, but also the nutrition of cattle, sheep, horses and other animal categories. The basic ingredients are cereals in proportion of 60-70 %. The aim of this thesis was to analyze the content of hazardous elements (copper, zinc, iron, manganese, cobalt, nickel, chromium, lead, cadmium, mercury in 15 samples of compound feeds and then evaluating their content in comparison with maximum limits laid down by Regulation of the Government of the Slovak Republic and Regulation Commission (EC.

  6. Elemental partitioning and isotopic fractionation of Zn between metal and silicate and geochemical estimation of the S content of the Earth's core

    CERN Document Server

    Mahan, B; Pringle, E A; Moynier, F


    Zinc metal-silicate fractionation provides experimental access to the conditions of core formation and Zn has been used to estimate the S contents of the Earth's core and of the bulk Earth, assuming that they share similar volatility and that Zn was not partitioned into the Earth's core. We have conducted a suite of partitioning experiments to characterize Zn metal-silicate elemental and isotopic fractionation as a function of time, temperature, and composition. Experiments were conducted at temperatures from 1473-2273K, with run durations from 5-240 minutes for four starting materials. Chemical and isotopic equilibrium is achieved within 10 minutes. Zinc metal-silicate isotopic fractionation displays no resolvable dependence on temperature, composition, or oxygen fugacity. Thus, the Zn isotopic composition of silicate phases can be used as a proxy for bulk telluric bodies. Results from this study and literature data were used to parameterize Zn metal-silicate partitioning as a function of temperature, pressu...

  7. Si isotope fractionation between Si-poor metal and silicate melt at pressure-temperature conditions relevant to metal segregation in small planetary bodies (United States)

    Kempl, J.; Vroon, P. Z.; Zinngrebe, E.; van Westrenen, W.


    Experimental investigations of Si isotope fractionation between Si-bearing metal alloy and silicate phases have to date been limited to high pressure (1-7 GPa) and high temperature (1800-2200 °C) conditions at highly reducing conditions, to optimize applicability of results to early core formation processes in the Earth. Here, we assess the extent and mechanism of Si isotopic fractionation at conditions relevant to metal segregation in small (km-scale) planetary bodies, using samples obtained from an industrial-scale blast furnace of Tata Steel (IJmuiden, the Netherlands). During the low-pressure, high-temperature process of steelmaking inhomogeneous blast furnace burden consisting of pre- and untreated iron ore, iron silicates and coke is reduced to oxygen fugacities near the C-CO buffer, resulting in the segregation of a metal phase containing only ∼0.3 wt% Si. Seven sample sets, each comprising a metal alloy and a silicate slag, were taken during tapping of the blast furnace at tapping temperatures between 1400 °C and 1600 °C. We find large isotopic mass fractionation between metal and silicate, with Δ30Sisilicate-metal varying between 0.7‰ and 1.6‰, values that are as high as previously obtained in high-pressure, highly reduced experiments. A model for metal-silicate Si isotope fractionation in blast furnaces can explain both the sense and magnitude of fractionation, if the presence of SiO-bearing vapour is explicitly taken into account. Our data indicate that significant Si isotope fractionation can occur between metal and silicate at low-pressure, high-temperature and only mildly reducing conditions for which Si solubility in molten Fe-rich metal is low. This suggests an important role for SiO at low confining pressures. Our data can be applied to models of aubrite meteorite formation through high-temperature differentiation of an enstatite chondrite parent body. Our calculations suggest a far larger degree of rehomogenisation during differentiation

  8. Photophoretic separation of metals and silicates: the formation of Mercury like planets and metal depletion in chondrites

    CERN Document Server

    Wurm, Gerhard; Rauer, Heike


    Mercury's high uncompressed mass density suggests that the planet is largely composed of iron, either bound within metal (mainly Fe-Ni), or iron sulfide. Recent results from the MESSENGER mission to Mercury imply a low temperature history of the planet which questions the standard formation models of impact mantle stripping or evaporation to explain the high metal content. Like Mercury, the two smallest extrasolar rocky planets with mass and size determination, CoRoT-7b and Kepler-10b, were found to be of high density. As they orbit close to their host stars this indicates that iron rich inner planets might not be a nuisance of the solar system but be part of a general scheme of planet formation. From undifferentiated chondrites it is also known that the metal to silicate ratio is highly variable which must be ascribed to pre-planetary fractionation processes. Due to this fractionation most chondritic parent bodies - most of them originated in the asteroid belt - are depleted in iron relative to average solar...

  9. Heterogeneous Earth Accretion and Incomplete Metal-Silicate Reequilibration at High Pressure During Core Formation (United States)

    Rubie, D. C.; Mann, U.; Frost, D. J.; Kegler, P.; Holzheid, A.; Palme, H.


    We present a new model of core formation, based on the partitioning of siderophile elements, that involves accreting the Earth through a series of collisions with smaller bodies that had already differentiated at low pressure. Each impact results in a magma ocean in which the core of the impactor reequilibrates with silicate liquid at high pressure before merging with the Earth's protocore. The oxygen contents of the chondritic compositions of the proto-Earth and impactors can be varied. The compositions of coexisting metal and silicate are determined through mass balance combined with partitioning equations for Ni, FeO, Si and other siderophile elements. The oxygen fugacity is fixed by the partitioning of FeO and is a function of P, T and bulk oxygen content. An important constraint for core formation is that core-mantle partition coefficients for Ni and Co must both converge to values of 23-28. Based on a recent study of the partitioning of Ni and Co over a wide P-T range (Kegler et al., EPSL, submitted) together with other published data, this constraint is not satisfied by a single- stage core formation model at any conditions because the partition coefficients converge at values that are much too low. In the present multi-stage model, the correct values can be reached if only part of each impactor core reequilibrates with silicate liquid in the magma ocean (as proposed by previous models based on Hf-W isotope studies). Physically, this would mean that impactor cores fail to emulsify completely as they sink through the magma ocean. Incorporating other elements (e.g. V and Cr) in the model requires, in addition, that the bulk composition of the impactors changes during accretion from reduced (FeO-poor) to oxidised FeO-rich). Then, with the resulting increase in fO2, incomplete reequilibration of the cores during the final 20-30% of Earth accretion is required to satisfy the Ni-Co constraint. In addition, this model enables the concentrations of O and Si in the

  10. On the metallicity dependence of crystalline silicates in oxygen-rich asymptotic giant branch stars and red supergiants

    CERN Document Server

    Jones, O C; Sargent, B A; McDonald, I; Gielen, C; Woods, Paul M; Sloan, G C; Boyer, M L; Zijlstra, A A; Clayton, G C; Kraemer, K E; Srinivasan, S; Ruffle, P M E


    We investigate the occurrence of crystalline silicates in oxygen-rich evolved stars across a range of metallicities and mass-loss rates. It has been suggested that the crystalline silicate feature strength increases with increasing mass-loss rate, implying a correlation between lattice structure and wind density. To test this, we analyse Spitzer IRS and Infrared Space Observatory SWS spectra of 217 oxygen-rich asymptotic giant branch stars and 98 red supergiants in the Milky Way, the Large and Small Magellanic Clouds and Galactic globular clusters. These encompass a range of spectral morphologies from the spectrally-rich which exhibit a wealth of crystalline and amorphous silicate features to 'naked' (dust-free) stars. We combine spectroscopic and photometric observations with the GRAMS grid of radiative transfer models to derive (dust) mass-loss rates and temperature. We then measure the strength of the crystalline silicate bands at 23, 28 and 33 microns. We detect crystalline silicates in stars with dust ma...

  11. Modified silicates applied in adsorption of heavy metal; Silicatos modificados aplicados na adsorcao de metal pesado

    Energy Technology Data Exchange (ETDEWEB)

    Farias, M.C.M. de [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Unidade Academica de Engenharia de Materiais; Raposo, C.M.O., E-mail: [Universidade Federal de Campina Grande (UFCG), Campina Grande, PB (Brazil). Unidade Academica de Mineracao e Geologia


    The levels of heavy metals in the environment has increased considerably in recent decades due to various human activities, which cause serious pollution problems, both in aquatic systems and in soil. The clay minerals present himself as amenable to the adsorption of metal ions and, sometimes, taking the advantage of being abundant and inexpensive. Vermiculite has intrinsic characteristics which favor its use as adsorbent. In this work, we investigate the adsorption of lead (II) from aqueous solutions by vermiculite fractions in commercial, fine to medium in molar concentration between 1-4 mmol (s). The samples provided by the Uniao Brasileira de Mineracao/Paraiba/Brazil were modified thermal and organically. The results of X-ray diffraction associated with the results of X-ray fluorescence showed that the average fraction vermiculite exfoliated organically modified responded most significantly to the adsorption process when compared to vermiculite fine fraction under the same conditions. (author)

  12. The Metal-Silicate Partitioning of Tungsten at Magma Ocean Conditions Using a Laser-Heated Diamond Anvil Cell (United States)

    Bennett, N.; Jackson, C.; Fei, Y.; Bullock, E. S.; Armstrong, J. T.


    The primitive upper mantle (PUM) represents the silicate residue of terrestrial core formation and should reflect element partitioning between metal and silicate melts that equilibrated in a magma ocean. Laboratory experiments suggest that the W/Mo ratio of PUM is only reproduced if S is added to the Earth during the late stages of accretion (Wade et al. 2012). Core-segregation, however, is posited to occur at >35 GPa and >3000 K; above the pressure range explored by existing W partitioning experiments and conditions under which O may also enter core-forming metal. The effect of light element solutes on a metallic Fe liquid can be modeled using experimentally determined interaction parameters (ɛ). On the basis of ɛ values determined at ambient pressure, both O and S should interact strongly with W (ɛw-o = 4.1, ɛw-s = 6.1), possibly complicating the history of W distribution during accretion. We have performed experiments to assess the metal-silicate partitioning of W at conditions directly relevant to those expected for the base of a magma ocean, under which O enters the metal phase. Experiments were performed at 15-50 GPa in a diamond anvil cell, using Re gaskets and an MgO pressure medium. In several instances, cells were loaded with two sample mixtures, containing W in either oxidized or reduced form. Heating spots subject to the same temperature and heating duration but different initial W oxidation state will be used to assess if heating times were sufficient to approach equilibrium. Samples were laser-heated at sector 13 of the Advanced Photon Source then recovered for analysis using a focused ion beam, to reveal cross-sections through the heated spot. Samples comprise a Fe-rich metal bleb, surrounded by silicate glass. The quenched metal contains exsolved spherules of a Si+O-rich phase, indicating significant solution of these elements at high pressure and temperature. Work is ongoing to quantify the element distribution between metal and silicate phases.

  13. The transition from carbon dust to silicates production in low-metallicity AGB and SAGB stars

    CERN Document Server

    Ventura, P; Schneider, R; Carini, R; Valiante, R; D'Antona, F; Gallerani, S; Maiolino, R; Tornambé, A


    We compute the mass and composition of dust produced by stars with masses in the range 1Msunmetallicity of Z=0.001 during their AGB and Super AGB phases. Stellar evolution is followed from the pre-main sequence phase using the code ATON which provides, at each timestep, the thermodynamics and the chemical stucture of the wind. We use a simple model to describe the growth of the dust grains under the hypothesis of a time-independent, spherically symmetric stellar wind. We find that the total mass of dust injected by AGB stars in the interstellar medium does not increase monotonically with stellar mass and ranges between a minimum of 10^{-6}Msun for the 1.5Msun stellar model, up to 2x10^{-4} Msun, for the 6Msun case. Dust composition depends on the stellar mass: low-mass stars (M < 3Msun) produce carbon-rich dust, whereas more massive stars, experiencing Hot Bottom Burning, never reach the carbon-star stage, and produce silicates and iron. This is in partial disagreement with previ...

  14. Siderophile elements in the upper mantle of the Earth: New clues from metal-silicate partition coefficients (United States)

    Holzheid, A.; Borisov, A.; Palme, H.


    New, precise data on the solubilities of Ni, Co, and Mo in silicate melts at 1400 C and fO2 from IW to IW-2 are presented. The results suggest NiO, CoO as stable species in the melt. No evidence for metallic Ni or Co was found. Equilibrium was ensured by reversals with initially high Ni and Co in the glass. Mo appears to change oxidation state at IW-1, from MoO3 to MoO2. Metal-silicate partition coefficients calculated from these data and recent data on Pd indicate similar partition coefficients for Pd and Mo at the conditions of core formation. This unexpected result constrains models of core formation in the Earth.

  15. Synthesis and Characterization of Amino-functionalized Meso-porous Silicate MCM-41 for Removal of Toxic Metal Ions

    Institute of Scientific and Technical Information of China (English)

    HAMID,Sepehrian; SYED,Waqif-Husain; MOHAMMAD,Ghannadi-Maragheh


    Amino-functionalized MCM-41 has been prepared by grafting amino containing functional groups onto mesoporous silicate MCM-41 and characterized by powder X-ray diffraction, N2 adsorption/desorption measure-ment, SEM, FT-IR, thermogravimetry and elemental analysis to confirm the ordered mesoporous structure and the functionalization of the amino groups. Sorption behavior for 18 metal ions on this sorbent has been studied and discussed.

  16. Leguminous plants nodulated by selected strains of Cupriavidus necator grow in heavy metal contaminated soils amended with calcium silicate. (United States)

    Avelar Ferreira, Paulo Ademar; Lopes, Guilherme; Bomfeti, Cleide Aparecida; de Oliveira Longatti, Silvia Maria; de Sousa Soares, Cláudio Roberto Fonseca; Guimarães Guilherme, Luiz Roberto; de Souza Moreira, Fatima Maria


    Increasing concern regarding mining area environmental contamination with heavy metals has resulted in an emphasis of current research on phytoremediation. The aim of the present study was to assess the efficiency of symbiotic Cupriavidus necator strains on different leguminous plants in soil contaminated with heavy metals following the application of inorganic materials. The application of limestone and calcium silicate induced a significant increase in soil pH, with reductions in zinc and cadmium availability of 99 and 94 %, respectively. In addition, improved nodulation of Mimosa caesalpiniaefolia, Leucaena leucocephala and Mimosa pudica in soil with different levels of contamination was observed. Significant increases in the nitrogen content of the aerial parts of the plant were observed upon nodulation of the root system of Leucaena leucocephala and Mimosa pudica by strain UFLA01-659 (36 and 40 g kg(-1)) and by strain UFLA02-71 in Mimosa caesalpiniaefolia (39 g kg(-1)). The alleviating effect of calcium silicate resulted in higher production of dry matter from the aerial part of the plant, an increase in nodule number and an increase in the nitrogen fixation rate. The results of the present study demonstrate that the combination of rhizobia, leguminous plants and calcium silicate may represent a key factor in the remediation of areas contaminated by heavy metals.

  17. Electrical characterization of thulium silicate interfacial layers for integration in high-k/metal gate CMOS technology (United States)

    Dentoni Litta, Eugenio; Hellström, Per-Erik; Henkel, Christoph; Östling, Mikael


    This work presents a characterization of the electrical properties of thulium silicate thin films, within the scope of a possible application as IL (interfacial layer) in scaled high-k/metal gate CMOS technology. Silicate formation is investigated over a wide temperature range (500-900 °C) through integration in MOS capacitor structures and analysis of the resulting electrical properties. The results are compared to those obtained from equivalent devices integrating lanthanum silicate interfacial layers. The thulium silicate IL is formed through a gate-last CMOS-compatible process flow, providing IL EOT of 0.1-0.3 nm at low formation temperature and interface state density at flatband condition below 2 × 1011 cm-2 eV-1. The effects of a possible integration in a gate-first process flow with a maximum thermal budget of 1000 °C are also evaluated, achieving an IL EOT of 0.2-0.5 nm, an interface state density at flatband condition ∼1 × 1011 cm-2 eV-1 and a reduction in gate leakage current density of one order of magnitude compared to the same stack without IL.

  18. Process for forming a metal compound coating on a substrate (United States)

    Sharp, D.J.; Vernon, M.E.; Wright, S.A.


    A method of coating a substrate with a thin layer of a metal compound by forming a dispersion of an electrophoretically active organic colloid and a precursor of the metal compound in an electrolytic cell in which the substrate is an electrode. Upon application of an electric potential, the electrode is coated with a mixture of the organic colloid and the precursor to the metal compound, and the coated substrate is then heated in the presence of an atmosphere or vacuum to decompose the organic colloid and form a coating of either a combination of metal compound and carbon, or optionally forming a porous metal compound coating by heating to a temperature high enough to chemically react the carbon.

  19. Are phenolic compounds released from the Mediterranean shrub Cistus albidus responsible for changes in N cycling in siliceous and calcareous soils? (United States)

    Eva Castells; Josep Peñuelas; David W. Valentine


    We studied the effects of Cistus albidus leaf leachates on nitrogen-cycling processes in two siliceous soils (granite and schist) and one calcareous soil. We compared those effects with gross N-transformation rates in soils sampled underneath Cistus. Our results show that although phenolic compounds leached from green foliage...

  20. Comparison of hafnium silicate thin films on silicon (1 0 0) deposited using thermal and plasma enhanced metal organic chemical vapor deposition

    Energy Technology Data Exchange (ETDEWEB)

    Rangarajan, Vishwanathan; Bhandari, Harish; Klein, Tonya M


    Hafnium silicate thin films were deposited by metal organic chemical vapor deposition (MOCVD) on Si at 400 deg. C using hafnium (IV) t-butoxide. Films annealed in O{sub 2} were compared to as-deposited films using X-ray photoelectron spectroscopy and X-ray diffraction. Hafnium silicate films were deposited by both thermal and plasma enhanced MOCVD using 2% SiH{sub 4} in He as the Si precursor. An O{sub 2} plasma increased Si content to as much as {approx}26 at.% Si. Both thermal and plasma deposited Hf silicates are amorphous as deposited, however, thermal films exhibit crystallinity after anneal. Surface roughness as measured by atomic force microscopy was found to be 1.1 and 5.1 nm for MOCVD hafnium silicate and plasma enhanced MOCVD hafnium silicate, respectively.

  1. XANES spectra of metal phytate compounds (United States)

    Metal speciation of phosphate and metal-phosphate interactions can be investigated by molecular-scale X-ray absorption near edge structure (XANES) spectroscopic analysis. Much of the effort, however, has been focused on inorganic P speciation (i. e. metal-orthophosphate interactions). Phytate (inosi...

  2. Experimental determination of Fe isotope fractionation between liquid metal, silicate and sulfide at high pressures and temperatures (United States)

    Williams, H. M.; Wood, B. J.; Halliday, A. N.


    There is evidence for significant equilibrium Fe isotope fractionation (≤0.26‰/amu) between metal and troilite (FeS) in iron meteorites (Williams et al., EPSL (250) 2006) and a smaller fractionation (Gessmann and Wood, EPSL (200) 2002; Wood et al., EPSL (in revision) 2007). Metal, sulfide and silicate fractions were separated from mounted and sectioned experimental charges using a computer-controlled micromill (New Wave-Merchantek). Sample dissolution, Fe purification and isotopic analysis followed established procedures (Williams et al., EPSL (235) 2005). In agreement with another preliminary high-pressure experimental study (Poitrasson and Roskosz, LPSC XXXVIII 2007) we find no appreciable fractionation between liquid iron metal and basaltic melt. However, there is a resolvable Fe isotope fractionation between silicate melt and Fe-S alloy which ranges from 0.12±0.04 to 0.15±0.04‰/amu for separate experiments (errors are propagated based on the 2 SD errors of replicate analyses). The Fe isotope compositions of coexisting phases from these experiments define a positive linear relationship with a slope that is, within error, equal to unity, implying isotopic equilibrium. No relationship between apparent fractionation factor and pressure or temperature is detectable within the range covered by the experiments. The fractionation factors determined from our experiments overlap with the average equilibrium fractionation factor obtained between silicate melt and pyrrhotite (Fe1-xS) of 0.18±0.02‰/amu at 0.5GPa and 1114-1274K (Schuessler et al., GCA (71) 2007) and are also broadly consistent with silicate-FeS fractionation factors inferred indirectly from iron meteorites and pallasites which range from ~0.16 to 0.24‰/amu. Taken together these observations suggest that resolvable stable isotope fractionation between Fe-S alloys and silicate melts can take place at extreme pressure and temperature conditions and that isotopically light Fe can be sequestered into

  3. A sulfur-poor terrestrial core inferred from metal-silicate partitioning experiments (United States)

    Suer, Terry-Ann; Siebert, Julien; Remusat, Laurent; Menguy, Nicolas; Fiquet, Guillaume


    As a siderophile and a volatile element, sulfur's partitioning behavior allows constraints to be placed on processes in the primitive Earth. Sulfur's core-mantle distribution during Earth's accretion has consequences for core content and implications for volatile accretion. In this study, metal-silicate partitioning experiments of sulfur were conducted in a diamond anvil cell at pressures from 46 to 91 GPa and temperatures between 3100 and 4100 K, conditions that are directly relevant to core segregation in a deep magma ocean. The sulfur partition coefficients measured from these experiments are an order of magnitude less than those obtained from extrapolation of previous results to core formation conditions (e.g., Rose-Weston et al., 2009; Boujibar et al., 2014). These measurements challenge the idea that sulfur becomes a highly siderophile element at high pressures and temperatures. A relationship was derived that describes sulfur's partitioning behavior at the pressure-temperature range of core formation. This relationship combined with an accretion model was used to explore the effects of varying impactor sizes and volatile compositions on the sulfur contents of the Earth's core and mantle. The results show that homogeneous delivery of sulfur throughout accretion would overenrich the mantle in sulfur relative to the present day observations of 200 ± 80 ppm (Lorand et al., 2013) unless the bulk Earth sulfur content is lower than its cosmochemical estimate of ∼6400 ppm (e.g., McDonough, 2003). On the other hand, the mantle's sulfur content is matched if sulfur is delivered with large bodies (3 to 10% Earth mass) during the last 20% of Earth's accretion, combined with a chondritic late veneer of 0.5% Earth mass. These results are conditional on the lowered equilibration efficiency of large impactor cores in a terrestrial magma ocean. In each accretion scenario, the core sulfur content remains below ∼2 wt.% in close agreement with cosmochemical estimates and

  4. Morphology of metal nanoparticles photodeposited on TiO2/silical gel and photothermal activity for destruction of ethylene

    Institute of Scientific and Technical Information of China (English)

    HU Chun; LIN Lan-yu; HU Xue-xiang


    The morphology of supported metal nanoparticles on TiO2/silical gel (TSO) and photothermal synergism were investigated for destruction of ethylene. During photocatalytic deposition of metal nanopartilces, the effects of pH and light intensity on the morphology of coated platinum, palladium, gold on TiO2/silical gel were studied. Moreover, these catalysts were characterized by TEM, UV-Vis DRS. The pH of preparing solution have strong influence on dispersion, size and sites of Pt, Pd and Au on TSO, which were controlled by the electrostatic binding of HPtCl6-, AuCl4- and TiOH2+, Pd2+and TiO- respectively. Platinum, gold and palladium nanoparticles were uniformly highly dispersed on the titanol sites not silanol of TiO2/silical gel under pH=2, pH =9.9 respectively. For the photodegradation of ethylene, they show higher photothermal efficiency than those prepared with other pH conditions under UV illumination in a non-circulating photoreactor. The optimum weight loadings of Pt. Au, and Pd were 0.25 wt%, 0.5 wt%, 1 wt%,respectively. The synergistic effect enhanced ethylene removal and CO2 production. These results verify that the best photothermal synergistic effect depends on the dispersion, size of noble metal nano-particles. FTIR analyses of the used Pt-, Pd-TSO catalysts indicated that no significant by-products were accumulated on the surface of the catalysts, leading to them longer lifetime.

  5. [Biological activity of selenorganic compounds at heavy metal salts intoxication]. (United States)

    Rusetskaya, N Y; Borodulin, V B


    Possible mechanisms of the antitoxic action of organoselenium compounds in heavy metal poisoning have been considered. Heavy metal toxicity associated with intensification of free radical oxidation, suppression of the antioxidant system, damage to macromolecules, mitochondria and the genetic material can cause apoptotic cell death or the development of carcinogenesis. Organic selenium compounds are effective antioxidants during heavy metal poisoning; they exhibit higher bioavailability in mammals than inorganic ones and they are able to activate antioxidant defense, bind heavy metal ions and reactive oxygen species formed during metal-induced oxidative stress. One of promising organoselenium compounds is diacetophenonyl selenide (DAPS-25), which is characterized by antioxidant and antitoxic activity, under conditions including heavy metal intoxication.

  6. Process for the conversion of sugars to lactic acid and 2-hydroxy-3-butenoic acid or esters thereof comprising a metallo-silicate material and a metal ion

    DEFF Research Database (Denmark)


    A process for the preparation of lactic acid and 2-hydroxy- 3-butenoic acid or esters thereof from a sugar in the presence of a metallo-silicate material, a metal ion and a solvent, wherein the metal ion is selected from one or more of the group consisting of potassium ions, sodium ions, lithium ...... ions, rubidium ions and caesium ions....

  7. Experimental investigation of the partitioning of phosphorus between metal and silicate phases - Implications for the earth, moon and eucrite parent body (United States)

    Newsom, H. E.; Drake, M. J.


    An experimental study is reported of the partitioning of Phosphorus between solid metal and basaltic silicate liquid as a function of temperature and oxygen fugacity and of the implications for the earth, moon and eucrite parent body (EPB). The relationship established between the partition coefficient and the fugacity is given at 1190 C by log D(P) = -1.12 log fO2 - 15.95 and by log D(P) = -1.53 log fO2 17.73 at 1300 C. The partition coefficient D(P) was determined, and it is found to be consistent with a valence state of 5 for P in the molten silicate. Using the determined coefficient the low P/La ratios of the earth, moon, and eucrites relative to C1 chondrites can be explained. The lowering of the P/La ratio in the eucrites relative to Cl chondrite by a factor of 40 can be explained by partitioning P into 20-25 wt% sulfur-bearing metallic liquid corresponding to 5-25% of the total metal plus silicate system. The low P/La and W/La ratios in the moon may be explained by the partitioning of P and W into metal during formation of a small core by separation of liquid metal from silicate at low degrees of partial melting of the silicates. These observations are consistent with independent formation of the moon and the earth.

  8. studies on transition metal complexes of herbicidal compounds. ii

    African Journals Online (AJOL)


    II: TRANSITION METAL COMPLEXES OF DERIVATIZED 2-CHLORO-4- ... Several compounds of this class like atrazine, simazine, prometryn, aziprotryn, etc. .... dissolve in water and most of the common polar organic solvents. ... coordination.

  9. Smart textile device using ion polymer metal compound. (United States)

    Nakamura, Taro; Ihara, Tadashi


    We have developed a smart textile device that detects angular displacement of attached surface using ion polymer metal compound. The device was composed of ion polymer metal compound (IPMC) which was fabricated from Nafion resin by heat-press and chemical gold plating. The generated voltage from IPMC was measured as a function of bending angle. Fabricated IPMC device was weaved into a cotton cloth and multidirectional movements were detected.

  10. Metal organic frameworks for removal of compounds from a fluid

    KAUST Repository

    Eddaoudi, Mohamed


    Embodiments provide a method of compound removal from a fluid. The method includes contacting one or more metal organic framework (MOF) compositions with a fluid and sorbing one or more compounds, such as CO2, H2S and condensable hydrocarbons. One or more of CO2, H2S and condensable hydrocarbons can be sorbed simultaneously or in series. The metal organic framework can be an M-soc-MOF.

  11. Heavy metal distribution in organic and siliceous marine sponge tissues measured by square wave anodic stripping voltammetry. (United States)

    Illuminati, S; Annibaldi, A; Truzzi, C; Scarponi, G


    May sponge spicules represent a "tank" to accumulate heavy metals? In this study we test this hypothesis determining the distribution of Cd, Pb and Cu concentrations between organic and siliceous tissues in Antarctic Demospongia (Sphaerotylus antarcticus, Kirkpatrikia coulmani and Haliclona sp.) and in the Mediterranean species Petrosia ficiformis. Results show that although, in these sponges, spicules represent about 80% of the mass content, the accumulation of pollutant is lower in the spicules than in the corresponding organic fraction. The contribution of tissues to the total sponge content of Cd, Pb and Cu is respectively 99%, 82% and 97% for Antarctic sponges and 96%, 95% and 96% for P. ficiformis, similar in polar and temperate organisms. These results pave the way to a better understanding of the role of marine sponges in uptaking heavy metals and to their possible use as monitor of marine ecosystems, recommend by the Water Framework Directive. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Preparation and characterization of starch-metal silicate Co-precipitates--evaluation as tablet superdisintegrant. (United States)

    Singh, Inderbir; Kaur, Birender; Juneja, Prateek


    Starch is a potential biomaterial used for various pharmaceutical applications because of its unique physicochemical and functional characteristics. A number of modification techniques, such as physical, chemical, enzymatic and genetic or a combination of any of these methods have been reported with the aim of enhancing the positive attributes and eliminating the shortcomings of the native starches. The present studies deal with the development of co-precipitates of corn starch with different silicates (Mg, Ca, Al) with an aim of using it as a tablet superdisintegrant. Co-precipitates of starch with different silicates were prepared and FTIR-ATR, XRD and SEM techniques were used for the characterization of conjugates. The conjugate were analyzed for various powder evaluation test like angle of repose, bulk density, tapped density, Hausner's ratio, Carr's index, swelling index and effective pore radius. The prepared co-precipitates were found to possess good powder flow properties. The swelling and effective pore radius of all co-precipitates (SMgC, SAlC and SCaC) was found in the range between 30-100% and 15.89-21.71 μm respectively. Different ratios of the prepared co-precipitates were used to formulate fast disintegrating tablets. Fast disintegrated tablets formulated using starch silicate conjugates as superdisintegrant were evaluated for diameter, thickness, hardness, friability, tensile strength, in vitro tablet disintegration, water absorption ratio, wetting time and in vitro dissolution studies. The effective pore radius and swelling of the co-precipitates were correlated with the in vitro disintegration, water absorption ratio and wetting time of the tablets. It was concluded that silicated co-precipitates of starch could be used as superdisintegrants in pharmaceutical tablet formulations.

  13. Understanding the defect chemistry of alkali metal strontium silicate solid solutions: insights from experiment and theory

    KAUST Repository

    Bayliss, Ryan D.


    © the Partner Organisations 2014. Recent reports of remarkably high oxide ion conduction in a new family of strontium silicates have been challenged. It has recently been demonstrated that, in the nominally potassium substituted strontium germanium silicate material, the dominant charge carrier was not the oxygen ion, and furthermore that the material was not single phase (R. D. Bayliss et. al., Energy Environ. Sci., 2014, DOI: 10.1039/c4ee00734d). In this work we re-investigate the sodium-doped strontium silicate material that was reported to exhibit the highest oxide ion conductivity in the solid solution, nominally Sr0.55Na0.45SiO2.775. The results show lower levels of total conductivity than previously reported and sub-micron elemental mapping demonstrates, in a similar manner to that reported for the Sr0.8K0.2Si0.5Ge0.5O2.9 composition, an inhomogeneous chemical distribution correlating with a multiphase material. It is also shown that the conductivity is not related to protonic mobility. A density functional theory computational approach provides a theoretical justification for these new results, related to the high energetic costs associated with oxygen vacancy formation. This journal is

  14. The assessment of mobility of heavy metals in technogenic soils by the combined approach for fractioning metal compounds (United States)

    Minkina, Tatiana; Motuzova, Galina; Mandzhieva, Saglara; Burachevskaya, Marina; Nazarenko, Olga; Nevidomskaya, Dina


    Introduction. Analysis of the fractional composition of heavy metals (HMs) compounds can reveal zonal and genetic features of soils and how natural and technogenic factors affect them. The aim of this work was to assess the state of HMs in soils subjected aerosol emissions from the Novocherkassk power station (NPS) on the basis of the fractional composition of their compounds. The emissions from the NPS comprise 1% of the total volume in the Russian Federation and up to 58% of the emissions in Rostov oblast. Materials and methods. Studies were conducted on the soils of monitoring plots distances from the NPS (1.0-20.0 km). The monitoring plots were located on fallow areas. Soil samples for the determination of soil properties and the contents of HM compounds were taken from a depth of 0-20 cm. The soil cover in the region under study consisted of ordinary chernozems, meadow-chernozemic soils, and alluvial meadow soils. The total amount of HMs in soils was determined by X-ray fluorescence. Metals in soil extracts were determined by atomic absorption spectroscopy. The fractional composition of HM were determined using combined fractionation (Minkina et al., 2008). A combined approach for fractioning metal compounds in soils on the basis of sequential (Tessier, 1979) and parallel extractions (1 N NH4Ac, pH 8; 1% EDTA in NH4Ac; and 1 N HCl). Results and discussion. The increasing of total content in soils of metals connected with technogenic emissions. In the contaminated soils, the increase in the total metal content is accompanied by changes in the proportions of metal compounds. In contrast to clean soils, where the metals strongly retained in the structure of silicate minerals are predominant (48-78% of the total amount), the content of LB metal compounds increases in the contaminated soils. The rise of metals mobility in the polluted soils and predominant participation of Cu, Pb, Mn, Cr and Ni organomineral complexes among their mobile species. The increasing of

  15. Stable chromium isotopic composition of meteorites and metal-silicate experiments: Implications for fractionation during core formation (United States)

    Bonnand, P.; Williams, H. M.; Parkinson, I. J.; Wood, B. J.; Halliday, A. N.


    We present new mass independent and mass dependent Cr isotope compositions for meteorites measured by double spike thermal ionisation mass spectrometry. Small differences in both mass independent 53Cr and 54Cr relative to the Bulk Silicate Earth are reported and are very similar to previously published values. Carbonaceous chondrites are characterised by an excess in 54Cr compared to ordinary and enstatite chondrites which make mass independent Cr isotopes a useful tool for distinguishing between meteoritic groups. Mass dependent stable Cr isotope compositions for the same samples are also reported. Carbonaceous and ordinary chondrites are identical within uncertainty with average δ53 Cr values of - 0.118 ± 0.040 ‰ and - 0.143 ± 0.074 ‰ respectively. The heaviest isotope compositions are recorded by an enstatite chondrite and a CO carbonaceous chondrite, both of which have relatively reduced chemical compositions implying some stable Cr isotope fractionation related to redox processes in the circumstellar disk. The average δ53 Cr values for chondrites are within error of the estimate for the Bulk Silicate Earth (BSE) also determined by double spiking. The lack of isotopic difference between chondritic material and the BSE provides evidence that Cr isotopes were not fractionated during core formation on Earth. A series of high-pressure experiments was also carried out to investigate stable Cr isotope fractionation between metal and silicate and no demonstrable fractionation was observed, consistent with our meteorites data. Mass dependent Cr isotope data for achondrites suggest that Cr isotopes are fractionated during magmatic differentiation and therefore further work is required to constrain the Cr isotopic compositions of the mantles of Vesta and Mars.

  16. Carcinogenic metal compounds: recent insight into molecular and cellular mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Beyersmann, Detmar [University of Bremen (Germany). Biochemistry, Department of Biology and Chemistry; Hartwig, Andrea [Technical University of Berlin (Germany). Institute of Food Technology and Food Chemistry


    Mechanisms of carcinogenicity are discussed for metals and their compounds, classified as carcinogenic to humans or considered to be carcinogenic to humans: arsenic, antimony, beryllium, cadmium, chromium, cobalt, lead, nickel and vanadium. Physicochemical properties govern uptake, intracellular distribution and binding of metal compounds. Interactions with proteins (e.g., with zinc finger structures) appear to be more relevant for metal carcinogenicity than binding to DNA. In general, metal genotoxicity is caused by indirect mechanisms. In spite of diverse physicochemical properties of metal compounds, three predominant mechanisms emerge: (1) interference with cellular redox regulation and induction of oxidative stress, which may cause oxidative DNA damage or trigger signaling cascades leading to stimulation of cell growth; (2) inhibition of major DNA repair systems resulting in genomic instability and accumulation of critical mutations; (3) deregulation of cell proliferation by induction of signaling pathways or inactivation of growth controls such as tumor suppressor genes. In addition, specific metal compounds exhibit unique mechanisms such as interruption of cell-cell adhesion by cadmium, direct DNA binding of trivalent chromium, and interaction of vanadate with phosphate binding sites of protein phosphatases. (orig.)

  17. Distribution of Precious Metals (Ag, Au, Pd, Pt, and Rh) Between Copper Matte and Iron Silicate Slag (United States)

    Avarmaa, Katri; Johto, Hannu; Taskinen, Pekka


    The distributions of precious metals (Ag, Au, Pd, Pt, and Rh) between copper matte and silica-saturated iron silicate slag were determined at 1523 K to 1623 K (1250 °C to 1350 °C), in controlled CO-CO2-SO2-Ar gas mixtures. The experiments were done in silica crucibles and a fixed partial pressure of sulfur dioxide for matte grades of 55, 65, and 75 wt pct Cu. High-temperature equilibration/quenching/electron probe X-ray microanalysis technique was used to obtain compositions of the equilibrated matte and slag. The technique was applied for the first time to the distributions of precious metals in simulated flash smelting conditions. The resolution of electron probe microanalysis became critical as the detection limits were insufficient to measure reliably the precious metals concentrations (except silver) in the slag. The distribution coefficient of silver, L m/s[Ag] = [wt pctAg in matte]/(wt pctAg in slag), was found to be between 200 and 300, which agrees well with the latest studies in the literature. For other precious metals, the minimum values of distribution coefficients were determined according to the detection limits in the slag. The values obtained were for gold and platinum >250, for palladium >1000, and for rhodium >900. The distribution coefficients of palladium, although locating above distribution coefficient of the detection limit, formed a clear dependency with a good repeatability as a function of the matte grade. It increased along with matte grade and was approximately 1000 at 50 pct Cu and 2000 to 3000 at 70 pct Cu. The precious metals replace metal in the matte structure and they are present as sulfides in the copper matte.

  18. Development of an immobilization process for heavy metal containing galvanic solid wastes by use of sodium silicate and sodium tetraborate

    Energy Technology Data Exchange (ETDEWEB)

    Aydın, Ahmet Alper, E-mail: [Chair of Urban Water Systems Engineering, Technische Universität München, Am Coulombwall, 85748 Garching (Germany); Aydın, Adnan [Istanbul Bilim University, School of Health, Esentepe, Istanbul, Sisli, 34394 (Turkey)


    Highlights: • A new physico-chemical process below 1000 °C for immobilization of galvanic sludges. • Sodium tetraborate and sodium silicate have been used as additives. • A strategy for adjustment of solid waste/additive mixture composition is presented. • Strategy is valid for wastes of hydrometallurgical and electro-plating processes. • Lower energy consumption and treated waste volume, shorter process time are provided. - Abstract: Heavy metal containing sludges from wastewater treatment plants of electroplating industries are designated as hazardous waste since their improper disposal pose high risks to environment. In this research, heavy metal containing sludges of electroplating industries in an organized industrial zone of Istanbul/Turkey were used as real-sample model for development of an immobilization process with sodium tetraborate and sodium silicate as additives. The washed sludges have been precalcined in a rotary furnace at 900 °C and fritted at three different temperatures of 850 °C, 900 °C and 950 °C. The amounts of additives were adjusted to provide different acidic and basic oxide ratios in the precalcined sludge-additive mixtures. Leaching tests were conducted according to the toxicity characteristic leaching procedure Method 1311 of US-EPA. X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscope-energy dispersive spectrometer (SEM-EDS) and flame atomic absorption spectroscopy (FAAS) have been used to determine the physical and chemical changes in the products. Calculated oxide molar ratios in the precalcined sludge-additive mixtures and their leaching results have been used to optimize the stabilization process and to determine the intervals of the required oxide ratios which provide end-products resistant to leaching procedure of US-EPA. The developed immobilization-process provides lower energy consumption than sintering-vitrification processes of glass–ceramics.

  19. Ferrous Silicate Spherules with Euhedral Fe,Ni-Metal Grains in CH Carbonaceous Chondrites: Evidence for Condensation Under Highly Oxidizing Conditions (United States)

    Krot, A. N.; Meibom, A.; Petaev, M. I.; Keil, K.; Zolensky, M. E.; Saito, A.; Mukai, M.; Ohsumi, K.


    A population of ferrous silicate spherules composed of cryptocrystalline ol-px-normative material, +/-SiO2-rich glass and rounded-to-euhedral Fe,Ni-metal grains preserved a condensation signature of the precursors formed under oxidizing conditions.

  20. Proficiency test for heavy metals in compound feed

    NARCIS (Netherlands)

    Pereboom, D.P.K.H.; Elbers, I.J.W.; Jong, de J.; Lee, van der M.K.; Nijs, de W.C.M.


    The here described proficiency test for heavy metals in compound feed was organised by RIKILT, Wageningen UR in accordance with ISO 17043. RIKILT Wageningen UR has an ISO/IEC 17043 accreditation for proficiency tests of residues in products of animal origin. However, this specific test is not part

  1. Mesoporous Silicate Materials in Sensing

    Directory of Open Access Journals (Sweden)

    Paul T. Charles


    Full Text Available Mesoporous silicas, especially those exhibiting ordered pore systems and uniform pore diameters, have shown great potential for sensing applications in recent years. Morphological control grants them versatility in the method of deployment whether as bulk powders, monoliths, thin films, or embedded in coatings. High surface areas and pore sizes greater than 2 nm make them effective as adsorbent coatings for humidity sensors. The pore networks also provide the potential for immobilization of enzymes within the materials. Functionalization of materials by silane grafting or through cocondensation of silicate precursors can be used to provide mesoporous materials with a variety of fluorescent probes as well as surface properties that aid in selective detection of specific analytes. This review will illustrate how mesoporous silicas have been applied to sensing changes in relative humidity, changes in pH, metal cations, toxic industrial compounds, volatile organic compounds, small molecules and ions, nitroenergetic compounds, and biologically relevant molecules.

  2. Covalent bonds against magnetism in transition metal compounds. (United States)

    Streltsov, Sergey V; Khomskii, Daniel I


    Magnetism in transition metal compounds is usually considered starting from a description of isolated ions, as exact as possible, and treating their (exchange) interaction at a later stage. We show that this standard approach may break down in many cases, especially in 4d and 5d compounds. We argue that there is an important intersite effect-an orbital-selective formation of covalent metal-metal bonds that leads to an "exclusion" of corresponding electrons from the magnetic subsystem, and thus strongly affects magnetic properties of the system. This effect is especially prominent for noninteger electron number, when it results in suppression of the famous double exchange, the main mechanism of ferromagnetism in transition metal compounds. We study this mechanism analytically and numerically and show that it explains magnetic properties of not only several 4d-5d materials, including Nb2O2F3 and Ba5AlIr2O11, but can also be operative in 3d transition metal oxides, e.g., in CrO2 under pressure. We also discuss the role of spin-orbit coupling on the competition between covalency and magnetism. Our results demonstrate that strong intersite coupling may invalidate the standard single-site starting point for considering magnetism, and can lead to a qualitatively new behavior.

  3. Raman scattering in transition metal compounds: Titanium and compounds of titanium

    Energy Technology Data Exchange (ETDEWEB)

    Jimenez, J.; Ederer, D.L.; Shu, T. [Tulane Univ., New Orleans, LA (United States)] [and others


    The transition metal compounds form a very interesting and important set of materials. The diversity arises from the many states of ionization the transition elements may take when forming compounds. This variety provides ample opportunity for a large class of materials to have a vast range of electronic and magnetic properties. The x-ray spectroscopy of the transition elements is especially interesting because they have unfilled d bands that are at the bottom of the conduction band with atomic like structure. This group embarked on the systematic study of transition metal sulfides and oxides. As an example of the type of spectra observed in some of these compounds they have chosen to showcase the L{sub II, III} emission and Raman scattering in some titanium compounds obtained by photon excitation.

  4. HRTEM/AEM study of trace metal behavior, sheet silicate reactions, and fluid/solid mass balances in porphyry copper hydrothermal systems

    Energy Technology Data Exchange (ETDEWEB)

    Veblen, D.R.; Ilton, E.S.


    Transmission electron microscopy has been used to investigate copper (Cu) incorporation into silicates and alteration reactions in porphyry copper deposits. High Cu in biotites results from submicroscopic inclusions of native Cu. The incorporation of Cu in low-temperature alteration lamellae suggests that Cu enrichment occurs during weathering, rather than during the hydrothermal event. Drill core from Cyprus Casa Grande, Arizona, shows systematic variation of Cu in sheet silicates as a function of depth in the weathering column. The aims of the present project are to apply the powerful techniques of transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and analytical electron microscopy (AEM) to understanding the geochemical processes in porphyry copper systems at the near-atomic scale. Our primary goals are to characterize the structural state of anomalously high Cu in silicates, determine the timing and conditions of Cu enrichment in silicates such as biotite, and use these data to suggest how base metals are released and subsequently immobilized under hydrothermal or weathering conditions; and to determine the submicroscopic, atomic-level reaction mechanisms responsible for silicate alteration in porphyry-copper hydrothermal systems, which will allow us to determine reaction stoichiometries and hence mass balances between minerals and hydrothermal fluid. 19 refs., 7 figs., 3 tabs.

  5. Trace metal contents of three tricalcium silicate materials: MTA Angelus, Micro Mega MTA and Bioaggregate. (United States)

    Kum, K Y; Kim, E-C; Yoo, Y-J; Zhu, Q; Safavi, K; Bae, K S; Chang, S W


    To investigate the levels of nine metals [aluminium (Al), antimony (Sb), arsenic (As), beryllium (Be), cadmium (Cd), chromium (Cr), iron (Fe), lead (Pb) and molybdenum (Mo)] in MTA Angelus, Micro Mega MTA and Bioaggregate using inductively coupled plasma-optical emission spectrometry (ICP-OES). Each material (0.2 g) was digested using a mixture of hydrochloric and nitric acids and then filtered. The levels of nine metals in the resulting filtrates were measured by ICP-OES. The results were statistically analysed using one-way anova and the Bonferroni test. MTA Angelus contained more aluminium, beryllium and chromium than Micro Mega MTA (P MTA Angelus and Micro Mega MTA contained small amounts of seven tested metal oxides. Bioaggregate only contained trace amounts of aluminium. © 2013 International Endodontic Journal. Published by John Wiley & Sons Ltd.

  6. Silicato de cálcio como amenizante da toxidez de metais pesados em mudas de eucalipto Calcium silicate to reduce heavy metal toxicity in eucalyptus seedlings

    Directory of Open Access Journals (Sweden)

    Adriana Maria de Aguiar Accioly


    Full Text Available O objetivo deste trabalho foi avaliar o efeito do silicato de cálcio na redução da toxidez de metais pesados no solo para Eucalyptus camaldulensis. Foram utilizadas cinco doses de silicato de cálcio (0, 1,6, 3,2, 4,8 e 6,4 g kg-1, em solos com diferentes graus de contaminação. O experimento foi conduzido em vasos com 1,5 kg de solo, com uma muda por vaso, em esquema fatorial 4x5 (quatro graus de contaminação x cinco doses de silicato. O silicato de cálcio reduziu a toxidez de metais pesados em E.camaldulensis, retardou o aparecimento dos sintomas de toxidez e diminuiu os teores de zinco e cádmio na parte aérea das plantas. Entretanto, não evitou totalmente a depressão no crescimento, nos solos com contaminação elevada. O efeito amenizante do silicato foi crescente com o aumento das doses e mais evidente nos solos com contaminação elevada. O efeito benéfico do silicato de cálcio está relacionado à redução da transferência do zinco para a parte aérea do eucalipto.The objective of this study was to evaluate the effect of calcium silicate to reduce heavy metal toxicity in Eucalyptus camaldulensis seedlings. Five doses of calcium silicate (0, 1.6, 3.2, 4.8, and 6.4 g kg-1 were used in soils with increasing levels of contamination. The experiment was carried out in pots with 1.5 kg of soil, with one plant each, in a 4x5 factorial array (four levels of contamination x five silicate doses. Calcium silicate minimized heavy metal toxicity to E.camaldulensis, delayed the onset of toxicity symptoms, and decreased zinc and cadmium shoot concentrations. However, calcium silicate did not completely overcome the depressive effect upon plant growth in soils with high metal concentrations. Calcium silicate effects increased with increasing doses and were more evident in highly contaminated soils. The beneficial effects of calcium silicate on metal toxicity were highly related to the decrease in zinc translocation to the eucalyptus shoots.

  7. Uptake of iodide by a mixture of metallic copper and cupric compounds

    Energy Technology Data Exchange (ETDEWEB)

    Lefevre, G.; Alnot, M.; Ehrhardt, J.J.; Bessiere, J. [Univ. Henri Poincare Nancy 1, Villers les Nancy (France). Lab. de Chimie Physique pour l`Environnement


    Environmental contaminants harmful to the health of present and future generations involve nuclear fission products as iodine radioisotopes. {sup 129}I is potentially one of the more mobile products because of its long half-life and its tendency to go into solution as an anion that is not retarded with silicate minerals. Ability of copper/cupric compound mixtures to remove iodide from solution was investigated to predict sorption of radioactive iodine in the environment and to assess their use in a nuclear reprocessing method. Thermodynamic calculations were performed to study the stability of such mixtures in solution and to obtain equilibrium constants of Cu(0)/Cu(II)/I{sup {minus}} and Cu(0)/Cu(II)/Cl{sup {minus}} systems. Both calculations and experimental results showed that a Cu(0)/Cu{sub 3}(OH){sub 2}(CO{sub 3}){sub 2} (azurite) mixture selectively uptakes iodide ions (initial concentrations: 10{sup {minus}2} and 10{sup {minus}1} M) in the presence of 10{sup {minus}1} M chloride ions. Reaction of iodide with copper powder and azurite crystal or copper plate and azurite powder have also been investigated, leading to precipitation of CuI onto massive copper phase. The different solids were separately analyzed by XPS and MEB-EDX, giving some insight in the uptake mechanism. It is proposed that soluble copper released by the cupric compound is reduced at the surface of metallic copper, leading to a preferential precipitation of CuI on copper surface.

  8. Elemental partitioning and isotopic fractionation of Zn between metal and silicate and geochemical estimation of the S content of the Earth's core (United States)

    Mahan, Brandon; Siebert, Julien; Pringle, Emily A.; Moynier, Frédéric


    Zinc metal-silicate fractionation provides experimental access to the conditions of core formation and Zn has been used to estimate the S contents of the Earth's core and of the bulk Earth, assuming that they share similar volatility and that Zn was not partitioned into the Earth's core. Therefore, Zn provides both direct and indirect information into the origin and eventual fate of volatile and siderophile elements on Earth. However, the partitioning of Zn between metal and silicate - as well as the associated isotopic fractionation - is not well known. We have conducted a suite of partitioning experiments to characterize Zn elemental partitioning and isotopic fractionation between metal and silicate as a function of time, temperature, and composition. Experiments were conducted at 2 GPa and temperatures from 1473 K to 2273 K in a piston cylinder apparatus, with run durations from 5 to 240 min for four distinct starting materials. Chemical and isotopic equilibrium is achieved within 10 min of experimental outset. Zinc metal-silicate isotopic fractionation displays no resolvable dependence on temperature, composition, or oxygen fugacity within the data set. Therefore, the Zn isotopic composition of silicate phases can be used as a proxy for bulk telluric bodies. Partitioning results from this study and data from literature were used to robustly parameterize Zn metal-silicate partitioning as a function of temperature, pressure, and redox state. Using this parametric characterization and viable formation conditions, we have estimated a range of Zn contents in the cores of iron meteorite parent bodies (i.e. iron meteorites) of ∼0.1-150 ppm, in good agreement with natural observations. We have also calculated the first geochemical estimates for the Zn contents of the Earth's core and of the bulk Earth, at 242 ± 107 ppm and 114 ± 34 ppm (respectively), that consider the slightly siderophile behavior of Zn. These estimates of the Zn contents of the Earth's core and

  9. Current noise in some transition-metal compounds

    NARCIS (Netherlands)

    Kleinpenning, Th.G.M.


    Measurements are reported on current noise in some single crystals of transition-metal compounds, namely: reduced Al-doped rutile (TiO2), Li-doped NiO, Li-doped CoO and Ga-doped CdCr2Se4. Also results obtained with polycrystalline Ga-doped CdCr2Se4 are reported. The current-noise spectra of the mate

  10. Evaluation of Three Chitin Metal Silicate Co-Precipitates as a Potential Multifunctional Single Excipient in Tablet Formulations

    Directory of Open Access Journals (Sweden)

    Rana Al-Shaikh Hamid


    Full Text Available The performance of the novel chitin metal silicate (CMS co-precipitates as a single multifunctional excipient in tablet formulation using direct compression and wet granulation methods is evaluated. The neutral, acidic, and basic drugs Spironolactone (SPL, ibuprofen (IBU and metronidazole (MET, respectively, were used as model drugs. Commercial Aldactone®, Fleximex® and Dumazole® tablets containing SPL, IBU and MET, respectively, and tablets made using Avicel® 200, were used in the study for comparison purposes. Tablets of acceptable crushing strength (>40 N were obtained using CMS. The friability values for all tablets were well below the maximum 1% USP tolerance limit. CMS produced superdisintegrating tablets (disintegration time < 1 min with the three model drugs. Regarding the dissolution rate, the sequence was as follow: CMS > Fleximex® > Avicel® 200, CMS > Avicel® 200 > Dumazole® and Aldactone® > Avicel® 200 > CMS for IBU, MET and SPL, respectively. Compressional properties of formulations were analyzed using density measurements and the compression Kawakita equation as assessment parameters. On the basis of DSC results, CMS co precipitates were found to be compatible with the tested drugs. Conclusively, the CMS co-precipitates have the potential to be used as filler, binder, and superdisintegrant, all-in-one, in the design of tablets by the direct compression as well as wet granulation methods.

  11. Metal-silicate partitioning during core formation on super-Earths (United States)

    Schaefer, L. K.; Jacobsen, S. B.; Petaev, M. I.; Sasselov, D. D.; Remo, J. L.


    Separation of the Earth into a rocky mantle and metallic Fe core is a problem long studied in the planetary science community (e.g. [1]). The timing of core formation influences the abundances of the siderophile elements found in the Earth's mantle, and the mechanism of core formation influences the degree of chemical equilibration between the rocky mantle and the core at the time of metal separation. However, limited work has been done on formation of metallic cores and its effects on mantle chemistry in rocky planets larger than the Earth. Super-Earths, exoplanets with masses up to ~ 5 Earth masses and radii up to ~1.6-1.7 Earth radii, have significantly larger internal pressures and consequently higher internal temperatures than the Earth, therefore conclusions from Earth-centric studies of core formation may be erroneous. Partitioning coefficients for many of the relevant elements (e.g. Fe, Ni, Si, O, etc.) are available in the literature, but only to relatively low pressures. The relevant pressures for super-Earths are significantly larger. However, data on Fe-O-Ni-Si partitioning at pressures (200-500 GPa) and temperatures relevant to super-Earths have been measured by laser-induced shocks with the ZBL laser at Sandia National Laboratory with a method described in [2]. We will present a model which integrates this data with lower pressure partition coefficients from the literature (e.g. [3],[4],[5]), with special emphasis on Fe and O, to describe partitioning behavior at high pressures and discuss its implications for core size and composition on rocky super-Earths. [1] Ringwood, A.E. (1977) Geochem. J. 11, 111-135. [2] Remo, J.L., Petaev, M.I., Jacobsen, S. B. (2008) LPSC abstract, 1420. [3] Frost, D.J. et al. (2010) JGR, B02202. [4] Kombayashi, T. (2014) JGR, 4164-4177. [5] Rubie, D.C. et al. (2011) EPSL, 301, 31-42. [5

  12. Volatile heavy metal mobility in silicate liquids: Implications for volcanic degassing and eruption prediction (United States)

    MacKenzie, Jason M.; Canil, Dante


    The volatilization of Cd, Re, Tl, Pb, Sb and Te from melts in the system CaO-MgO-Al 2O 3-SiO 2 (CMAS) and Na 2O-MgO-Al 2O 3-SiO 2 (NMAS) has been investigated at 0.1 MPa and 1200-1350 °C. Experiments were conducted in air using metal-doped melts in Pt crucibles. Analysis of quenched glasses by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) normal to the melt/gas interface produced concentration profiles for Cd, Re, Tl, Pb, Sb and Te to which a semi-infinite one-dimensional diffusion model could be applied to extract diffusion coefficients ( D). The melt was also doped with Cu, Zn, In, Mo, Sn and W but concentration profiles for these metals did not develop. In the CMAS composition at 1300 °C, the fastest diffusing element was Cd having a log DCd = - 6.5 ± 0.2. The slowest element was Re with log DRe = - 7.5 ± 0.3. Diffusivities of Sb, Te, Pb and Tl have intermediate values where log DSb = - 7.1 ± 0.1, log DTe = - 7.2 ± 0.3, log DPb = - 7.1 ± 0.2, log DTl = - 7.0 ± 0.2 cm 2/s. In the NMAS composition, log DRe = - 6.5 ± 0.2, log DSb = - 6.0 ± 0.2, log DPb = - 6.1 ± 0.1, log DTl = - 5.8 ± 0.2 cm 2/s (values for Cd and Te were not determined). Differences in diffusivity of volatile heavy metal ions to a melt-gas interface lead to significant fractionation between these metals in magmas during degassing. Given the observed differences in Cd and Re diffusivities in the CMAS composition, we predict an increase in the normalized Cd/Re ratio in the gas phase with increasing bubble growth rate. Monitoring of the Cd/Re ratios in aerosols from degassing volcanoes may provide a tool for predicting volcanic eruption.

  13. Metal-silicate Partitioning of Uranium and Thorium up to 138 GPa and 5500 K and Implications for Stratified Layer at the Top of the Outer Core (United States)

    Nomura, R.; Hirose, K.; Kimura, J. I.; Chang, Q.


    The excess abundances of siderophile elements in the mantle can be explained by metal-silicate equilibrium at mid-mantle depths in magma ocean of the growing Earth. The final equilibrium pressure and temperature would reach 37-60 GPa and melting temperature of the mantle at this pressure (Wade et al. 2012; Siebert et al., 2013). Much severe conditions (>6000 K) have been supposed at the final stage of the Earth's formation immediate aftermath the moon-forming giant impact (e.g. Canup, 2004), evoking the additional chemical equilibrium between core materials of the giant impactor and the surrounding silicate materials. Previous studies on partitioning of U up to 20 GPa and 2700 K by multi-anvil press have shown very small partition coefficients (D ~10^-5) in S-poor system with oxygen fugacity at around IW-1.5 (Wheeler et al., 2006; Bouhifd et al., 2013). Such a very small D make it difficult to examine the partitioning at higher P-T using laser-heated diamond anvil cell (LH-DAC) and electron microprobe since the small size of each phase introduce artificial error by such as secondary fluorescent effect (Wade and Wood, 2012). 1% contamination from surrounding silicate may increase D by three orders (i.e. D =10^-2), artificially. One solution is to use laser ablation ICP-MS by carefully ablating only a metallic portion. Here, we introduced FIB to isolate the metallic phase from the surrounding silicate melt by slicing off surrounding silicate potion. Consequently, we have successfully obtained the metal-silicate partitioning data of U and Th up to 138 GPa and 5500 K in S-free/S-poor system using LH-DAC. The results show a large temperature dependence of partition coefficient of uranium and thorium, approaching to 0.1~1 at temperature near 5500 K. The pressure dependence was not observed clearly. The large temperature dependence suggests that only the core material of the giant impactor can be enriched in U and Th, which may stratify at the top of the liquid core.

  14. Spontaneously formed interfacial metal silicates and their effect on the magnetism of superparamagnetic FeCo/SiO₂ core/shell nanoparticles. (United States)

    Desautels, Ryan D; Rowe, Michael P; Jones, Michael; Whallen, Amanda; van Lierop, Johan


    The integration of superparamagnetic core/shell nanoparticles into devices and other nanoscale technological applications requires a detailed understanding of how the intimate contact between core and shell nanophases affects the magnetism. We report how, for single-domain FeCo nanoparticles, an FeCo phase unique to the nanoscale with silica shells of increasing thicknesses spontaneously formed interfacial metal silicates between the core and shell (such as Fe2SiO4 and Co2SiO4) and altered the overall magnetism of the nanomaterial significantly. The influence of this previously overlooked phenomenon on magnetic properties is reported. Evidence of these metal silicate interfacial layers was observed by X-ray absorption spectroscopy (XAS) collected over the L3,2 absorption edges of Fe and X-ray photoelectron spectra (XPS) collected over the 2p transitions of Fe and Co. Through the correlation of magnetometry and XPS data, the evolution of nanoparticle magnetic anisotropy is shown to increase with the metal silicate.

  15. Spectral properties of erbium-doped heavy metal oxyfluoride silicate glasses for broadband amplification

    Institute of Scientific and Technical Information of China (English)

    徐时清; 杨中民; 戴世勋; 杨建虎; 戴能利; 林傲翔; 胡丽丽; 姜中宏


    Erbium-doped glasses showing a wide 1.55?m emission band are reported ina novel heavy metal oxyfluoride glass system SiO2-PbO-PbF2 and their optical properties such as emission spectra,fluorescence lifetime and the refractive index have been investigated.The broad and flat 4I13/2 →4I15/2 emission of Er3+ ions around 1.55μm can be used as host materials for potential optical amplifiers in wavelength-division-multiplexing network system.We find that with increasing PbF2 content in the glass composition,the fluorescence full width at half maximum and fluorescence lifetime of the 4I13/2 level of Er3+ increase,while refractive index and density decrease.

  16. Trace element composition and U-Pb age of zircons from Estherville: Constraints on the timing of the metal-silicate mixing event on the mesosiderite parent body (United States)

    Haba, Makiko K.; Yamaguchi, Akira; Kagi, Hiroyuki; Nagao, Keisuke; Hidaka, Hiroshi


    Mesosiderites are a group of stony-iron meteorites, which are thought to be the result of mixing of silicates with Fe-Ni metal. In this study, we combined textural observations with geochemical and chronological studies of two zircon grains found in the Estherville mesosiderite. One of the zircons (Zrc1) occurs with pyroxene, plagioclase, troilite, and silica, and the other (Zrc2) is located at a boundary between Fe-Ni metal and a silicate part mainly composed of pyroxene and plagioclase. The textural observations demonstrate that Zrc1 is relatively homogenous, whereas Zrc2 is composed of at least two chemically distinct domains. Trace element analyses of Zrc2 resolve large concentration gradients within this single grain with variations that are an order of magnitude for rare earth elements (REE) and two orders of magnitude for U and Th. The lowest trace element concentration in Zrc2 is more than an order of magnitude lower than those of lunar and eucritic zircons. However, it is similar to those of Zrc1 and a zircon from the Vaca Muerta mesosiderite. The calculated REE composition of the melt in equilibrium with Zrc2 shows that Zrc2 and perhaps also Zrc1 did not crystallize from a melt that was produced by fractional crystallization of the primary magmatic mineral assemblages. The zircons with low REE, U, and Th concentrations can be interpreted to have formed in a residual melt after incorporation of large amounts of REE, U, and Th into secondary phosphate minerals, which formed during the metal-silicate mixing event. The large concentration gradients observed in Zrc2 suggest significant heterogeneities in the melt from which the zircon crystallized. Alternatively, either mixing or diffusion between a relict zircon and a newly formed zircon could explain the observed concentration gradients. However, the REE patterns of Zrc2 cannot be explained by mixing or diffusion between the two distinct generations of zircons. These considerations suggest that Zrc1 and Zrc2

  17. Investigations on organogermanium compounds XI. Preparation and structure of trialkylgermyl alkali metal compounds in hexamethylphosphoric triamide (HMPT)

    NARCIS (Netherlands)

    Bulten, E.J.; Noltes, J.G.


    In this paper a full report is given of our investigations into the preparation of trialkylgermyl alkali metal compounds. The most satisfactory route to these compounds involves the cleavage of hexaalkyldigermanes with alkali metals in HMPT at room temperature. The structure, thermal stability and

  18. Experimental observations on noble metal nanonuggets and Fe-Ti oxides, and the transport of platinum group elements in silicate melts (United States)

    Anenburg, Michael; Mavrogenes, John A.


    Platinum group element (PGE) nanonuggets are a nuisance in experimental studies designed to measure solubility or partitioning of noble metals in silicate melts. Instead of treating nanonuggets as experimental artifacts, we studied their behaviour motivated by recent discoveries of PGE nanonuggets in a variety of natural settings. We used an experimental setup consisting of AgPd, Pt or AuPd capsules and Fe(-Ti) oxide-saturated hydrous peralkaline silicate melts to maximise nanonugget production. TABS (Te, As, Bi, Sb, Sn) commonly occur in PGM (platinum group minerals), prompting addition of Bi to our experiments to investigate its properties as well. Three-dimensional optical examination by 100× objective and immersion oil reveals variable colour which correlates with nanonugget size and shape due to plasmon resonance effects. We observe two textural types: (1) intermediate-sized nanonuggets dispersed in the glass and adhering to oxides, and (2) abundant fine nanonuggets dispersed in the glass with coarse euhedral crystals in contact with oxides. Slow cooling removes dispersed nanonuggets and greatly coarsens existing oxide-associated metal crystals. Nanonugget-free halos are commonly observed around oxide grains. All metal phases are composed of major (Ag, Pd) and trace (Pt, Ir, Au) capsule material. Our results show reduction processes, imposed by growing oxides, causing local metal saturation in the oxide rich zones with preferential nucleation on smaller oxide grains. The redox gradient then blocks additional metals from diffusing into oxide rich zones, forming halos. As the entire experimental charge is reduced throughout the run, nanonuggets form in the distal glass. Bismuth contents of metal phases do not depend on Bi2O3 amounts dissolved in the melt. Further PGM crystallisation consumes nanonuggets as feedstock. We conclude that the appearance of metallic PGE phases happens in two stages: first as nanonuggets and then as larger PGM. Once formed

  19. Metal-silicate partitioning of U: Implications for the heat budget of the core and evidence for reduced U in the mantle (United States)

    Chidester, Bethany A.; Rahman, Zia; Righter, Kevin; Campbell, Andrew J.


    Earth's core might require an internal heat source, such as radioactive decay, to explain the presence of the magnetic field through geologic time. To investigate whether U would be an important heat source in the core, we performed metal-silicate partitioning experiments of U at P-T (up to 67 GPa and 5400 K) conditions more relevant to a magma ocean scenario than has previously been reported. This study finds the partitioning of U to be strongly dependent on ƒO2, temperature, the S content of the metal and the SiO2 content of the silicate during core-mantle differentiation. Differentiation at mean conditions of 42-58 GPa and 3900-4200 K would put 1.4-3.5 ppb U (2-8 wt% S) in the core, amounting to a maximum of 1.4 (+1/-0.7) TW of heat 4.5 billion years ago. This is likely not enough heat to mitigate early widespread mantle melting. It was also found that U likely exists in the 2+ oxidation state in silicate melts in the deep Earth, a state which has not been previously observed in nature.

  20. Process for the preparation of composite crystalline aluminium silicates and their use as catalyst (carrier)

    Energy Technology Data Exchange (ETDEWEB)

    Van Erp, W.A.; Huizinga, T.; Seelen-Kruijssen, J.


    A process is presented for the preparation of a composite crystalline aluminum silicate by maintaining an aqueous alkaline starting mixture comprising one or more silicon compounds, one or more aluminium compounds, one or more compounds of metals from Group Ia of the Periodic Table and organic nitrogen compounds at an elevated temperature, until composite crystalline aluminium silicate has formed. Subsequently, crystalline silicate is separated from the mother liquor, wherein the various compounds are present in the starting mixture in defined molar ratios. These silicates can be used as catalyst or catalyst carrier in dewaxing hydrocarbon oils, to which process this invention further relates. To be used in such a process, the alkali metal content of the composite silicates must be reduced to less than 0.1 wt%. If desired, the performance of the silicates can be improved by using them simultaneously as carrier for one or more catalytically active metals from Groups VIb, VIIb and VIII8 of the Periodic Table or compounds thereof. The hydrocarbon oils which are to be dewaxed are preferably selected from the group consisting of lubricating oils and transformer oils (in order to reduce their pour point), and kerosenes and gas oils (in order to reduce their freezing point). Additionally, this invention relates to hydrocarbon oils which have been dewaxed according to the process of the invention. Furthermore, the invention relates to molecular sieves which comprise a composite crystalline aluminum silicate prepared as hereinbefore described, and to the application of such molecular sieves in a process for separating hydrocarbons. 5 tabs.

  1. Ionic liquids for extraction of metals and metal containing compounds from communal and industrial waste water. (United States)

    Fischer, Lisa; Falta, Thomas; Koellensperger, Gunda; Stojanovic, Anja; Kogelnig, Daniel; Galanski, Markus; Krachler, Regina; Keppler, Bernhard K; Hann, Stephan


    In a fundamental study the potential of ionic liquids based on quaternary ammonium- and phosphonium cations and thiol-, thioether-, hydroxyl-, carboxylate- and thiocyanate-functionalized anions has been assessed for future application in advanced sewage treatment. The elimination of the metal(oid)s Ag, As, Cd, Cr, Cu, Hg, Ni, Pb, Pt, Sn, Zn and the cancerostatic platinum compounds cisplatin and carboplatin was screened using a liquid phase micro-extraction set-up. The analytical tool-set consisted of ICP-SFMS and LC-ICP-MS for quantification of metal(oid)s and cancerostatic platinum compounds, respectively. The purity of the ILs was assessed for the investigated metal(oid)s on the base of present EU environmental quality standards and was found to be sufficient for the intended use. In model solutions at environmental relevant concentrations extraction efficiencies≥95% could be obtained for Ag, Cu, Hg and Pt with both phosphonium- and ammonium-based ILs bearing sulphur functionality in the form of thiosalicylate and 2-(methylthiobenzoate) anions, as well as with tricaprylmethylammonium thiocyanate within an extraction time of 120 min. All other metals were extracted to a lower extent (7-79%). In the case of cancerostatic platinum compounds a phosphonium-based IL bearing thiosalicylate functionality showed high extraction efficiency for monoaquacisplatin. For the first time, liquid phase micro extraction with ionic liquids was applied to industrial and communal waste water samples. The concentration of all investigated metal(oid)s could be significantly reduced. The degree of elimination varied with the initial concentration of metals, pH and the amount of suspended particulate matter.

  2. A study on transformation of some transition metal oxides in molten steelmaking slag to magnetically susceptible compounds

    Directory of Open Access Journals (Sweden)

    Shatokha V.


    Full Text Available Sustainable development of steelmaking requires solving a number of environmental problems. Economically feasible and environmentally friendly recycling of slag wastes is of special concern. Research of the team representing National Metallurgical Academy of Ukraine, Royal Institute of Technology, Carnegie Mellon University and URS Corp revealed a possibility of the controlled phase transformations in the liquid silicate melts followed by formation of the magnetically susceptible compounds. This approach enables selective recovery of metal values from slag. In this paper, the results obtained and further research directions are discussed. A possibility to exploit physical properties of the transition metals, typical for the metallurgical slags (such as Fe, Mn, V and others, and corresponding specific properties of their compounds, such as non-stoichiometry, mixed valency, pseudomorphosis, thermodynamic stability etc, in production of value-added materials from slag wastes is discussed. The results of the studies of thermodynamics and kinetics of oxidation in slags followed by phase transformation with binary, ternary and complex oxides under various physicochemical conditions are discussed in the view of their application for production of the materials with predefined physical properties. Peculiarities of precipitation in slags with various basicities are analysed and demonstrate capacity of the proposed approach in the production of the material with a given structure and size - for example, nano-sized crystals with structure of spinel. The approaches towards industrial realization of the developed method are also discussed.

  3. The W-W02 Oxygen Fugacity Buffer at High Pressures and Temperatures: Implications for f02 Buffering and Metal-silicate Partitioning (United States)

    Shofner, G. A.; Campbell, A. J.; Danielson, L.; Righter, K.


    a higher fO2 than the IW buffer at pressures lower than 40 GPa, and the magnitude of this difference decreases at higher pressures. This qualitatively indicates an increasingly lithophile character for W at higher pressures. The WWO buffer was quantitatively applied to W metal-silicate partitioning by using the WWO-IW buffer difference in combination with literature data on W metal-silicate partitioning to model the exchange coefficient (KD) for the Fe-W exchange reaction. This approach captures the pressure dependence of W metal-silicate partitioning using the WWO-IW buffer difference and models the activities of the components in the silicate and metallic phases using an expression of the Gibbs excess energy of mixing. Calculation of KD along a peridotite liquidus predicts a decrease in W siderophility at higher pressures that supports the qualitative behavior predicted by the WWO-IW buffer difference, and agrees with findings of others. Comparing the competing effects of temperature and pressure on W metal-silicate partitioning, our results indicate that pressure exerts a greater effect.

  4. Separation of metal chelates and organometallic compounds by SFC and SFE/GC. (United States)

    Wai, C M; Wang, S


    Supercritical fluid chromatography (SFC) combines the high diffusion coefficients of gas chromatography (GC) and the solubility properties of liquid chromatography (LC). SFC generally requires lower temperatures for chromatographic separations and thus is more suitable for analyzing thermally labile compounds including a number of metal chelates and organometallic compounds. SFC also allows interfacing between supercritical fluid extraction (SFE) and chromatographic analysis of metal-containing compounds. A large number of metal chelates and organometallic compounds can be separated by SFC. This article summarizes SFC separation of various chelates of transition metals, heavy metals, lanthanides and actinides as well as organometallic compounds of lead, mercury, and tin reported in the recent literature. This article also discusses SFC detection systems and the determination of solubility of organometallic compounds by SFC.

  5. Stable chromium isotopic composition of meteorites and metal-silicate experiments:Implications for fractionation during core formation


    Bonnand, P; WILLIAMS, H. M.; Parkinson, I. J.; Wood, B.J.; Halliday, A. N.


    We present new mass independent and mass dependent Cr isotope compositions for meteorites measured by double spike thermal ionisation mass spectrometry. Small differences in both mass independent 53Cr and 54Cr relative to the Bulk Silicate Earth are reported and are very similar to previously published values. Carbonaceous chondrites are characterised by an excess in 54Cr compared to ordinary and enstatite chondrites which make mass independent Cr isotopes a useful tool for distinguishing bet...

  6. Chronology and shock history of the Bencubbin meteorite: A nitrogen, noble gas, and Ar-Ar investigation of silicates, metal and fluid inclusions (United States)

    Marty, Bernard; Kelley, Simon; Turner, Grenville


    We have investigated the distribution and isotopic composition of nitrogen and noble gases, and the Ar-Ar chronology of the Bencubbin meteorite. Gases were extracted from different lithologies by both stepwise heating and vacuum crushing. Significant amounts of gases were found to be trapped within vesicles present in silicate clasts. Results indicate a global redistribution of volatile elements during a shock event caused by an impactor that collided with a planetary regolith. A transient atmosphere was created that interacted with partially or totally melted silicates and metal clasts. This atmosphere contained 15N-rich nitrogen with a pressure ⩾3 × 10 5 hPa, noble gases, and probably, although not analyzed here, other volatile species. Nitrogen and noble gases were re-distributed among bubbles, metal, and partly or totally melted silicates, according to their partition coefficients among these different phases. The occurrence of N 2 trapped in vesicles and dissolved in silicates indicates that the oxygen fugacity ( fO2) was greater than the iron-wüstite buffer during the shock event. Ar-Ar dating of Bencubbin glass gives an age of 4.20 ± 0.05 Ga, which probably dates this impact event. The cosmic-ray exposure age is estimated at ˜40 Ma with two different methods. Noble gases present isotopic signatures similar to those of "phase Q" (the major host of noble gases trapped in chondrites) but elemental patterns enriched in light noble gases (He, Ne and Ar) relative to Kr and Xe, normalized to the phase Q composition. Nitrogen isotopic data together with 40Ar/ 36Ar ratios indicate mixing between a 15N-rich component (δ 15N = +1000‰), terrestrial N, and an isotopically normal, chondritic N. Bencubbin and related 15N-rich meteorites of the CR clan do not show stable isotope (H and C) anomalies, precluding contribution of a nucleosynthetic component as the source of 15N enrichments. This leaves two possibilities, trapping of an ancient, highly fractionated

  7. Thin Films from Solvated Metal Atoms and Metal-Metal Bonded Compounds (United States)


    Departamento de Quimica , Universidad de Con- palladium colloids. cepcion, Casilla 3-C, Concepcion, Chile. (2) Department of Physics. (3) Turkevich, J.; Stevenson... change would be the period before particle stabilization that is important. realized. Indeed, with this procedure the resulting Pd And if controlled by concentration effects. 21 With palladium we electrophoretic behavior changed markedly, and mea- , invariably obtained particle sizes

  8. Thorium silicate compound as a solid-state target for production of isomeric thorium-229 nuclei by electron beam irradiation (United States)

    Borisyuk, P. V.; Vasilyev, O. S.; Lebedinskii, Y. Y.; Krasavin, A. V.; Tkalya, E. V.; Troyan, V. I.; Habibulina, R. F.; Chubunova, E. V.; Yakovlev, V. P.


    In this paper, we discuss an idea of the experiment for excitation of the isomeric transition in thorium-229 nuclei by irradiating with electron beam targets with necessary physical characteristics. The chemical composition and bandgap of ThSi10O22 were determined by X-ray photoelectron spectroscopy and reflection electron energy loss spectroscopy. It was found that the energy gap is equal to 7.7 eV and does not change when the target is exposed to a medium energy electron beam for a long time. This indicates that the compound possesses high electron-beam resistance. A quantitative estimation of the output function of isomeric thorium-229 nuclei generated by interaction of nuclei with the secondary electron flow formed by irradiating the solid-state ThSi10O22-based target is given. The estimation shows that ThSi10O22 is a promising thorium-containing target for investigating excitation of the nuclear low-lying isomeric transition in the thorium-229 isotope using medium-energy electrons.

  9. Thorium silicate compound as a solid-state target for production of isomeric thorium-229 nuclei by electron beam irradiation

    Directory of Open Access Journals (Sweden)

    P. V. Borisyuk


    Full Text Available In this paper, we discuss an idea of the experiment for excitation of the isomeric transition in thorium-229 nuclei by irradiating with electron beam targets with necessary physical characteristics. The chemical composition and bandgap of ThSi10O22 were determined by X-ray photoelectron spectroscopy and reflection electron energy loss spectroscopy. It was found that the energy gap is equal to 7.7 eV and does not change when the target is exposed to a medium energy electron beam for a long time. This indicates that the compound possesses high electron-beam resistance. A quantitative estimation of the output function of isomeric thorium-229 nuclei generated by interaction of nuclei with the secondary electron flow formed by irradiating the solid-state ThSi10O22-based target is given. The estimation shows that ThSi10O22 is a promising thorium-containing target for investigating excitation of the nuclear low-lying isomeric transition in the thorium-229 isotope using medium-energy electrons.

  10. Hydrogen Adsorption by Alkali Metal Graphite Intercalation Compounds (United States)

    Purewal, Justin

    Adsorption occurs whenever a solid surface is exposed to a gas or liquid, and is characterized by an increase in fluid density near the interface. Adsorbents have drawn attention in the current effort to engineer materials that store hydrogen at high densities within moderate temperature and pressure regimes. Carbon adsorbents are a logical choice as a storage material due to their low costs and large surface areas. Unfortunately, carbon adsorbents suffer from a low binding enthalpy for H2 (about 5 kJ mol-1), well below the 15 to 18 kJ mol-1) that is considered optimal for hydrogen storage systems. Binding interactions can be increased by the following methods: (1) adjusting the graphite interplanar separation with a pillared structure, and (2) introducing dopant species that interact with H2 molecules by strong electrostatic forces. Graphite intercalation compounds are a class of materials that contain both pillared structures and chemical dopants, making them an excellent model system for studying the fundamentals of hydrogen adsorption in nanostructured carbons. Pressure-composition-temperature diagrams of the MC24(H 2)x graphite intercalation compounds were measured for M = (K, Rb, Cs). Adsorption enthalpies were measured as a function of H2 concentration. Notably, CsC24 had an average adsorption enthalpy of 14.9 kJ mol-1), nearly three times larger than that of pristine graphite. The adsorption enthalpies were found to be positively correlated with the alkali metal size. Adsorption capacities were negatively correlated with the size of the alkali metal. The rate of adsorption is reduced at large H2 compositions, due to the effects of site-blocking and correlation on the H2 diffusion. The strong binding interaction and pronounced molecular-sieving behavior of KC24 is likely to obstruct the translational diffusion of adsorbed H2 molecules. In this work, the diffusion of H2 adsorbed in KC24 was studied by quasielastic neutron scattering measurements and molecular

  11. Anomalous peaks in NMR spectra of iron-containing silicate minerals: pseudo-contact shifts and the potential for mapping the distributions of transition metal ions (United States)

    Stebbins, J. F.; Kelsey, K. E.


    High-resolution nuclear magnetic resonance (NMR) spectroscopy has now been applied to problems of mineral structure for more than 25 years. Early attempts to collect MAS spectra on natural minerals rich in iron (or other cations with unpaired electron spins, e.g. more than a few % FeO) showed serious peak broadening, loss of signal, and thus loss of structural information. Spectroscopists have thus largely avoided such materials and have worked either with low-Fe natural minerals (e.g. zeolites) or with Fe-free synthetic compositions. While this problem remains, it has recently become apparent that in silicates with minor contents of such elements (100's to 1000's of ppm), or, in special cases, with much higher contents (at least 4% FeO), NMR spectra of nuclides such as Si-29 and Al-27 may indeed provide interesting and useful structural information that may eventually reveal new details of cation distribution, ordering, clustering, etc. Here we report on the early stages of this new application. In a recent report (Stebbins, Panero, Smyth and Frost, Am. Min. in press) we noted the presence of a variety of tiny "extra" peaks in Si-29 spectra of forsterite and wadsleyite, both containing 10's to 1000's of ppm of transition metal impurities. Some of these have chemical shifts well outside the known range for diamagnetic silicates, and were hypothesized to result from "pseudo-contact" interactions with unpaired electrons, which depend strongly on local structure. Peak shifts of this type have long been known in Sn-119 and Y-89 spectra for oxides such as rare-earth stannates (Grey et al.), but have apparently not been previously reported for silicates. New data on Si-29 and Al-27 NMR of synthetic pyrope (0.6 % CoO) and natural pyropes from the Dora Maira massif (1.5 to 3.5 wt % FeO) also show "anomalous" resonances, some of which again fall well outside the range of normal chemical shifts (e.g. +140 ppm in a Si-29 spectrum, 70 and 35 ppm in the Al-27 spectrum of a

  12. Final report on the safety assessment of aluminum silicate, calcium silicate, magnesium aluminum silicate, magnesium silicate, magnesium trisilicate, sodium magnesium silicate, zirconium silicate, attapulgite, bentonite, Fuller's earth, hectorite, kaolin, lithium magnesium silicate, lithium magnesium sodium silicate, montmorillonite, pyrophyllite, and zeolite. (United States)

    Elmore, Amy R


    This report reviews the safety of Aluminum, Calcium, Lithium Magnesium, Lithium Magnesium Sodium, Magnesium Aluminum, Magnesium, Sodium Magnesium, and Zirconium Silicates, Magnesium Trisilicate, Attapulgite, Bentonite, Fuller's Earth, Hectorite, Kaolin, Montmorillonite, Pyrophyllite, and Zeolite as used in cosmetic formulations. The common aspect of all these claylike ingredients is that they contain silicon, oxygen, and one or more metals. Many silicates occur naturally and are mined; yet others are produced synthetically. Typical cosmetic uses of silicates include abrasive, opacifying agent, viscosity-increasing agent, anticaking agent, emulsion stabilizer, binder, and suspending agent. Clay silicates (silicates containing water in their structure) primarily function as adsorbents, opacifiers, and viscosity-increasing agents. Pyrophyllite is also used as a colorant. The International Agency for Research on Cancer has ruled Attapulgite fibers >5 microm as possibly carcinogenic to humans, but fibers mining and processing of Aluminum Silicate, Calcium Silicate, Zirconium Silicate, Fuller's Earth, Kaolin, Montmorillonite, Pyrophyllite, and Zeolite. The Cosmetic Ingredient Review (CIR. The Cosmetic Ingredient Review (CIR) Expert Panel concluded that the extensive pulmonary damage in humans was the result of direct occupational inhalation of the dusts and noted that lesions seen in animals were affected by particle size, fiber length, and concentration. The Panel considers that most of the formulations are not respirable and of the preparations that are respirable, the concentration of the ingredient is very low. Even so, the Panel considered that any spray containing these solids should be formulated to minimize their inhalation. With this admonition to the cosmetics industry, the CIR Expert Panel concluded that these ingredients are safe as currently used in cosmetic formulations. The Panel did note that the cosmetic ingredient, Talc, is a hydrated magnesium silicate

  13. Production of High Molecular Weight Organic Compounds on the Surfaces of Amorphous Iron Silicate Catalysts: Implications for Organic Synthesis in the Solar Nebula (United States)

    Gilmour, I.; Hill, H. G. M.; Pearson, V. K.; Sephton, M. A.; Nuth, J. A., III


    The high molecular weight organic products of Fischer-Tropsch/Haber-Bosch syntheses on the surfaces of Fe-silicate catalysts have been studied by GCMS. Additional information is contained in the original extended abstract.

  14. Production of High Molecular Weight Organic Compounds on the Surfaces of Amorphous Iron Silicate Catalysts: Implications for Organic Synthesis in the Solar Nebula (United States)

    Gilmour, I.; Hill, H. G. M.; Pearson, V. K.; Sephton, M. A.; Nuth, J. A., III


    The high molecular weight organic products of Fischer-Tropsch/Haber-Bosch syntheses on the surfaces of Fe-silicate catalysts have been studied by GCMS. Additional information is contained in the original extended abstract.

  15. Transformation of Heavy Metal Compounds during the Remediation of Contaminated Soils

    Directory of Open Access Journals (Sweden)

    Tatiana Minkina


    Full Text Available The effect of ameliorants, chalk, glauconite and semidecomposed cattle manure, on ordinary chernozem contaminated with Zn and Pb was studied in a long-term field experiment. The application of ameliorants significantly decreased the mobility of metals. Their effect depended on the ameliorant and was most significant at the simultaneous application of chalk and manure. This effect was presumably due to the strong binding of metals by carbonates through chemisorption and formation of lowsoluble Zn and Pb compounds and to the additional fixation in the form of complexes at the addition of organic material. The share of loosely bound metal compounds in the contaminated soils decreased to the level typical for the clean soils or even below. The general evolution of the transformation of metal compounds (from less to more firmly bound compounds accelerated by ameliorants remained for both metals.

  16. Formation of alkali-metal nanoparticles in alkali-silicate glasses under electron irradiation and thermal processing (United States)

    Bochkareva, E. S.; Sidorov, A. I.; Ignat'ev, A. I.; Nikonorov, N. V.; Podsvirov, O. A.


    Experiments and numerical simulation show that the irradiation of alkali-containing glasses using electrons at an energy of 35 keV and the subsequent thermal processing at a temperature above the vitrification point lead to the formation of spherical metal (lithium, sodium, and potassium) nanoparticles with oxide sheaths that exhibit plasmon resonances in the visible spectral range. Glasses containing two alkali metals exhibit mutual effect of metals on the formation of nanoparticles with two compositions due to the difference of ion radii and mobilities of metal ions.

  17. Titanium coordination compounds: from discrete metal complexes to metal-organic frameworks. (United States)

    Assi, Hala; Mouchaham, Georges; Steunou, Nathalie; Devic, Thomas; Serre, Christian


    Owing to their promise in photocatalysis and optoelectronics, titanium based metal-organic frameworks (MOFs) are one of the most appealing classes of MOFs reported to date. Nevertheless, Ti-MOFs are still very scarce because of their challenging synthesis associated with a poor degree of control of their chemistry and crystallization. This review aims at giving an overview of the recent progress in this field focusing on the most relevant existing titanium coordination compounds as well as their promising photoredox properties. Not only Ti-MOFs but also Ti-oxo-clusters will be discussed and particular interest will be dedicated to highlight the different successful synthetic strategies allowing to overcome the still "unpredictable" reactivity of titanium ions, particularly to afford crystalline porous coordination polymers.

  18. Metallization and packaging of compound semiconductor devices at Sandia National Laboratories

    Energy Technology Data Exchange (ETDEWEB)

    Seigal, P.K.; Armendariz, M.G.; Rieger, D.J.; Lear, K.L.; Sullivan, C.T.


    Recent advances in compound semiconductor technology utilize a variety of metal thin films fabricated by thermal and electron-beam evaporation, and electroplating. An overview of metal processes used by Sandia`s Compound Semiconductor Research Laboratory is presented. Descriptions of electrical n-type and p-type ohmic contact alloys, interconnect metal, and metal layers specifically included for packaging requirements are addressed. Several illustrations of devices incorporating gold plated air bridges are included. ``Back-end`` processes such as flip-chip under bump metallurgy with fluxless solder reflow and plated solder processes are mentioned as current research areas.

  19. A Tale of Two Melt Rocks: Equilibration and Metal/Sulfide-Silicate Segregation in the L7 Chondrites PAT 91501 and LEW 88663 (United States)

    Harvey, R. P.


    Type 7 ordinary chondrites have experienced temperatures near or beyond those necessary for partial melting. Two recently collected Antarctic specimens, PAT91501 (PAT) and LEW88663 (LEW), have been tentatively identified as L7 chondrites based on mineral and oxygen isotope compositions [1,2]. The petrology and mineralogy of these meteorites suggests that they have undergone significant metal/sulfide-silicate segregation, with implications for meteorite parent bodies. PAT consists of an equigranular contact-framework of nearly euhedral olivine grains, with interstitial spaces filled by plagioclase, pyroxenes, and several minor phases. Ortho- and clinopyroxene occur in an exsolution relationship. Olivine and pyroxene are highly equilibrated, varying PAT using the methods of [3] are self-consistent at about 1180 degrees C. In thin section, PAT contains only traces of metal, as tiny isolated blebs in sulfide grains; large (>1 cm) globular sulfide inclusions are seen in hand-sample [1], but are not present in the section examined. LEW was originally classified as an achondrite with olivine and pyroxene compositions similar to those in L chondrites [2]. Metal is absent in LEW, although the specimen is small and heavily rusted, making it impossible to gauge the original metal content. Olivine grains are commonly rounded in shape and seldom in contact with more than a few other grains. LEW olivine and pyroxene are also highly equilibrated. Veins of Ni-bearing metal oxides and sulfides are common. Both low- and high-Ca pyroxene occur as discrete grains, orthopyroxene often poikilitically enclosing olivine. Pyroxene equilibration temperatures for LEW are more variable than those for PAT and consistently lower, with an average around 900 degrees C. The various textural and compositional characteristics of PAT and LEW suggest they have experienced partial melting to varying degrees. Both visually resemble charges from experimental melting of ordinary chondrites [4-6]. The

  20. Half-metallic ferromagnetism in the CsSe compound by density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Karaca, Mustafa; Kervan, Selçuk; Kervan, Nazmiye, E-mail:


    Graphical abstract: The ferromagnetic ground state of the CsSe compound is the most stable with CsCl-type structure with a total magnetic moment of 1 μ{sub B}/f.u. although this compound does not include transition metal atoms. The CsSe compound is half-metallic ferromagnet with a half-metallic band gap of 3.75 eV. The half-metallicity is also found to be robust with respect to the lattice distortion in the CsCl-type structure. The Curie temperature is estimated to be 390 K in the mean field approximation (MFA). - Highlights: • The CsSe compound is the most stable with CsCl-type structure. • The half-metallic band gap is about 3.5 eV for all types of structure. • The total magnetic moment is of 1 μ{sub B}/f.u. • The Curie temperature is estimated to be 390 K. - Abstract: The full-potential linearized augmented plane wave (FPLAPW) method based on the density functional theory is used to investigate the structural, magnetic and half-metallic properties of the CsSe compound in the CsCl-type, NaCl-type, ZnS-type, NiAs-type and wurtzite structures. The results show that the ferromagnetic ground state of the CsSe compound is the most stable with CsCl-type structure with a total magnetic moment of 1 μ{sub B}/f.u. although this compound does not include transition metal atoms. The CsSe compound is half-metallic ferromagnet for all types of structure. The half-metallic band gap is about 3.5 eV for all types of structure. The Curie temperature is estimated to be 390 K in the mean field approximation (MFA)

  1. Selective retention of basic compounds by metal aquo-ion affinity chromatography. (United States)

    Asakawa, Yoshiki; Yamamoto, Eiichi; Asakawa, Naoki


    A novel metal aquo-ion affinity chromatography has been developed for the analysis of basic compounds using heat-treated silica gel containing hydrated metal cations (metal aquo-ions) as the packing material. The packing materials of the metal aquo-ion affinity chromatography were prepared by the immobilization of a single metal component such as Fe(III), Al(III), Ag(I), and Ni(II) on silica gel followed by extensive heat treatment. The immobilized metals form aquo-ions to present cation-exchange ability for basic analytes and the cation-exchange ability for basic analytes depends on pKa of the immobilized metal species. In the present study, to evaluate the retention characteristics of metal aquo-ion affinity chromatography, the on-line solid-phase extraction of drugs was investigated. Obtained data clearly evidence the selective retention capability of metal aquo-ion affinity chromatography for basic analytes with sufficient capacity.

  2. Non-conductive nanomaterial enhanced electrochemical response in stripping voltammetry: The use of nanostructured magnesium silicate hollow spheres for heavy metal ions detection. (United States)

    Xu, Ren-Xia; Yu, Xin-Yao; Gao, Chao; Jiang, Yu-Jing; Han, Dong-Dong; Liu, Jin-Huai; Huang, Xing-Jiu


    Nanostructured magnesium silicate hollow spheres, one kind of non-conductive nanomaterials, were used in heavy metal ions (HMIs) detection with enhanced performance for the first time. The detailed study of the enhancing electrochemical response in stripping voltammetry for simultaneous detection of ultratrace Cd(2+), Pb(2+), Cu(2+) and Hg(2+) was described. Electrochemical properties of modified electrodes were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The operational parameters which have influence on the deposition and stripping of metal ions, such as supporting electrolytes, pH value, and deposition time were carefully studied. The anodic stripping voltammetric performance toward HMIs was evaluated using square wave anodic stripping voltammetry (SWASV) analysis. The detection limits achieved (0.186nM, 0.247nM, 0.169nM and 0.375nM for Cd(2+), Pb(2+), Cu(2+) and Hg(2+)) are much lower than the guideline values in drinking water given by the World Health Organization (WHO). In addition, the interference and stability of the modified electrode were also investigated under the optimized conditions. An interesting phenomenon of mutual interference between different metal ions was observed. Most importantly, the sensitivity of Pb(2+) increased in the presence of certain concentrations of other metal ions, such as Cd(2+), Cu(2+) and Hg(2+) both individually and simultaneously. The proposed electrochemical sensing method is thus expected to open new opportunities to broaden the use of SWASV in analysis for detecting HMIs in the environment. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. Structurally defined allyl compounds of main group metals: coordination and reactivity. (United States)

    Lichtenberg, Crispin; Okuda, Jun


    Organometallic allyl compounds are important as allylation reagents in organic synthesis, as polymerization catalysts, and as volatile metal precursors in material science. Whereas the allyl chemistry of synthetically relevant transition metals such as palladium and of the lanthanoids is well-established, that of main group metals has been lagging behind. Recent progress on allyl complexes of Groups 1, 2, and 12-16 now provides a more complete picture. This is based on a fundamental understanding of metal-allyl bonding interactions in solution and in the solid state. Furthermore, reactivity trends have been rationalized and new types of allyl-specific reactivity patterns have been uncovered. Key features include 1) the exploitation of the different types of metal-allyl bonding (highly ionic to predominantly covalent), 2) the use of synergistic effects in heterobimetallic compounds, and 3) the adjustment of Lewis acidity by variation of the charge of allyl compounds.

  4. Metal-Element Compounds of Titanium, Zirconium, and Hafnium as Pyrotechnic Fuels (United States)


    1-11 1 METAL-ELEMENT COMPOUNDS OF TITANIUM, ZIRCONIUM , AND HAFNIUM AS PYROTECHNIC FUELS Anthony P. Shaw,* Rajendra K. Sadangi, Jay C...have started to explore the pyrotechnic properties of other inorganic compounds, particularly those of titanium, zirconium , and hafnium. The...The group 4 metals—titanium, zirconium , and hafnium—are potent pyrotechnic fuels. However, the metals themselves are often pyrophoric as fine

  5. The influence of heavy metals on the polymorphs of dicalcium silicate in the belite-rich clinkers produced from electroplating sludge. (United States)

    Chen, Ying-Liang; Shih, Pai-Haung; Chiang, Li-Choung; Chang, Yi-Kuo; Lu, Hsing-Cheng; Chang, Juu-En


    The purpose of this study is to utilize an electroplating sludge for belite-rich clinker production and to observe the influence of heavy metals on the polymorphs of dicalcium silicate (C(2)S). Belite-rich clinkers prepared with 0.5-2% of NiO, ZnO, CuO, and Cr(2)O(3) were used to investigate the individual effects of the heavy metals in question. The Reference Intensity Ratio (RIR) method was employed to determine the weight fractions of gamma-C(2)S and beta-C(2)S in the clinkers, and their microstructures were examined by the transmission electron microscopy (TEM). The results showed that nickel, zinc, and chromium have positive effects on beta-C(2)S stabilization (Cr(3+)>Ni(2+)>Zn(2+)), whereas copper has a negative effect. The addition of up to 10% electroplating sludge did not have any negative influence on the formation of C(2)S. It was observed that gamma-C(2)S decreased while beta-C(2)S increased with a rise in the addition of the electroplating sludge. Moreover, nickel and chromium mainly contributed to stabilizing beta-C(2)S in the belite-rich clinkers produced from the electroplating sludge.


    Energy Technology Data Exchange (ETDEWEB)

    Hobbs, D.


    Sodium titanates are ion-exchange materials that effectively bind a variety of metal ions over a wide pH range. Sodium titanates alone have no known adverse biological effects but metal-exchanged titanates (or metal titanates) can deliver metal ions to mammalian cells to alter cell processes in vitro. In this work, we test a hypothesis that metal-titanate compounds inhibit bacterial growth; demonstration of this principle is one prerequisite to developing metal-based, titanate-delivered antibacterial agents. Focusing initially on oral diseases, we exposed five species of oral bacteria to titanates for 24 h, with or without loading of Au(III), Pd(II), Pt(II), and Pt(IV), and measuring bacterial growth in planktonic assays through increases in optical density. In each experiment, bacterial growth was compared with control cultures of titanates or bacteria alone. We observed no suppression of bacterial growth by the sodium titanates alone, but significant (p < 0.05, two-sided t-tests) suppression was observed with metal-titanate compounds, particularly Au(III)-titanates, but with other metal titanates as well. Growth inhibition ranged from 15 to 100% depending on the metal ion and bacterial species involved. Furthermore, in specific cases, the titanates inhibited bacterial growth 5- to 375-fold versus metal ions alone, suggesting that titanates enhanced metal-bacteria interactions. This work supports further development of metal titanates as a novel class of antibacterials.

  7. Development and characterization of diamond film and compound metal surface high current photocathodes

    Energy Technology Data Exchange (ETDEWEB)

    Shurter, R.P.; Moir, D.C.; Devlin, D.J.; Springer, R.W.; Archuleta, T.A.


    High current photocathodes operating in vacuum environments as high as 8xE-5 torr are being developed at Los Alamos for use in a new generation of linear induction accelerators. We report quantum efficiencies in wide bandgap semiconductors, pure metals, and compound metal surfaces photocathode materials illuminated by ultraviolet laser radiation.

  8. Electronic Structure and Geometries of Small Compound Metal Clusters

    Energy Technology Data Exchange (ETDEWEB)



    During the tenure of the DOE grant DE-FG05-87EI145316 we have concentrated on equilibrium geometries, stability, and the electronic structure of transition metal-carbon clusters (met-cars), clusters designed to mimic the chemistry of atoms, and reactivity of homo-nuclear metal clusters and ions with various reactant molecules. It is difficult to describe all the research the authors have accomplished as they have published 38 papers. In this report, they outline briefly the salient features of their work on the following topics: (1) Designer Clusters: Building Blocks for a New Class of Solids; (2) Atomic Structure, Stability, and Electronic Properties of Metallo-Carbohedrenes; (3) Reactivity of Metal Clusters with H{sub 2} and NO; and (4) Anomalous Spectroscopy of Li{sub 4} Clusters.

  9. Electronic Structure and Geometries of Small Compound Metal Clusters

    Energy Technology Data Exchange (ETDEWEB)



    During the tenure of the DOE grant DE-FG05-87EI145316 we have concentrated on equilibrium geometries, stability, and the electronic structure of transition metal-carbon clusters (met-cars), clusters designed to mimic the chemistry of atoms, and reactivity of homo-nuclear metal clusters and ions with various reactant molecules. It is difficult to describe all the research the authors have accomplished as they have published 38 papers. In this report, they outline briefly the salient features of their work on the following topics: (1) Designer Clusters: Building Blocks for a New Class of Solids; (2) Atomic Structure, Stability, and Electronic Properties of Metallo-Carbohedrenes; (3) Reactivity of Metal Clusters with H{sub 2} and NO; and (4) Anomalous Spectroscopy of Li{sub 4} Clusters.

  10. Production of magnesium metal (United States)

    Blencoe, James G [Harriman, TN; Anovitz, Lawrence M [Knoxville, TN; Palmer, Donald A [Oliver Springs, TN; Beard, James S [Martinsville, VA


    A process of producing magnesium metal includes providing magnesium carbonate, and reacting the magnesium carbonate to produce a magnesium-containing compound and carbon dioxide. The magnesium-containing compound is reacted to produce magnesium metal. The carbon dioxide is used as a reactant in a second process. In another embodiment of the process, a magnesium silicate is reacted with a caustic material to produce magnesium hydroxide. The magnesium hydroxide is reacted with a source of carbon dioxide to produce magnesium carbonate. The magnesium carbonate is reacted to produce a magnesium-containing compound and carbon dioxide. The magnesium-containing compound is reacted to produce magnesium metal. The invention further relates to a process for production of magnesium metal or a magnesium compound where an external source of carbon dioxide is not used in any of the reactions of the process. The invention also relates to the magnesium metal produced by the processes described herein.

  11. Single crystal growth of europium and ytterbium based intermetallic compounds using metal flux technique

    Indian Academy of Sciences (India)

    Sumanta Sarkar; Sebastian C Peter


    This article covers the use of indium as a potential metal solvent for the crystal growth of europium and ytterbium-based intermetallic compounds. A brief view about the advantage of metal flux technique and the use of indium as reactive and non-reactive flux are outlined. Large single crystals of EuGe2, EuCoGe3 and Yb2AuGe3 compounds were obtained in high yield from the reactions of the elements in liquid indium. The results presented here demonstrate that considerable advances in the discovery of single crystal growth of complex phases are achievable utilizing molten metals as solvents.

  12. The Systematic Study of the Organotransition Metal Compounds. (United States)

    Carriedo, Gabino A.


    Discussed is an extension of the conventional method for studying the organometallic chemistry of transition metals that may be useful to show how the various existing types of low-valence complexes can be constructed. This method allows students to design new types of complexes that may still be nonexistent. (CW)

  13. Prediction of reduction potentials from calculated electron affinities for metal-salen compounds

    Directory of Open Access Journals (Sweden)

    Sarah B. Bateni


    Full Text Available The electron affinities (EAs of a training set of 19 metal-salen compounds were calculated using density functional theory. Concurrently, the experimental reduction potentials for the training set were measured using cyclic voltammetry. The EAs and reduction potentials were found to be linearly correlated by metal. The reduction potentials of a test set of 14 different metal-salens were then measured and compared to the predicted reduction potentials based upon the training set correlation. The method was found to work well, with a mean unsigned error of 99 mV for the entire test set. This method could be used to predict the reduction potentials of a variety of metal-salen compounds, an important class of coordination compounds used in synthetic organic electrochemistry as electrocatalysts.

  14. Electron correlations in transition metal-telluride cluster compounds

    NARCIS (Netherlands)

    Palstra, T.T.M.; Steigerwald, M.L.; Ramirez, A.P.; Zaanen, J.


    We report the magnetic properties of a new class of materials: Ni9Te6n+ and Co6Te8n+ with n = 0, 1, 2. These cluster compounds, which can be charged by chemical means from neutral to 2 +, provide a unique and novel way to change the Fermi level. For most charge states, we observe quenching of the

  15. Effect of H2O on metal-silicate partitioning of Ni, Co, V, Cr, Mn and Fe: Implications for the oxidation state of the Earth and Mars (United States)

    Clesi, V.; Bouhifd, M. A.; Bolfan-Casanova, N.; Manthilake, G.; Fabbrizio, A.; Andrault, D.


    This study investigates the metal-silicate partitioning of Ni, Co, V, Cr, Mn and Fe during core mantle differentiation of terrestrial planets under hydrous conditions. For this, we equilibrated a molten hydrous CI chondrite model composition with various Fe-rich alloys in the system Fe-C-Ni-Co-Si-S in a multi-anvil over a range of P, T, fO2 and water content (5-20 GPa, 2073-2500 K, from 1 to 5 log units below the iron-wüstite (IW) buffer and for XH2O varying from 500 ppm to 1.5 wt%). By comparing the present experiments with the available data sets on dry systems, we observes that the effect of water on the partition coefficients of moderately siderophile elements is only moderate. For example, for iron we observed a decrease in the partition coefficient of Fe (Dmet/silFe) from 9.5 to 4.3, with increasing water content of the silicate melt, from 0 to 1.44 wt%, respectively. The evolution of metal-silicate partition coefficients of Ni, Co, V, Cr, Mn and Fe are modelled based on sets of empirical parameters. These empirical models are then used to refine the process of core segregation during accretion of Mars and the Earth. It appears that the likely presence of 3.5 wt% water on Mars during the core-mantle segregation could account for ∼74% of the FeO content of the Martian mantle. In contrast, water does not play such an important role for the Earth; only 4-6% of the FeO content of its mantle could be due to the water-induced Fe-oxidation, for a likely initial water concentration of 1.8 wt%. Thus, in order to reproduce the present-day FeO content of 8 wt% in the mantle, the Earth could initially have been accreted from a large fraction (between 85% and 90%) of reducing bodies (similar to EH chondrites), with 10-15% of the Earth's mass likely made of more oxidized components that introduced the major part of water and FeO to the Earth. This high proportion of enstatite chondrites in the original constitution of the Earth is consistent with the 17O,48Ca,50Ti,62Ni




    The objective of the submitted work was to prepare and to characterize two types of silicate coatings prepared by the sol-gel method using the dip-coating technique on a titanium substrate. Efforts have been made to use mechanical properties of bio-inert titanium and bioactive properties of a silicate layer enriched with an admixture of compounds identified below. The first group consisted of silicate coatings containing silver, brushite and monetite. The other group of silicate coatings cont...

  17. Effects of complexing compounds on sorption of metal ions to cement

    Energy Technology Data Exchange (ETDEWEB)

    Loevgren, Lars [Umeaa Univ. (Sweden). Inorganic chemistry


    This present report is a literature review addressing the effects of complexing ligands on the sorption of radionuclides to solid materials of importance for repositories of radioactive waste. Focus is put on laboratory studies of metal ion adsorption to cement in presence of chelating agents under strongly alkaline conditions. As background information, metal sorption to different mineral and cement phases in ligand free systems is described. Furthermore, surface complexation model (SCM) theories are introduced. According to surface complexation theories these interactions occur at specific binding sites at the particle/water interface. Adsorption of cationic metals is stronger at high pH, and the adsorption of anions occurs preferentially at low pH. The adsorption of ions to mineral surfaces is a result of both chemical bonding and electrostatic attraction between the ions and charged mineral surfaces. By combining uptake data with spectroscopic information the sorption can be explained on a molecular level by structurally sound surface complexation models. Most of the metal sorption studies reviewed are dealing with minerals exhibiting oxygen atoms at their surfaces, mainly oxides of Fe(II,III) and Al(III), and aluminosilicates. Investigations of radionuclides are focused on clay minerals, above all montmorillonite and illite. Which mechanism that is governing the metal ion adsorption to a given mineral is to a large extent depending on the metal adsorbed. For instance, sorption of Ni to montmorillonite can occur by formation of inner-sphere mononuclear surface complexes located at the edges of montmorillonite platelets and by formation of a Ni phyllosilicate phase parallel to montmorillonite layers. Also metal uptake to cement materials can occur by different mechanisms. Cationic metals can both be attached to cement (calcium silicate hydrate, CSH) and hardened cement paste (HCP) by formation of inner-sphere complexes at specific surface sites and by

  18. S-S bond reactivity in metal-perthiocarboxylato compounds. (United States)

    Mas-Ballesté, Rubén; Guijarro, Alejandro; González-Prieto, Rodrigo; Castillo, Oscar; Sanz Miguel, Pablo J; Zamora, Félix


    While M-percarboxylato species are elusive intermediates, their sulfur containing analogues are known in some cases. The feasibility of isolation of M-perthioacetato compounds allowed, in this work, to obtain new insights into the pathways that follow the reactivity of M-E-ER (E = O, S) fragments. Herein we report on the isolation of two new M-perthioacetato compounds: trans-[Pt(CH(3)CS(2)S)(2)] () and [Ni(CH(3)CSS)(CH(3)CS(2)S)] (), which have been fully characterized, including X-ray structures. Reactivity of these compounds towards PPh(3) has been studied combining UV-vis monitorization and NMR measurements. Overall the accumulated data suggest that the evolution of the perthioacetato ligand in complexes and by reaction with PPh(3) consists of a complex multistep pathway in which the sulfur transfer is preceded by electron transfer. Cyclic voltammetry measurements indicate that the transference of two electrons from the phosphorus to the sulfur atom is not concerted, suggesting that the first step of the reaction with PPh(3) is the monoelectronic electron transfer followed by P-S bond formation. The results presented here show a novel pathway in the field of S-S bond reactivity processes relevant in biological, synthetic systems and in hydrocarbon desulfurization processes.

  19. Carbon based secondary compounds do not provide protection against heavy metal road pollutants in epiphytic macrolichens. (United States)

    Gauslaa, Yngvar; Yemets, Olena A; Asplund, Johan; Solhaug, Knut Asbjørn


    Lichens are useful monitoring organisms for heavy metal pollution. They are high in carbon based secondary compounds (CBSCs) among which some may chelate heavy metals and thus increase metal accumulation. This study quantifies CBSCs in four epiphytic lichens transplanted for 6months on stands along transects from a highway in southern Norway to search for relationships between concentrations of heavy metals and CBSCs along a gradient in heavy metal pollutants. Viability parameters and concentrations of 21 elements including nutrients and heavy metals in these lichen samples were reported in a separate paper. Medullary CBSCs in fruticose lichens (Ramalina farinacea, Usnea dasypoga) were reduced in the most polluted sites, but not in foliose ones (Parmelia sulcata, Lobaria pulmonaria), whereas cortical CBSC did not change with distance from the road in any species. Strong positive correlations only occurred between the major medullary compound stictic acid present in L. pulmonaria and most heavy metals, consistent with a chelating role of stictic acid, but not of other studied CBSCs or in other species. However, heavy metal chelating did not protect L. pulmonaria against damage because this species experienced the strongest reduction in viability in the polluted sites. CBSCs with an accumulation potential for heavy metals should be quantified in lichen biomonitoring studies of heavy metals because they, like stictic acid, could overshadow pollutant inputs in some species rendering biomonitoring data less useful. In the two fruticose lichen species, CBSCs decreased with increasing heavy metal concentration, probably because heavy metal exposure impaired secondary metabolism. Thus, we found no support for a heavy metal protection role of any CBSCs in studied epiphytic lichens. No intraspecific relationships occurred between CBSCs versus N or C/N-ratio. Interspecifically, medullary CBSCs decreased and cortical CBSCs increased with increasing C/N-ratio.

  20. Synthesis and characterization of graphite-metal fluoride intercalation compounds

    Energy Technology Data Exchange (ETDEWEB)

    McQuillan, B.W.


    The compound C/sub x/AsF/sub 5/ was prepared and characterized by x-ray diffraction and x-ray absorption, which show the presence of As(III) and As(V), and the As-F bond distances are consistent with AsF/sub 3/ and AsF/sup -//sub 6/, C/sup +//sub 8/AsF/sup -//sub 6/ and C/sup +//sub 8/OsF/sup -//sub 6/ were synthesized. The C/sub x/AsF/sub 6/ and numerous standard arsenic-flourine compounds were studied by x-ray absorption. Magnetic susceptibility of C/sup +//sub 8/OsF/sup -//sub 6/ confirms the high degree of oxidation in this compound. X-ray absorption studies were begun to determine the species present within the graphite when BrF/sub 3/ or GeF/sub 4/ + F/sub 2/ are added. In the BrF/sub 3/ case, Br/sub 2/ is evolved and only Br(III) is present in the graphite. The binary phase diagram XeF/sub 2/:Xe/sup +//sub 5/AsF/sup -//sub 6/ was investigated by melting point determination and Raman spectroscopy. This mixture near 1.3:1 forms a kinetically stable glass at room temperature and is molten at 50/sup 0/C. Several new species or phases are observed in the Raman spectra. These species have been assigned tentative structures.

  1. The use of Bacillus genus to dressing of silicate raw materials

    Directory of Open Access Journals (Sweden)

    Štyriaková Iveta


    Full Text Available Bacteria of Bacillus genus from Banská Hodruša ore deposit and from Horná Prievrana kaolin deposit caused a more intensive destruction of silicate minerals by their activity, especially by the metabolites production. Their activity resulted to the development of corrosive and enantiomorphic holes on silicate minerals surface when sulphidic minerals were released and the metals were extracted into solution.The monitoring of Bacillus spp. occurrence in various deposits with silicate minerals composition suggested that these bacteria can be found in several deposits and waste dumps with silicate minerals at Slovakia. The widest species representation was detected in samples from the Horná Prievrana kaolin deposit.The experiments with primary silicates showed either a more intensive destruction of silicate minerals accompanied by sulphides releasing from these minerals or a more intensive metals extraction from sulphidic minerals after ore dressing. The important percentage of precious metals extraction (30% of gold and 30% of argentine from silicate minerals can suggest a possibility of the regulation of cyanides use in precious metals winning. A process for biological removal of elements from the samples was the result of the cultivation of organic acids - producing strains of the genus Bacillus. Hovewer, these bacteria synthesized also polysaccharides during bioleaching. Extensive acidic mucopolysaccharide films, which entrapped mineral particles, were identified by the ruthenium red staining. Ore bioleaching can not compete with physical and chemical methods in the rapidity of metal extraction from rich ores without ecological criterion. However, biotechnology becomes an alternative way in metals extraction from poor ores or wastes from the economical as well as the ecological view.The laboratory experiments with secondary silicates confirmed various forms of iron binding in kaolins and an important influence of the iron binding form on the


    Directory of Open Access Journals (Sweden)

    Vasilii Gutsanu


    Full Text Available Using the Mossbauer spectroscopy and other physical methods it was demonstrated the presence of different iron compounds like β-FeOOH, α-Fe2O3, and jarosite mineral type compounds: (R4N,H3O[Fe3(OH6(SO42] or coordination modes: {RCOO-Fe(L4-OOCR}1+, {R-CO2=Fe(X2=O2C-R}n, {R-COO-Fe(X4-OOC-R}n, and {(-NCH2CH2N-= Fe(X2 =(-NCH2CH2N-}, where X= H2O, OH-, SO42-., n= from 3- to 1+ in the ion-exchange resins (KU-2, AN-31, AV-17, Varian – AD, EDE-10P after the contact with sulphate of iron(III solutions at different conditions: type of solvent, temperature, air atmosphere. In special conditions the ultrafine superparamagnetic particles of Fe2O3 have been obtained

  3. Modeling of Intermetallic Compounds Growth Between Dissimilar Metals (United States)

    Wang, Li; Wang, Yin; Prangnell, Philip; Robson, Joseph


    A model has been developed to predict growth kinetics of the intermetallic phases (IMCs) formed in a reactive diffusion couple between two metals for the case where multiple IMC phases are observed. The model explicitly accounts for the effect of grain boundary diffusion through the IMC layer, and can thus be used to explore the effect of IMC grain size on the thickening of the reaction layer. The model has been applied to the industrially important case of aluminum to magnesium alloy diffusion couples in which several different IMC phases are possible. It is demonstrated that there is a transition from grain boundary-dominated diffusion to lattice-dominated diffusion at a critical grain size, which is different for each IMC phase. The varying contribution of grain boundary diffusion to the overall thickening kinetics with changing grain size helps explain the large scatter in thickening kinetics reported for diffusion couples produced under different conditions.

  4. Reduction of Nitroaromatic Compounds on the Surface of Metallic Iron: Quantum Chemical Study

    Directory of Open Access Journals (Sweden)

    Jerzy Leszczynski


    Full Text Available Abstract: The initial reduction steps of nitroaromatic compounds on the surface of metallic iron have been studied theoretically using nitrobenzene (NB as a representative of nitroaromatic compounds. The quantum chemical cluster approximation within the semiempirical Neglect of Diatomic Differential Overlap for Metal Compounds method was applied to model the Fe(110 crystallographic surface, taken as a representative reactive surface for granular iron. This surface was modeled as a 39-atom two-layer metal cluster with rigid geometry. The associative and dissociative adsorption of nitrobenzene was considered. Based on our quantum chemical analysis, we suggest that the direct electron donation from the metal surface into the π* orbital of NB is a decisive factor responsible for subsequent transformation of the nitro group. Molecularly adsorbed NB interacts with metal iron exclusively through nitro moiety oxygens which occupy tri-coordinated positions on surface The charge transfer from metal to NB of approximately 2 atomic units destablizes the nitro group. As a result, the first dissociation of the N-O bond goes through a relatively low activation barrier. The adsorbed nitrosobenzene is predicted to be a stable surface species, though still quiet labile.

  5. Metal-chelating compounds produced by ectomycorrhizal fungi collected from pine plantations. (United States)

    Machuca, A; Pereira, G; Aguiar, A; Milagres, A M F


    To investigate the in vitro production of metal-chelating compounds by ectomycorrhizal fungi collected from pine plantations in southern Chile. Scleroderma verrucosum, Suillus luteus and two isolates of Rhizopogon luteolus were grown in solid and liquid modified Melin-Norkans (MMN) media with and without iron addition and the production of iron-chelating compounds was determined by Chrome Azurol S (CAS) assay. The presence of hydroxamate and catecholate-type compounds and organic acids was also investigated in liquid medium. All isolates produced iron-chelating compounds as detected by CAS assay, and catecholates, hydroxamates as well as oxalic, citric and succinic acids were also detected in all fungal cultures. Scleroderma verrucosum produced the greatest amounts of catecholates and hydroxamates whereas the highest amounts of organic acids were detected in S. luteus. Nevertheless, the highest catecholate, hydroxamate and organic acid concentrations did not correlate with the highest CAS reaction which was observed in R. luteolus (Yum isolate). Ectomycorrhizal fungi produced a variety of metal-chelating compounds when grown in liquid MMN medium. However, the addition of iron to all fungi cultures reduced the CAS reaction, hydroxamate and organic acid concentrations. Catecholate production was affected differently by iron, depending on the fungal isolate. The ectomycorrhizal fungi described in this study have never been reported to produce metal-chelating compound production. Moreover, apart from some wood-rotting fungi, this is the first evidence of the presence of catecholates in R. luteolus, S. luteus and S. verrucosum cultures.

  6. A study on compound contents for plastic injection molding products of metallic resin pigment

    Energy Technology Data Exchange (ETDEWEB)

    Park, Young Whan; Kwak, Jae Seob [Dept. of Mechanical Engineering, Pukyong National University, Busan (Korea, Republic of); Lee, Gyu Sang [Alliance Molding Engineering TeamLG Electronics Inc., Osan (Korea, Republic of)


    Injection molding process is widely used for producing most plastic products. In order to make a metal-colored plastic product especially in modern luxury home alliances, metallic pigments which are mixed to a basic resin material for injection molding are available. However, the process control for the metal-colored plastic product is extremely difficult due to non-uniform melt flow of the metallic resin pigments. To improve the process efficiency, a rapid mold cooling method by a compressed cryogenic fluid and electricity mold are also proposed to decrease undesired compound contents within a molded plastic product. In this study, a quality of the metal-colored plastic product is evaluated with process parameters; injection speed, injection pressure, and pigment contents, and an influence of the rapid cooling and heating system is demonstrated.


    Directory of Open Access Journals (Sweden)

    V. N. Yaglov


    Full Text Available The paper proposes a technology for obtaining bricks on the basis of lime-silica mixtures where chemical interactions are practically completely realized in dispersive state at the stage of preparation of binding contact maturing and raw mixture as a whole. The role of forming operation (moulding is changed in principle because in this case conversion of dispersive system into a rock-like solid occurs and due to this the solid obtains complete water-resistance in contact with water immediately after forming operation. Theoretical basis for the developed technology is capability of silicate dispersive substances (hydrated calcium silicate to transit in non-stable state, to form a rock-like water-resistant solid in the moment of mechanical load application during forming process. Specific feature of the proposed method is an exclusion of additional operations for autoclaving of products from the process of obtaining a silicate brick.Synthetic hydrated calcium silicate in contrast to natural ones are more uniform in composition and structure, they contain less impurities and they are characterized by dispersive composition and due to the mentioned advantages they find wider practical application. Contact-condensation binders permit to manipulate product properties on their basis and ensure maximum correspondence to the requirements of the concrete application. Raw material sources for obtaining synthetic hydrated calcium silicates are practically un-limited because calcium-silicon containing substances are found as in various technogenic wastes so in natural compounds as well. So the problem for obtaining hydrated calcium silicates having contact-condensation ability for structure formation becomes more and more actual one. This transition is considered as dependent principally on arrangement rate of substance particles which determined the level of its instability.

  8. A standardized evaluation of artifacts from metallic compounds during fast MR imaging

    DEFF Research Database (Denmark)

    Murakami, Shumei; Verdonschot, Rinus G; Kataoka, Miyoshi


    OBJECTIVE: Metallic compounds present in the oral and maxillofacial regions (OMR) cause large artifacts during MR scanning. We quantitatively assessed these artifacts embedded within a phantom according to standards set by the American Society for Testing and Materials (ASTM). MATERIALS AND METHO...

  9. Development and Characterization of Diamond Film and Compound Metal Surface High Current Photocathodes (United States)

    Shurter, R. P.; Moir, D. C.; Shurter, R. P.; Moir, D. C.


    High current photocathodes operating in vacuum environments as high as 10-5 torr are being developed at Los Alamos for use in a new generation of linear induction accelerators. We report high quantum efficiencies and high current densities in wide bandgap semiconductor and compound metal surface thermally augmented photocathode materials illuminated by ultraviolet laser radiation.

  10. Technologies for Extracting Valuable Metals and Compounds from Geothermal Fluids

    Energy Technology Data Exchange (ETDEWEB)

    Harrison, Stephen [SIMBOL Materials


    Executive Summary Simbol Materials studied various methods of extracting valuable minerals from geothermal brines in the Imperial Valley of California, focusing on the extraction of lithium, manganese, zinc and potassium. New methods were explored for managing the potential impact of silica fouling on mineral extraction equipment, and for converting silica management by-products into commercial products.` Studies at the laboratory and bench scale focused on manganese, zinc and potassium extraction and the conversion of silica management by-products into valuable commercial products. The processes for extracting lithium and producing lithium carbonate and lithium hydroxide products were developed at the laboratory scale and scaled up to pilot-scale. Several sorbents designed to extract lithium as lithium chloride from geothermal brine were developed at the laboratory scale and subsequently scaled-up for testing in the lithium extraction pilot plant. Lithium The results of the lithium studies generated the confidence for Simbol to scale its process to commercial operation. The key steps of the process were demonstrated during its development at pilot scale: 1. Silica management. 2. Lithium extraction. 3. Purification. 4. Concentration. 5. Conversion into lithium hydroxide and lithium carbonate products. Results show that greater than 95% of the lithium can be extracted from geothermal brine as lithium chloride, and that the chemical yield in converting lithium chloride to lithium hydroxide and lithium carbonate products is greater than 90%. The product purity produced from the process is consistent with battery grade lithium carbonate and lithium hydroxide. Manganese and zinc Processes for the extraction of zinc and manganese from geothermal brine were developed. It was shown that they could be converted into zinc metal and electrolytic manganese dioxide after purification. These processes were evaluated for their economic potential, and at the present time Simbol

  11. The Mammary Gland Carcinogens: The Role of Metal Compounds and Organic Solvents

    Directory of Open Access Journals (Sweden)

    Stephen Juma Mulware


    Full Text Available The increased rate of breast cancer incidences especially among postmenopausal women has been reported in recent decades. Despite the fact that women who inherited mutations in the BRCA1 and BRCA2 genes have a high risk of developing breast cancer, studies have also shown that significant exposure to certain metal compounds and organic solvents also increases the risks of mammary gland carcinogenesis. While physiological properties govern the uptake, intracellular distribution, and binding of metal compounds, their interaction with proteins seems to be the most relevant process for metal carcinogenicity than biding to DNA. The four most predominant mechanisms for metal carcinogenicity include (1 interference with cellular redox regulation and induction of oxidative stress, (2 inhibition of major DNA repair, (3 deregulation of cell proliferation, and (4 epigenetic inactivation of genes by DNA hypermethylation. On the other hand, most organic solvents are highly lipophilic and are biotransformed mainly in the liver and the kidney through a series of oxidative and reductive reactions, some of which result in bioactivation. The breast physiology, notably the parenchyma, is embedded in a fat depot capable of storing lipophilic xenobiotics. This paper reviews the role of metal compounds and organic solvents in breast cancer development.

  12. Cytotoxicity of dust constituents towards alveolar macrophages: interactions of heavy metal compounds. (United States)

    Geertz, R; Gulyas, H; Gercken, G


    The interactions between different heavy metal compounds which affect their cytotoxicity towards rabbit alveolar macrophages were investigated. The cells were exposed in vitro to combinations of As3+, Cd2+, Hg2+, Ni2+, or V5+ with different concentrations of another heavy metal compound. Toxicity was determined as the depression of zymosan-induced release of superoxide anion radicals. Significant antagonisms occurred in the combinations Cd2+/Zn2+, Hg2+/As3+, and Hg2+/Se4+, while significant synergisms were exhibited by the combinations Cd2+/Cu2+, Cd2+/Sn2+, Hg2+/Cu2+, Ni2+/Cd2+, Ni2+/Cu2+, Ni2+/Sn2+ and V5+/Cu2+. In the combinations As3+/Zn2+, Hg2+/Cd2+ and Hg2+/Zn2+, both kinds of interactions were observed depending on the concentrations of the heavy metal compounds. An interpretation of the measured heavy metal interactions with reference to the toxicity of heavy metal-containing dusts is attempted.

  13. Intrinsic luminescence of alkali silicate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Arbuzov, V.I.; Grabovskis, V.Y.; Tolstoi, M.N.; Vitol, I.K.


    This study obtains additional information on L centers and their role in electron excitation and intrinsic luminescence of a whole series. (Li, Na, K, Rb, and Cs) of alkali silicate glasses. The authors compare the features of the interaction with radiation of specimens of glass and crystal of a similar chemical composition, since silicates of alkali metals can be obtained in both the glassy and crystalline states.

  14. Biological metals and metal-targeting compounds in major neurodegenerative diseases. (United States)

    Barnham, Kevin J; Bush, Ashley I


    Multiple abnormalities occur in the homeostasis of essential endogenous brain biometals in age-related neurodegenerative disorders, Alzheimer's disease, Parkinson's disease, Huntington's disease and amyotrophic lateral sclerosis. As a result, metals both accumulate in microscopic proteinopathies, and can be deficient in cells or cellular compartments. Therefore, bulk measurement of metal content in brain tissue samples reveal only the "tip of the iceberg", with most of the important changes occurring on a microscopic and biochemical level. Each of the major proteins implicated in these disorders interacts with biological transition metals. Tau and the amyloid protein precursor have important roles in normal neuronal iron homeostasis. Changes in metal distribution, cellular deficiencies, or sequestration in proteinopathies all present abnormalities that can be corrected in animal models by small molecules. These biochemical targets are more complex than the simple excess of metals that are targeted by chelators. In this review we illustrate some of the richness in the science that has developed in the study of metals in neurodegeneration, and explore its novel pharmacology.

  15. Adsorption of volatile organic compounds in porous metal-organic frameworks functionalized by polyoxometalates (United States)

    Ma, Feng-Ji; Liu, Shu-Xia; Liang, Da-Dong; Ren, Guo-Jian; Wei, Feng; Chen, Ya-Guang; Su, Zhong-Min


    The functionalization of porous metal-organic frameworks (Cu 3( BTC) 2) was achieved by incorporating Keggin-type polyoxometalates (POMs), and further optimized via alkali metal ion-exchange. In addition to thermal gravimetric analysis, IR, single-crystal X-ray diffraction, and powder X-ray diffraction, the adsorption properties were characterized by N 2 and volatile organic compounds (VOCs) adsorption measurements, including short-chain alcohols ( C<4), cyclohexane, benzene, and toluene. The adsorption enthalpies estimated by the modified Clausius-Clapeyron equation provided insight into the impact of POMs and alkali metal cations on the adsorption of VOCs. The introduction of POMs not only improved the stability, but also brought the increase of adsorption capacity by strengthening the interaction with gas molecules. Furthermore, the exchanged alkali metal cations acted as active sites to interact with adsorbates and enhanced the adsorption of VOCs.

  16. Light-induced catalytic and cytotoxic properties of phosphorescent transition metal compounds with a d8 electronic configuration. (United States)

    To, Wai-Pong; Zou, Taotao; Sun, Raymond Wai-Yin; Che, Chi-Ming


    Transition metal compounds are well documented to have diverse applications such as in catalysis, light-emitting materials and therapeutics. In the areas of photocatalysis and photodynamic therapy, metal compounds of heavy transition metals are highly sought after because they can give rise to triplet excited states upon photoexcitation. The long lifetimes (more than 1 μs) of the triplet states of transition metal compounds allow for bimolecular reactions/processes such as energy transfer and/or electron transfer to occur. Reactions of triplet excited states of luminescent metal compounds with oxygen in cells may generate reactive oxygen species and/or induce damage to DNA, leading to cell death. This article recaps the recent findings on photochemical and phototoxic properties of luminescent platinum(II) and gold(III) compounds both from the literature and experimental results from our group.

  17. Synthesis and light-emitting properties of organic electroluminescent compounds and their metal complexes

    Institute of Scientific and Technical Information of China (English)

    CUI Jianzhong; Kim Sung-Hoon


    Several organic electroluminescent (EL) compounds, 2,2′-(1,4-phenylenedivinylene)bis-3,3-dimethyl-in- dolenine (1), 2,2′-(1,4-phenylenedivinylene)bis-benzoxazole (2), 2,2′-(1,4-phenylenedivinylene)bis-benzothiazole (3), 4,4′- (1,4-phenylenedivinylene)bis-quinoline (4), 2,2′-(1,4-phenyle- nedivinylene)bis-quinoline (5), 2,2′-(1,4-phenylenedivinyle- ne)bis-1,3,3-trimethyl-indolenine dichlo ride (6), 2,2′-(1,4- phenylene-divinylene)bis-1-hydro-3,3-dimethyl-indolenine dichloride (7), 2,2′-(1,4-phenylenedivinylene)bis-8-acetoxy- quinoline (8), 2,2′-(1,4-phenylenedivinylene)bis-8-hydroxyq- uinoline (9) and metal complexes of 9, Al(PHQ) (10) and Zn(PHQ) (11), have been synthesized and characterized. The crystal structure of 6 was determined. Light emitting properties of the prepared compounds have been investigated. 1 produces an orange-yellow emission (λmax = 575 nm). The cation, 6, gives a red emission (λmax = 607 nm), which is shifted 32 nm to the red compared to 1. 8 produces a yellow emission (λmax = 567 nm). The metal complex 10 gives a red emission (λmax = 610 nm), which is a red shift of 43 nm compared to 8. The change in structure in the prepared compound caused a change in the electron distribution in the compounds, which induces a large wavelength shift of the emitted-light. Thermal analysis showed that the decomposition temperatures of the metal complexes (10, 11) were higher than those for the smaller organic molecular compounds (1-9). Therefore, metal complexes (10, 11) can be used as EL materials over a larger temperature range.

  18. Bifunctional compounds for controlling metal-mediated aggregation of the aβ42 peptide. (United States)

    Sharma, Anuj K; Pavlova, Stephanie T; Kim, Jaekwang; Finkelstein, Darren; Hawco, Nicholas J; Rath, Nigam P; Kim, Jungsu; Mirica, Liviu M


    Abnormal interactions of Cu and Zn ions with the amyloid β (Aβ) peptide are proposed to play an important role in the pathogenesis of Alzheimer's disease (AD). Disruption of these metal-peptide interactions using chemical agents holds considerable promise as a therapeutic strategy to combat this incurable disease. Reported herein are two bifunctional compounds (BFCs) L1 and L2 that contain both amyloid-binding and metal-chelating molecular motifs. Both L1 and L2 exhibit high stability constants for Cu(2+) and Zn(2+) and thus are good chelators for these metal ions. In addition, L1 and L2 show strong affinity toward Aβ species. Both compounds are efficient inhibitors of the metal-mediated aggregation of the Aβ(42) peptide and promote disaggregation of amyloid fibrils, as observed by ThT fluorescence, native gel electrophoresis/Western blotting, and transmission electron microscopy (TEM). Interestingly, the formation of soluble Aβ(42) oligomers in the presence of metal ions and BFCs leads to an increased cellular toxicity. These results suggest that for the Aβ(42) peptide-in contrast to the Aβ(40) peptide-the previously employed strategy of inhibiting Aβ aggregation and promoting amyloid fibril dissagregation may not be optimal for the development of potential AD therapeutics, due to formation of neurotoxic soluble Aβ(42) oligomers.

  19. Technology Development and Production of Certain Chemical Platinum Metals Compounds at JSC "Krastsvetmet"

    Institute of Scientific and Technical Information of China (English)



    In recent years JSC "Krastsvetmet" has successfully developed the production of chemically pure compounds of precious metals.Currently methods have been developed and facilities have been provided for industrial production of the following platinum metals compounds:- Rhodium (Ⅲ) chloride hydrate,rhodium (Ⅲ) chloride solution,rhodium ( Ⅲ) nitrate solution,rhodium ( Ⅲ)iodide,rhodium ( Ⅲ) sulfate,hydrated rhodium ( Ⅲ) oxide,ammonium hexachlororodiate,rhodium ( Ⅲ)phosphate solution,rhodium electrolytes;Iridium (Ⅳ) chloride hydrate,iridium (Ⅲ) chloride hydrate,ammonium hexachloroiridate (Ⅳ),hexachloriridium acid solution,hexachloriridium crystalline acid;- Ruthenium (Ⅲ) chloride hydrate,ruthenium (Ⅳ) hydroxide chloride,ruthenium (Ⅳ) hydroxide chloride solution,ammonium hexachlororuthenate,ruthenium (Ⅲ) chloride solution,potassium,diaquaoctachloronitrido diruthenate.The quality of the production meets the requirements of Russian and foreign consumers.

  20. Thermodynamic Properties and Mixing Thermodynamic Parameter of Binary Metallic Melt Involving Compound Formation

    Institute of Scientific and Technical Information of China (English)

    ZHANG Jian


    Based on the coexistence theory of metallic melts involving compound formation,the theoretical cal culation equations of mixing thermodynamic parameters are established by giving up some empirical parameters in the associated solution model.For Fe-Al,Mn-Al and Ni-Al,the calculated results agree well with the experimental values,testifying that these equations can exactly embody mixing thermodynamic characteristics of these melts.

  1. DRIFT and DRUV spectroscopy methods for studying the interaction of metal compounds with native cellulose


    Visekruna, Jovana


    Dissertação de mestrado, Qualidade em Análises, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2015 Cellulose, the most abundant organic polymer on earth, has numerous applications including the application in pharmacy as excipient in different kinds of pharmaceutical formulations where it comes in contact with metal compounds used in therapeutic purposes. Chemically, is composed of hundreds to thousands of β 1→4 linked D glucopyranose units. It is insoluble in water and most...


    Institute of Scientific and Technical Information of China (English)

    J. Zhang


    Based on the atomicity and molecularity as well as the consistency of thermodynamicproperties and activities of metallic melts with their structures, the coexistence the-ory of metallic melts structure involving compound has been suggested. According tothis theory, the calculating models of mass action concentrations for different binarymetallic melts have been formulated. The calculated mass action concentrations agreewell with corresponding measured activities, which confirms that the suggested theorycan reflect the structural characteristics of metallic melts involving compound and thatthe mass action law is widely applicable to this kind of metallic melts.

  3. Mixed valence transition metal 2D-oxides: Comparison between delafossite and crednerite compounds (United States)

    Martin, Christine; Poienar, Maria


    Transition metal oxides offer large opportunities to study relationships between structures and properties. Indeed these compounds crystallize in numerous frameworks corresponding to different dimensionalities and, accordingly, show a huge variety of properties (as high Tc superconductivity, colossal magnetoresistivity, multiferroicity..). The control of the oxidation state of the transition metal, via the monitoring of the oxygen content, is of prime importance to understand and optimize the properties, due to the strong coupling that exists between the lattice and the charges and spins of the transition metals. In this large playground for chemists, we reinvestigated several 2D-compounds derived from delafossite structure. Considering this paper as a very short review, we report here the results obtained on CuMO2 compounds (with M = Cr, Mn or Mn+Cu) by using a combination of techniques, as X-ray, neutrons and/or electrons diffraction on poly-crystals for structural characterisations that are correlated with electrical and/or magnetic properties. The complementarity of studies is also addressed by the synthesis and characterization of single crystals in addition to poly-crystals. Moreover the comparison of the structures of similar Cr and Mn based oxides highlights the crucial role of the Jahn-Teller effect of trivalent manganese to lift the degeneracy, which is responsible of the magnetic frustration in CuCrO2.

  4. Strongly correlated transition metal compounds investigated by soft X-ray spectroscopies and multiplet calculations

    Energy Technology Data Exchange (ETDEWEB)

    Jiménez-Mier, J., E-mail: [Instituto de Ciencias Nucleares, UNAM, 04510 México, DF (Mexico); Olalde-Velasco, P. [Instituto de Ciencias Nucleares, UNAM, 04510 México, DF (Mexico); The Advanced Light Source, Lawrence Berkeley Laboratory, Berkeley, CA 94720 (United States); Herrera-Pérez, G.; Carabalí -Sandoval, G. [Instituto de Ciencias Nucleares, UNAM, 04510 México, DF (Mexico); Chavira, E. [Instituto de Investigaciones en Materiales, UNAM, 04510 México, DF (Mexico); Yang, W.-L.; Denlinger, J. [The Advanced Light Source, Lawrence Berkeley Laboratory, Berkeley, CA 94720 (United States)


    Direct probe of Mott–Hubbard (MH) to charge-transfer (CT) insulator transition in the MF{sub 2} (M = Cr–Zn) family of compounds was observed by combining F K and M L X-ray emission spectra (XES). This transition is evident as a crossover of the F-2p and M-3d occupied states. By combining F K XES data with F K edge X-ray absorption (XAS) data we directly obtained values for the M-3d Hubbard energy (U{sub dd}) and the F-2p to M-3d charge-transfer energy (Δ{sub CT}). Our results are in good agreement with the Zaanen–Sawatzky–Allen theory. We also present three examples where X-ray absorption at the transition metal L{sub 2,3} edges is used to study the oxidation state of various strongly correlated transition metal compounds. The metal oxidation state is obtained by direct comparison with crystal field multiplet calculations. The compounds are CrF{sub 2}, members of the La{sub 1−x}Sr{sub x}CoO{sub 3} family, and the MVO{sub 3} (M = La and Y) perovskites.

  5. Evolution of phenolic compounds and metal content of wine during alcoholic fermentation and storage. (United States)

    Bimpilas, Andreas; Tsimogiannis, Dimitrios; Balta-Brouma, Kalliopi; Lymperopoulou, Theopisti; Oreopoulou, Vassiliki


    Changes in the principal phenolic compounds and metal content during the vinification process and storage under modified atmosphere (50% N2, 50% CO2) of Merlot and Syrah wines, from grapes cultivated in Greece, have been investigated. Comparing the variation of metals at maceration process, with the variation of monomeric anthocyanins and flavonols, an inverse relationship was noticed, that can be attributed to complexing reactions of polyphenols with particular trace elements. Cu decreased rapidly, whereas a similar behavior that could be expected for Fe and Mn was not confirmed. Differences in the profile of anthocyanins and flavonols in the fresh Merlot and Syrah wines are reported. During 1 year of storage monomeric anthocyanins declined almost tenfold, probably due to polymerization reactions and copigmentation. Also, a decrease in flavonol glycosides and increase in the respective aglycones was observed, attributed to enzymatic hydrolysis. The concentration of total phenols and all metals remained practically constant.

  6. Design, synthesis, and biological properties of triazole derived compounds and their transition metal complexes. (United States)

    Chohan, Zahid H; Hanif, Muhammad


    Triazole derived Schiff bases and their metal complexes (cobalt(II), copper(II), nickel(II), and zinc(II)) have been prepared and characterized using IR, (1)H and (13)C NMR, mass spectrometry, magnetic susceptibility and conductivity measurements, and CHN analysis data. The structure of L(2), N-[(5-methylthiophen-2-yl)methylidene]-1H-1,2,4-triazol-3-amine, has also been determined by the X-ray diffraction method. All the metal(II) complexes showed octahedral geometry except the copper(II) complexes, which showed distorted octahedral geometry. The triazole ligands and their metal complexes have been screened for their in vitro antibacterial, antifungal, and cytotoxic activity. All the synthesized compounds showed moderate to significant antibacterial activity against one or more bacterial strains. It is revealed that all the synthesized complexes showed better activity than the ligands, due to coordination.

  7. Metal-based ethanolamine-derived compounds: a note on their synthesis, characterization and bioactivity. (United States)

    Amjad, Muhammad; Sumrra, Sajjad H; Akram, Muhammad Safwan; Chohan, Zahid H


    Metal-based ethanolamines, (L(1))-(L(4)) coordinated with Co(II), Cu(II), Ni(II) and Zn(II) metals in 1:2 (metal:ligand) molar ratio to produce new compounds have been reported. These compounds were screened for their bactericidal/fungicidal activity against a number of bacterial (Escherichia coli, Shigella flexneri, Pseudomonas aeruginosa, Salmonella typhi, Staphylococcus aureus and Bacillus subtilis) and fungal strains (Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani and Candida glabrata) alongside against a shrimp species known as Artemia salina. The screening results indicated that metal complexes have significantly higher activity than uncomplexed ligands against one or more bacterial/fungal species due to chelation. The ligand (L(4)) displayed good bacterial and fungal activity as compared to other ligands. The antibacterial results revealed that the Zn(II) complex (16) of (L(4)) was found to be the most active complex and Co(II) complex (14) of the same ligand (L(4)), demonstrated the highest antifungal activity.

  8. Analysis of trace metals and perfluorinated compounds in 43 representative tea products from South China. (United States)

    Zheng, Hai; Li, Jian-Long; Li, Hai-Hang; Hu, Guo-Cheng; Li, Hua-Shou


    Six trace metals (Cd, Pb, Cr, Cu, Zn, and Mn) and 2 perfluorinated compounds (PFCs), perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), were analyzed in 43 representative tea products (including 18 green, 12 Oolong, and 13 black teas) from 7 main tea production provinces in China, using the atomic absorption spectrophotometer for trace metals analysis and HPLC-MS/MS for PFOS and PFOA analysis. The average contents of the 3 essential metals Mn, Cu, and Zn ions in the tea samples were 629.74, 17.75, and 37.38 mg/kg, whereas 3 toxic metals Cd, Cr, and Pb were 0.65, 1.02, and 1.92 mg/kg, respectively. The contents of heavy metals in the 3 types of tea were in the order of black tea > Oolong tea > green tea. Both PFOS and PFOA contents were low and PFOA content was higher than PFOS in the tea samples. The highest concentration of PFOA was 0.25 ng/g dry weight found in a Hunan green tea. The Principal component analysis was performed with the trace metals and PFCs to analyze the relationships of these indices. The results showed that black teas had higher trace metals and PFCs than green and Oolong teas, and the teas from Hunan and Zhejiang provinces had higher Pb and Cr than others. This paper reports trace metals, and perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in wide range of tea products produced in the south China area. This paper also warns the low PFOS and PFOA pollution in tea. © 2014 Institute of Food Technologists®

  9. High-temperature thermochemistry of transition metal borides, silicides and related compounds. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Klemppa, Ole J.


    Earlier this year in collaboration with Dr. Susan V. Meschel we prepared a major review paper which gives a comprehensive summary of what our laboratory has accomplished with support from DOE. This paper is No.43 in the List of Publications provided. It was presented to TMS at its National Meeting in Nashville, TN last March. A copy of the manuscript of this paper was recently mailed to DOE. It has been submitted for publication in Journal of Alloys and Compounds. This review paper summarizes our observed trends in the enthalpies of formation of TR-X and RE-X compounds (where X is a IIIB or IVB element) in their dependence of the atomic number of the transition metal (TR) and the lanthanide metal (RE). In this paper our measured enthalpies of formation for each alloy family are compared for the 3d, 4d and 5d transition metal elements. We also compare our experimental results with predicted values based on Miedema's semi-empirical model. Data are presented for the carbides, silicides, germanides and stannides in Group IVB, and for the borides and aluminides in Group IIIB. During the past year (1999-2000) we have extended our work to compounds of the 3d, 4d and 5d elements with gallium (see papers No.40, No.41, and No.45 in the List of Publications). Fig. 1 (taken from No.45) presents a systematic picture of our experimental values for the most exothermic gallide compounds formed with the transition elements. This figure is characteristic of the other systematic pictures which we have found for the two other IIIB elements which we have studied and for the four IVB elements. These figures are all presented in Ref. No.43. This paper also illustrates how the enthalpy of formation of compounds of the IIIB and IVB elements with the lanthanide elements (with the exception of Pm, Eu and Yb) depend on the atomic number of RE. Finally our results for the RE-X compounds are compared with the predictions of Gschneidner (K.A. Gschneidner, Jr., J. Less Common Metals 17, 1

  10. The effect of coupling agents on silicate-based nanofillers/carbon black dual filler systems on the properties of a natural rubber/butadiene rubber compound

    NARCIS (Netherlands)

    Poikelispää, M.; Das, A.; Dierkes, W.K.; Vuorinen, J.


    Nanofillers have been introduced a few years ago, but their application in elastomers is still a challenge. With the existing rubber processing equipment and constraints of rubber mixing, dispersion of nanofillers is difficult. The processability and performance of compounds containing plate- or tub

  11. The fatty acids and alkanes of Satureja adamovicii Silic and Satureja fukarekii Silic (NOTE

    Directory of Open Access Journals (Sweden)



    Full Text Available The content and composition of fatty acids and alkanes of Satureja adamovicii Silic and Satureja fukarekii Silic were analized by GC. It was found that unsaturated acids prevailed and that the major components were palmitic, oleic, linoleic and linolenic acids. The hydrocarbon fractions of pentane extracts were shown to consist of the alkane homologues (C17 to C34 with nonacosane and hentriacontane being prevailing compounds.

  12. Metallomics insights into the programmed cell death induced by metal-based anticancer compounds. (United States)

    Tan, Cai-Ping; Lu, Yi-Ying; Ji, Liang-Nian; Mao, Zong-Wan


    Since the discovery of cisplatin more than 40 years ago, enormous research efforts have been dedicated to developing metal-based anticancer agents and to elucidating the mechanisms involved in the action of these compounds. Abnormal metabolism and the evasion of apoptosis are important hallmarks of malignant transformation, and the induction of apoptotic cell death has been considered to be a main pathway by which cytotoxic metal complexes combat cancer. However, many cancers have cellular defects involving the apoptotic machinery, which results in an acquired resistance to apoptotic cell death and therefore reduced chemotherapeutic effectiveness. Over the past decade, it has been revealed that a growing number of cell death pathways induced by metal complexes are not dependent on apoptosis. Metal complexes specifically triggering these alternative cell death pathways have been identified and explored as novel cancer treatment options. In this review, we discuss recent examples of metallomics studies on the different types of cell death induced by metal-based anticancer drugs, especially on the three major forms of programmed cell death (PCD) in mammalian cells: apoptosis, autophagy and regulated necrosis, also called necroptosis.

  13. Nanostructured silicate polymer concrete

    Directory of Open Access Journals (Sweden)

    Figovskiy Oleg L'vovich


    Full Text Available It has been known that acid-resistant concretes on the liquid glass basis have high porosity (up to 18~20 %, low strength and insufficient water resistance. Significant increasing of silicate matrix strength and density was carried out by incorporation of special liquid organic alkali-soluble silicate additives, which block superficial pores and reduce concrete shrinkage deformation. It was demonstrated that introduction of tetrafurfuryloxisilane additive sharply increases strength, durability and shock resistance of silicate polymer concrete in aggressive media. The experiments showed, that the strength and density of silicate polymer concrete increase in case of decreasing liquid glass content. The authors obtained optimal content of silicate polymer concrete, which possesses increased strength, durability, density and crack-resistance. Diffusive permeability of concrete and its chemical resistance has been investigated in various corroding media.

  14. Exploring the reactivity of flavonoid compounds with metal-associated amyloid-β species. (United States)

    He, Xiaoming; Park, Hyun Min; Hyung, Suk-Joon; DeToma, Alaina S; Kim, Cheal; Ruotolo, Brandon T; Lim, Mi Hee


    Metal ions associated with amyloid-β (Aβ) peptides have been suggested to be involved in the development of Alzheimer's disease (AD), but this remains unclear and controversial. Some attempts to rationally design or select small molecules with structural moieties for metal chelation and Aβ interaction (i.e., bifunctionality) have been made to gain a better understanding of the hypothesis. In order to contribute to these efforts, four synthetic flavonoid derivatives FL1-FL4 were rationally selected according to the principles of bifunctionality and their abilities to chelate metal ions, interact with Aβ, inhibit metal-induced Aβ aggregation, scavenge radicals, and regulate the formation of reactive oxygen species (ROS) were studied using physical methods and biological assays. The compounds FL1-FL3 were able to chelate metal ions, but showed limited solubility in aqueous buffered solutions. In the case of FL4, which was most compatible with aqueous conditions, its binding affinities for Cu(2+) and Zn(2+) (nM and μM, respectively) were obtained through solution speciation studies. The direct interaction between FL4 and Aβ monomer was weak, which was monitored by NMR spectroscopy and mass spectrometry. Employing FL1-FL4, no noticeable inhibitory effect on metal-mediated Aβ aggregation was observed. Among FL1-FL4, FL3, having 3-OH, 4-oxo, and 4'-N(CH(3))(2) groups, exhibited similar antioxidant activity to the vitamin E analogue, Trolox, and ca. 60% reduction in the amount of hydrogen peroxide (H(2)O(2)) generated by Cu(2+)-Aβ in the presence of dioxygen (O(2)) and a reducing agent. Overall, the studies here suggest that although four flavonoid molecules were selected based on expected bifunctionality, their properties and metal-Aβ reactivity were varied depending on the structure differences, demonstrating that bifunctionality must be well tuned to afford desirable reactivity.

  15. Transition-Metal Planar Boron Clusters: a New Class of Aromatic Compounds with High Coordination (United States)

    Wang, Lai-Sheng


    Photoelectron spectroscopy in combination with computational studies over the past decade has shown that boron clusters possess planar or quasi-planar structures, in contrast to that of bulk boron, which is dominated by three-dimensional cage-like building blocks. All planar or quasi-planar boron clusters are observed to consist of a monocyclic circumference with one or more interior atoms. The propensity for planarity has been found to be due to both σ and π electron delocalization throughout the molecular plane, giving rise to concepts of σ and π double aromaticity. We have found further that the central boron atoms can be substituted by transition metal atoms to form a new class of aromatic compounds, which consist of a central metal atom and a monocyclic boron ring (M B_n). Eight-, nine-, and ten-membered rings of boron have been observed, giving rise to octa-, ennea-, and deca-coordinated aromatic transition metal compounds [1-3]. References: [1] ``Aromatic Metal-Centered Monocyclic Boron Rings: Co B_9^- and Ru B_9^-" (Constantin Romanescu, Timur R. Galeev, Wei-Li Li, A. I. Boldyrev, and L. S. Wang), Angew. Chem. Int. Ed. {50}, 9334-9337 (2011). [2] ``Transition-Metal-Centered Nine-Membered Boron Rings: M B_9 and M B_9^- (M = Rh, Ir)" (Wei-Li Li, Constantin Romanescu, Timur R. Galeev, Zachary Piazza, A. I. Boldyrev, and L. S. Wang), J. Am. Chem. Soc. {134}, 165-168 (2012). [3] ``Observation of the Highest Coordination Number in Planar Species: Decacoordinated Ta B10^- and Nb B_9^- Anions" (Timur R. Galeev, Constantin Romanescu, Wei-Li Li, L. S. Wang, and A. I. Boldyrev), Angew. Chem. Int. Ed. {51}, 2101-2105 (2012).

  16. Recent insights on the medicinal chemistry of metal-based compounds: hints for the successful drug design. (United States)

    Hernandes, M Z; de S Pontes, F J; Coelho, L C D; Moreira, D R M; Pereira, V R A; Leite, A C L


    Although more complex than usually described, the anticancer action mechanism of cisplatin is based on binding to DNA. Following this line of reasoning, most the metal-based compounds discovered soon after cisplatin were designed to acting as DNA-binding agents and their pharmacological properties were thought to be correlated with this mechanism. Apart from the DNA structure, a significant number of proteins and biochemical pathways have been described as drug targets for metal-based compounds. This paper is therefore aimed at discussing the most recent findings on the medicinal chemistry of metal-based drugs. It starts illustrating the design concept behind the bioinorganic chemistry of anticancer complexes. Anticancer metallic compounds that inhibit the protein kinases are concisely discussed as a case study. The accuracy and limitations of molecular docking programs currently available to predict the binding mode of metallic complexes in molecular targets are further discussed. Finally, the advantages and disadvantages of different in vitro screenings are briefly commented.

  17. Optical Parameters and Absorption of Azo Dye and Its Metal-Substituted Compound Thin Films

    Institute of Scientific and Technical Information of China (English)

    魏斌; 吴谊群; 顾冬红; 干福熹


    We determine the complex refractive indices N ( N = n - ik), dielectric constants ε(ε = ε1 - iε2), and absorption coefficients α of a new azo dye [2-(6-methyl-2-benzothiazolyazo)-5-diethylaminophenol(MBADP)]-doped polymer and its nickel- and zinc-substituted compounds(Ni-MBADP and Zn-MBADP) spin-coated thin films from a scanning ellipsometer in the wavelength 400-700 nm region. Metal chelation strongly (about one times) enhances the optical and dielectric parameters at the peaks and results in a large bathochromic shift (50-60nm) of absorption band. Bathochromic shift of Ni-MBADP is about 10nm larger than that of Zn-MBADP due to different spatial configurations formed in the metal-azo complexes.

  18. Composite materials obtained by the ion-plasma sputtering of metal compound coatings on polymer films (United States)

    Khlebnikov, Nikolai; Polyakov, Evgenii; Borisov, Sergei; Barashev, Nikolai; Biramov, Emir; Maltceva, Anastasia; Vereshchagin, Artem; Khartov, Stas; Voronin, Anton


    In this article, the principle and examples composite materials obtained by deposition of metal compound coatings on polymer film substrates by the ion-plasma sputtering method are presented. A synergistic effect is to obtain the materials with structural properties of the polymer substrate and the surface properties of the metal deposited coatings. The technology of sputtering of TiN coatings of various thicknesses on polyethylene terephthalate films is discussed. The obtained composites are characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), and scanning tunneling microscopy (STM) is shown. The examples of application of this method, such as receiving nanocomposite track membranes and flexible transparent electrodes, are considered.

  19. Stability of Weyl points in magnetic half-metallic Heusler compounds (United States)

    Chadov, Stanislav; Wu, Shu-Chun; Felser, Claudia; Galanakis, Iosif


    We employ ab initio fully relativistic electronic structure calculations to study the stability of the Weyl points in the momentum space within the class of the half-metallic ferromagnetic full Heusler materials, by focusing on Co2TiAl as a well-established prototype compound. Here we show that both the number of the Weyl points together with their k -space coordinates can be controlled by the orientation of the magnetization. This alternative degree of freedom, which is absent in other topological materials (e.g., in Weyl semimetals), introduces functionalities that are specific for the class of half-metallic ferromagnets. Of special interest are crossing points which are preserved irrespective of any arbitrary rotation of the magnetization axis.

  20. The metal-driven biogeochemistry of gaseous compounds in the environment

    CERN Document Server

    Kroneck, Peter MH


    MILS-14 provides a most up-to-date view of the exciting biogeochemistry of gases in our environment as driven mostly by microorganisms. These employ a machinery of sophisticated metalloenzymes, where especially transition metals (such as Fe, Ni, Cu, Mo, W) play a fundamental role, that is, in the activation, transformation and syntheses of gases like dihydrogen, methane, carbon monoxide, acetylene and those of the biological nitrogen and sulfur cycles. The Metal-Driven Biogeochemistry of Gaseous Compounds in the Environment is a vibrant research area based mainly on structural and microbial biology, inorganic biological chemistry and environmental biochemistry. All this is covered in an authoritative manner in 11 stimulating chapters, written by 26 internationally recognized experts and supported by nearly 1200 references, informative tables and about 100 illustrations (two thirds in color). MILS-14 also provides excellent information for teaching. Peter M. H. Kroneck is a bioinorganic chemist who is explorin...

  1. The effect of various naturally occurring metal-binding compounds on the electrochemical behavior of aluminum

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, D.C.; McCafferty, E. [Naval Research lab., Washington, DC (United States)


    Naturally occurring biological molecules are of considerable interest as possible corrosion inhibitors because of increased attention on the development of environmentally compatible, nonpolluting corrosion inhibitors. A hydroxamate yeast siderophore (rhodotorulic acid), a catecholate bacterial siderophore (parabactin), an adhesive protein from the blue mussel Mytilus edulis, and two metal-binding compounds isolated from the tomato and sunflower roots, namely, chlorogenic and caffeic acid, respectively, were adsorbed from solution onto pure aluminum (99.9995%) and their effect on the critical pitting potential and polarization resistance in deaerated 0.1 M NaCl was measured. These measurements were made using anodic polarization and ac impedance spectroscopy. The catechol-containing siderophore has an inhibitive effect on the critical pitting potential of aluminum in 0.1 M NaCl and increases the polarization resistance of the metal over time. The adhesive protein from the blue mussel is also effective in inhibiting the pitting of aluminum.

  2. Enhancement of nonlinear optical properties of compounds of silica glass and metallic nanoparticle

    Indian Academy of Sciences (India)



    The aim of this paper is to introduce a method for enhancing the nonlinear optical properties in silica glass by using metallic nanoparticles. First, the T-matrix method is developed to calculate the effective dielectric constant for the compound of silica glass and metallic nanoparticles, both of which possess nonlinear dielectric constants. In the second step, the Maxwell–Garnetttheory is exploited to replace the spherical nanoparticles with cylindrical and ellipsoidal ones, facilitating the calculation of the third-order nonlinear effective susceptibility for a degenerate four-wave mixing case. The results are followed by numerical computations for silver, copper and gold nanoparticles. It is shown, graphically, that the maximum and minimum of the real part of thereflection coefficient for nanoparticles of silver occurs in smaller wavelengths compared to that of copper and gold. Further, it is found that spherical nanoparticles exhibit greater figure-of-merit compared to those with cylindrical or ellipsoidal geometries.

  3. Physical chemistry of evaporation and deposition of metals, alloys and their compounds

    Energy Technology Data Exchange (ETDEWEB)

    Kato, Eiichi


    The thermodynamics, reaction kynetics and chemical vapor deposition(CVD) process were explained on evaporation and deposition to indicate that the chemical metallurgy was effective for the process analysis of various materials, mainly for metals. Firstly, gaseous phase growth of diamond was explained, evaporated molecular species were studied, vapor species of metal compounds were illustrated and vapor pressure data were dealed with. Fundamentals on evaporation coefficient and condensation coefficient were explained concerning the reaction kinetics and the measurements of Langumuir evaporation coefficient were illustrated. Further, the acceleration and inhibition of evaporation were described with examples of molten alloys. Thermal CVD process in which process is comparatively simple, was taken up from various CVD processes and Si thinfoil formation was studied. The relationship between reaction rate and temperature was described along with reaction process. Finally, the analysis of B and TiN deposition was detailed. (19 figs, 4 tabs, 30 refs)

  4. High-resolution x-ray absorption spectroscopy studies of metal compounds in neurodegenerative brain tissue (United States)

    Collingwood, J. F.; Mikhaylova, A.; Davidson, M. R.; Batich, C.; Streit, W. J.; Eskin, T.; Terry, J.; Barrea, R.; Underhill, R. S.; Dobson, J.


    Fluorescence mapping and microfocus X-ray absorption spectroscopy are used to detect, locate and identify iron biominerals and other inorganic metal accumulations in neurodegenerative brain tissue at sub-cellular resolution (reviewed. Synchrotron X-rays are used to map tissue sections for metals of interest, and XANES and XAFS are used to characterise anomalous concentrations of the metals in-situ so that they can be correlated with tissue structures and disease pathology. Iron anomalies associated with biogenic magnetite, ferritin and haemoglobin are located and identified in an avian tissue model with a pixel resolution ~5 microns. Subsequent studies include brain tissue sections from transgenic Huntington's mice, and the first high-resolution mapping and identification of iron biominerals in human Alzheimer's and control autopsy brain tissue. Technical developments include use of microfocus diffraction to obtain structural information about biominerals in-situ, and depositing sample location grids by lithography for the location of anomalies by conventional microscopy. The combined techniques provide a breakthrough in the study of both intra- and extra-cellular iron compounds and related metals in tissue. The information to be gained from this approach has implications for future diagnosis and treatment of neurodegeneration, and for our understanding of the mechanisms involved.

  5. Soft X-ray spectroscopy of transition metal compounds: a theoretical perspective (United States)

    Bokarev, S. I.; Hilal, R.; Aziz, S. G.; Kühn, O.


    To date, X-ray spectroscopy has become a routine tool that can reveal highly local and element-specific information on the electronic structure of atoms in complex environments. Here, we report on the development of an efficient and versatile theoretical methodology for the treatment of soft X-ray spectra of transition metal compounds based on the multi-configurational self-consistent field electronic structure theory. A special focus is put on the L-edge photon-in/photon-out and photon-in/electron-out processes, i.e. X-ray absorption, resonant inelastic scattering, partial fluorescence yield, and photoelectron spectroscopy, all treated on the same theoretical footing. The investigated systems range from small prototypical coordination compounds and catalysts to aggregates of biomolecules.

  6. Gadolinium(III)-sensitized fluorescence of europium in its mixed-metal compounds with trifluroacetate (United States)

    Kalinovskaya, I. V.; Zadorozhnaya, A. N.


    The fluorescence properties of mixed-metal compounds of Eu(III) and Gd(III) with trifluoroacetic acid, Eu1-xGdx(C2F3O2)3·yD·zH2O, where D - 1,10-phenanthroline, 2,2-dipyridil, diphenylguanidine, x = 0, 0.25, 0.5, or 0.7, were studied. Luminescence spectroscopic evidence and the examination of excitation spectra indicate the occurrence of efficient energy transfer from the gadolinium to the europium ion. The greatest promotion of Eu3+ photoluminescence at 615 nm is observed when Eu:Gd = 1:1.

  7. Micro- and Nanostructured Metal Oxide Chemical Sensors for Volatile Organic Compounds (United States)

    Alim, M. A.; Penn, B. G.; Currie, J. R., Jr.; Batra, A. K.; Aggarwal, M. D.


    Aeronautic and space applications warrant the development of chemical sensors which operate in a variety of environments. This technical memorandum incorporates various kinds of chemical sensors and ways to improve their performance. The results of exploratory investigation of the binary composite polycrystalline thick-films such as SnO2-WO3, SnO2-In2O3, SnO2-ZnO for the detection of volatile organic compound (isopropanol) are reported. A short review of the present status of the new types of nanostructured sensors such as nanobelts, nanorods, nanotube, etc. based on metal oxides is presented.

  8. Fluorite and mixed-metal Kagome-related topologies in metal-organic framework compounds: synthesis, structure, and properties. (United States)

    Mahata, Partha; Raghunathan, Rajamani; Banerjee, Debamalya; Sen, Diptiman; Ramasesha, S; Bhat, S V; Natarajan, S


    Two new three-dimensional metal-organic frameworks (MOFs) [Mn(2)(mu(3)-OH)(H(2)O)(2)(BTC)] x 2 H(2)O, I, and [NaMn(BTC)], II (BTC = 1,2,4-benzenetricarboxylate = trimellitate) were synthesized and their structures determined by single-crystal X-ray diffraction (XRD). In I, the Mn(4) cluster, [Mn(4)(mu(3)-OH)(2)(H(2)O)(4)O(12)], is connected with eight trimellitate anions and each trimellitate anion connects to four different Mn(4) clusters, resulting in a fluorite-like structure. In II, the Mn(2)O(8) dimer is connected with two Na(+) ions through carboxylate oxygen to form mixed-metal distorted Kagome-related two-dimensional -M-O-M- layers, which are pillared by the trimellitate anions forming the three-dimensional structure. The extra-framework water molecules in I are reversibly adsorbed and are also corroborated by powder XRD studies. The formation of octameric water clusters involving free and coordinated water molecules appears to be new. Interesting magnetic behavior has been observed for both compounds. Electron spin resonance (ESR) studies indicate a broadening of the signal below the ordering temperature and appear to support the findings of the magnetic studies.

  9. Effects of Ga substitution on the structural and magnetic properties of half metallic Fe2MnSi Heusler compound (United States)

    Pedro, S. S.; Caraballo Vivas, R. J.; Andrade, V. M.; Cruz, C.; Paixão, L. S.; Contreras, C.; Costa-Soares, T.; Caldeira, L.; Coelho, A. A.; Carvalho, A. Magnus G.; Rocco, D. L.; Reis, M. S.


    The so-called half-metallic magnets have been proposed as good candidates for spintronic applications due to the feature of exhibiting a hundred percent spin polarization at the Fermi level. Such materials follow the Slater-Pauling rule, which relates the magnetic moment with the valence electrons in the system. In this paper, we study the bulk polycrystalline half-metallic Fe2MnSi Heusler compound replacing Si by Ga to determine how the Ga addition changes the magnetic, the structural, and the half-metal properties of this compound. The material does not follow the Slater-Pauling rule, probably due to a minor structural disorder degree in the system, but a linear dependence on the magnetic transition temperature with the valence electron number points to the half-metallic behavior of this compound.

  10. Pressure induced structural phase transition in IB transition metal nitrides compounds

    Energy Technology Data Exchange (ETDEWEB)

    Soni, Shubhangi; Kaurav, Netram, E-mail:; Jain, A. [Department of Physics, Govt. Holkar Science college, A. B. Road, Indore-452001 India (India); Shah, S. [Department of Physics, P. M. B. Gujarati Science College, Indore-452001 (India); Choudhary, K. K. [Department of Physics, National Defence Academy, Khadakwasla, Pune-411 0231 India (India)


    Transition metal mononitrides are known as refractory compounds, and they have, relatively, high hardness, brittleness, melting point, and superconducting transition temperature, and they also have interesting optical, electronic, catalytic, and magnetic properties. Evolution of structural properties would be an important step towards realizing the potential technological scenario of this material of class. In the present study, an effective interionic interaction potential (EIOP) is developed to investigate the pressure induced phase transitions in IB transition metal nitrides TMN [TM = Cu, Ag, and Au] compounds. The long range Coulomb, van der Waals (vdW) interaction and the short-range repulsive interaction upto second-neighbor ions within the Hafemeister and Flygare approach with modified ionic charge are properly incorporated in the EIOP. The vdW coefficients are computed following the Slater-Kirkwood variational method, as both the ions are polarizable. The estimated value of the phase transition pressure (Pt) and the magnitude of the discontinuity in volume at the transition pressure are consistent as compared to the reported data.

  11. Two-dimensional topological crystalline quantum spin Hall effect in transition metal intercalated compounds (United States)

    Zhou, Jian; Jena, Puru


    While most of the two-dimensional (2D) topological crystalline insulators (TCIs) belong to group IV-VI narrow-band-gap semiconductors in a square lattice, in the present work we predict a TCI family based on transition metal intercalated compounds in a hexagonal lattice. First-principles calculations combined with a substrate-fixed globally optimal structural search technique show that a layer of Os prefers a uniform distribution between two graphene sheets. Band dispersion calculations reveal a Dirac point and a Dirac nodal ring near the Fermi level. The Dirac point is ascribed to the hybridization of e2 and e2* orbitals, and the Dirac ring is formed due to dispersion of s and e1* orbitals. Upon inclusion of spin-orbit coupling, these Dirac states open topologically nontrivial local band gaps, which are characterized by nonzero mirror Chern numbers. The quantum spin Hall effect is also observed by integrating the spin Berry curvature in the Brillouin zone. In contrast to the 2D group IV-VI TCIs whose band inversions at X and Y points are "locked" by C4 rotation symmetry, here the relative energy of two local band gaps can be manipulated by in-plane biaxial strains. Some other similar intercalation compounds are also shown to be topologically nontrivial. Our work extends the 2D TCI family into a hexagonal lattice composed of transition metals.

  12. Sorption of uranyl(VI) cations on suspended silicate: effects of N-donor ligands, carboxylic acids, organic cosolvents, and metal ions

    Energy Technology Data Exchange (ETDEWEB)

    Pathak, P.N.; Choppin, G.R. [Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry


    Sorption of uranyl ion, UO{sub 2}{sup 2+}, on silicate particles (3.00g/L) was studied in sodium perchlorate solution as a function of pcH and ionic strength at 298 K. The effects of different ligands (e.g., N-donors, carboxylic acids) on the uranyl sorption were investigated. At I = 0.20 M (NaClO{sub 4}), uranyl sorption on silicate increased from ca. 6% (pcH 3.0) to ca. 99% (at pcH 6.5), above which a small decrease was observed. A synergistic enhancement in uranyl sorption was observed in the presence of N-donor ligands such as 1,10-phenanthroline and ethylenediamine in the pcH range 3 to 4.5 as compared to that in the absence of ligands. Carboxylic acids inhibited the sorption in the order: citric acid > malonic acid > nitrilotriacetic acid > iminodiacetic acid > sulfosalicylic acid > succinic acid > glycolic acid. The presence of organic cosolvents such as dimethylsulfoxide, glycerol and tetrahydrofuran had no significant influence on the uranyl sorption profile. Uranyl sorption decreased marginally in the presence of 1.00 x 10{sup -3} M Eu(III). (orig.)

  13. A standardized evaluation of artefacts from metallic compounds during fast MR imaging. (United States)

    Murakami, Shumei; Verdonschot, Rinus G; Kataoka, Miyoshi; Kakimoto, Naoya; Shimamoto, Hiroaki; Kreiborg, Sven


    Metallic compounds present in the oral and maxillofacial regions (OMRs) cause large artefacts during MR scanning. We quantitatively assessed these artefacts embedded within a phantom according to standards set by the American Society for Testing and Materials (ASTM). Seven metallic dental materials (each of which was a 10-mm(3) cube embedded within a phantom) were scanned [i.e. aluminium (Al), silver alloy (Ag), type IV gold alloy (Au), gold-palladium-silver alloy (Au-Pd-Ag), titanium (Ti), nickel-chromium alloy (NC) and cobalt-chromium alloy (CC)] and compared with a reference image. Sequences included gradient echo (GRE), fast spin echo (FSE), gradient recalled acquisition in steady state (GRASS), a spoiled GRASS (SPGR), a fast SPGR (FSPGR), fast imaging employing steady state (FIESTA) and echo planar imaging (EPI; axial/sagittal planes). Artefact areas were determined according to the ASTM-F2119 standard, and artefact volumes were assessed using OsiriX MD software (Pixmeo, Geneva, Switzerland). Tukey-Kramer post hoc tests were used for statistical comparisons. For most materials, scanning sequences eliciting artefact volumes in the following (ascending) order FSE-T1/FSE-T2 < FSPGR/SPGR < GRASS/GRE < FIESTA < EPI. For all scanning sequences, artefact volumes containing Au, Al, Ag and Au-Pd-Ag were significantly smaller than other materials (in which artefact volume size increased, respectively, from Ti < NC < CC). The artefact-specific shape (elicited by the cubic sample) depended on the scanning plane (i.e. a circular pattern for the axial plane and a "clover-like" pattern for the sagittal plane). The availability of standardized information on artefact size and configuration during MRI will enhance diagnosis when faced with metallic compounds in the OMR.

  14. Polymer-Layer Silicate Nanocomposites

    DEFF Research Database (Denmark)

    Potarniche, Catalina-Gabriela

    Nowadays, some of the material challenges arise from a performance point of view as well as from recycling and biodegradability. Concerning these aspects, the development of polymer layered silicate nanocomposites can provide possible solutions. This study investigates how to obtain polymer layered...... silicate nanocomposites and their structure-properties relationship. In the first part of the thesis, thermoplastic layered silicates were obtained by extrusion. Different modification methods were tested to observe the intercalation treatment effect on the silicate-modifier interactions. The silicate...

  15. Safety Evaluation of Osun River Water Containing Heavy Metals and Volatile Organic Compounds (VOCs) in Rats. (United States)

    Azeez, L; Salau, A K; Adewuyi, S O; Osineye, S O; Tijani, K O; Balogun, R O


    This study evaluated the pH, heavy metals and volatile organic compounds (VOCs) in Osun river water. It also evaluated its safety in rats. Heavy metals were determined by atomic absorption spectrophotometry (AAS) while VOCs were determined by gas chromatography coupled with flame ionization detector (GC-FID). Male and female rats were exposed to Osun river water for three weeks and then sacrificed. The abundance of heavy metals in Osun river followed the trend Pb > Cd > Zn > Fe > Cr > Cu while VOCs followed the trend benzene < ethylbenzene < toluene < xylene. The concentrations of Pb, Cd and benzene were higher than the permissible limits of Standards Organization of Nigeria (SON) and World Health Organization (WHO) respectively. Rats exposed to Osun river water for three weeks had increased WBC, thiobarbituric acid reactive substances (TBARS), serum proteins and serum aminotransferases. There were also significant decreases in HCT, PLT, liver aminotransferases and liver glutathione compared to the control. These results show that the pollutants in Osun river water are capable of inducing hematological imbalance and liver cell injury. The toxicity induced in blood was sex-dependent affecting female rats more than male rats.

  16. Preparation of Metallic Aluminum Compound Particles by Submerged Arc Discharge Method in Aqueous Media (United States)

    Liao, Chih-Yu; Tseng, Kuo-Hsiung; Lin, Hong-Shiou


    Fine metal particles are produced by chemical methods, which add surfactants to control particle size and concentration. This study used the submerged arc discharge method (SADM) to prepare metal fluid containing nanoparticles and submicron particles in pure dielectric fluid (deionized water or alcohol). The process is fast and simple, and it does not require the addition of chemical agents. The SADM uses electrical discharge machining (EDM) equipment, and the key parameters of the production process include discharge voltage, current, and pulse discharge on-off duration. This study added a capacitive component between the electrodes and the electrode Z-axis regulation in the control parameters to render the aluminum fluid process smooth, which is the main difference of this article from the literature. The experimental results showed that SADM can produce aluminum particles from nanometer to submicron grade, and it can obtain different compounds from different dielectric fluids. The dielectric fluids used in this study were deionized water and ethanol, and aluminum hydroxide Al(OH)3 particles with suspending power and precipitated aluminum particles were obtained, respectively. The preparations of metal colloid and particles by the SADM process have the characteristics of low cost, high efficiency, high speed, and mass production. Thus, the process has high research value and developmental opportunities.

  17. Tunable hydrogen storage in magnesium-transition metal compounds: First-principles calculations (United States)

    Er, Süleyman; Tiwari, Dhirendra; de Wijs, Gilles A.; Brocks, Geert


    Magnesium dihydride (MgH2) stores 7.7wt% hydrogen but it suffers from a high thermodynamic stability and slow (de)hydrogenation kinetics. Alloying Mg with lightweight transition metals (TM) (=Sc,Ti,V,Cr) aims at improving the thermodynamic and kinetic properties. We study the structure and stability of MgxTM1-xH2 compounds, x=[0-1] , by first-principles calculations at the level of density functional theory. We find that the experimentally observed sharp decrease in hydrogenation rates for x≳0.8 correlates with a phase transition of MgxTM1-xH2 from a fluorite to a rutile phase. The stability of these compounds decreases along the series Sc, Ti, V, and Cr. Varying the TM and the composition x , the formation enthalpy of MgxTM1-xH2 can be tuned over the substantial range of 0-2 eV/f.u. Assuming however that the alloy MgxTM1-x does not decompose upon dehydrogenation, the enthalpy associated with reversible hydrogenation of compounds with a high magnesium content (x=0.75) is close to that of pure Mg.

  18. Quinazolinone derivative: Model compound for determination of dipole moment, solvatochromism and metal ion sensing (United States)

    Al-Sehemi, Abdullah G.; Pannipara, Mehboobali; Kalam, Abul


    A dihydroquinazolinone derivative 2-(2,4-Dimethoxy-phenyl)-2,3-dihydro-1H-quinazolin-4-one (1) was synthesized and characterized by 1H NMR, 13C NMR and FT-IR and its spectral, photophysical, intramolecular charge transfer characteristics were studied by absorption and emission spectroscopy. The compound exhibits significant changes in their photophysical properties depending on the solvent polarity. The observed bathochromic emission band and difference in Stokes shift on changing the polarity of the solvents clearly demonstrate the highly polar character of the excited state, which is also supported by the enhancement of dipole moment of the molecule upon photoexcitation. Solvatochromic shift methods based on Lippert-Mataga, Bakhshiev-Kawski and Reichardt's correlations were applied to calculate the ground, excited and change in dipole moments. The effect of solute-solvent interactions on compound 1 was studied using multi-parameter solvent polarity scales proposed by Kamlet-Taft and Catalan. The interactions of various metal ions on compound 1 were also studied using steady state fluorescence measurements. The emission profile reveals that it acts as on-off type fluorescent chemosensor for selective and sensitive detection of Hg2 + ions. Complexation stoichiometry and mechanism of quenching were determined from Benesi-Hildebrand and Stern-Volmer plot.

  19. Half-metallicity and magnetism of quaternary Heusler compounds CoRuTiZ (Z=Si, Ge, and Sn) (United States)

    Bahramian, S.; Ahmadian, F.


    First-principle calculations based on the density functional theory for new quaternary Heusler compounds CoRuTiZ (Z=Si, Ge, and Sn) were performed. It was found that all three compounds were stable at YI structure in ferromagnetic state. The CoRuTiSi, CoRuTiGe, and CoRuTiSn were half-metal with integer magnetic moments of 1.00 μB per formula unit and half-metallic gaps of 0.13, 0.10, and 0.01 eV at their equilibrium volume, respectively. The density of states (DOSs) and band structures of these compounds were studied and the origin of half-metallicity was discussed. The CoRuTiSi, CoRuTiGe, and CoRuTiSn compounds showed half-metallic characteristics at lattice constants ranges of 5.77-6.36 Å, 5.66-6.16 Å, and 5.83-6.23 Å, indicating the lattice distortion did not affect the half-metallic properties of these compounds which makes them interesting materials in the spintronic field.

  20. Perspectives from ab-initio and tight-binding: Applications to transition metal compounds and superlattices (United States)

    Venkataraman, Vijay Shankar

    The experimental and theoretical study of transition metal compounds have occupied condensed matter physicists for the best part of the last century. The rich variety of physical behaviour exhibited by these compounds owes its origin to the subtle balance of the energy scales at play for the d orbitals. In this thesis, we study three different systems comprised of transition metal atoms from the third, the fourth, and the fifth group of the periodic table using a combination of ab-initio density functional theory (DFT) computations and effective tight-binding models for the electronic properties. We first consider the electronic properties of artificially fabricated perovskite superlattices of the form [(SrIrO3)m / SrTiO3] with integer m denoting the number of layers of SrIrO3. After discussing the results of experiments undertaken by our collaborators, we present the results of our DFT calculations and build tight-binding models for the m = 1 and m = 2 superlattices. The active ingredient is found to be the 5d orbitals with significant spin-orbit coupling. We then study the energies of magnetic ground states within DFT and compare and contrast our results with those obtained for the bulk Ruddlesden-Popper iridates. Together with experimental measurements, our results suggest that these superlattices are an exciting venue to probe the magnetism and metal-insulator transitions that occur from the intricate balance of the spin-orbit coupling and electron interactions, as has been reported for their bulk counterparts. Next, we consider alpha-RuCl3, a honeycomb lattice compound. We first show using DFT calculations in conjunction with experiments performed by our collaborators, how spin-orbit coupling in the 4d orbitals of Ru is essential to understand the insulating state realized in this compound. Then, in the latter half of the chapter, we study the magnetic ground states of a two-dimensional analogue of alpha-RuCl3 in weak and strong-coupling regimes obtained from

  1. A tomato stem cell extract, containing antioxidant compounds and metal chelating factors, protects skin cells from heavy metal-induced damages. (United States)

    Tito, Annalisa; Carola, Antonietta; Bimonte, Marida; Barbulova, Ani; Arciello, Stefania; de Laurentiis, Francesco; Monoli, Irene; Hill, Jacqueline; Gibertoni, Simone; Colucci, Gabriella; Apone, Fabio


    Heavy metals can cause several genotoxic effects on cells, including oxidative stress, DNA sequence breakage and protein modification. Among the body organs, skin is certainly the most exposed to heavy metal stress and thus the most damaged by the toxic effects that these chemicals cause. Moreover, heavy metals, in particular nickel, can induce the over-expression of collagenases (enzymes responsible for collagen degradation), leading to weakening of the skin extracellular matrix. Plants have evolved sophisticated mechanisms to protect their cells from heavy metal toxicity, including the synthesis of metal chelating proteins and peptides, such as metallothioneins and phytochelatins (PC), which capture the metals and prevent the damages on the cellular structures. To protect human skin cells from heavy metal toxicity, we developed a new cosmetic active ingredient from Lycopersicon esculentum (tomato) cultured stem cells. This product, besides its high content of antioxidant compounds, contained PC, effective in the protection of skin cells towards heavy metal toxicity. We have demonstrated that this new product preserves nuclear DNA integrity from heavy metal damages, by inducing genes responsible for DNA repair and protection, and neutralizes the effect of heavy metals on collagen degradation, by inhibiting collagenase expression and inducing the synthesis of new collagen. © 2011 Arterra Bioscience srl. ICS © 2011 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

  2. Unified explanation of chemical ordering, the Slater-Pauling rule, and half-metallicity in full Heusler compounds (United States)

    Faleev, Sergey V.; Ferrante, Yari; Jeong, Jaewoo; Samant, Mahesh G.; Jones, Barbara; Parkin, Stuart S. P.


    In the present work we developed an orbital coupling model for cubic full Heusler compounds that provides a unified set of rules that account for the chemical ordering, magnetic moment, and composition of the most promising candidates for half-metallicity. The origin and limitations of the rules are clearly described. To the best of our knowledge all of the several dozen half-metallic Heusler compounds known in the literature that follow the Mt=Nt-24 or Mt=Nt-28 generalized Slater-Pauling behavior satisfy the derived half-metallicity rule. Calculations performed by using density functional theory—performed for 259 compounds—confirm the validity of our model and derived rules for broad classes of Heusler compounds.

  3. Pioneering Metal-Free Oxidative Coupling Strategy of Aromatic Compounds Using Hypervalent Iodine Reagents. (United States)

    Kita, Yasuyuki; Dohi, Toshifumi


    We started our hypervalent iodine research about 30 years ago in the mid-1980s. We soon successfully developed the single-electron-transfer oxidation ability of a hypervalent iodine reagent, specifically, phenyliodine(III) bis(trifluoroacetate) (PIFA), toward aromatic rings of phenyl ethers for forming aromatic cation radicals. This was one of the exciting and unexpected events in our research studies so far, and the discovery was reported in 1991. It also led to the next challenge, developing the metal-free oxidative couplings for C-H functionalizations and direct couplings between the C-H bonds of valuable aromatic compounds in organic synthesis. In order to realize the effective oxidative coupling, pioneering new aromatic ring activations was essential and several useful methodologies have been found for oxidizable arenes. The achievements regarding this objective obtained in our continuous research are herein summarized with classification of the aromatic ring activation strategies.

  4. Structures of rare earth-transition metal rich compounds derived from CaCu5 type

    Institute of Scientific and Technical Information of China (English)


    The properties of materials have a close connect ion to their crystal structures. Rare earth (R)-transition metal (T) rich compo und are the focus of investigation in the search for new hard magnetic materials . As the basis for the study of stabilized effect of the third component on the fo rmation of RT5 derivative and its influence of the occupied sites on magnetic properties, in this paper, the possible derivative compounds based on the RT5 primitive unit cell of the CaCu5 structure type formed through the ordered or disordered substitution of dumbbell pair 2T atoms for the R atoms at some sit es, and the structural relationship between the derivatives and the prototype ar e summarized.

  5. Structural and property studies on metal-organic compounds with 3-D supramolecular network (United States)

    Zhang, Qi-Ying; Ma, Ke-Fang; Xiao, Hong-Ping; Li, Xin-Hua; Shi, Qian


    Two carboxylato-bridged allomeric compounds, {[Cu2(dbsa)2(hmt) (H2O)4]1/2·2H2O}n (1), {[Ni(dbsa)(H2O)2]1/2[Ni(dbsa)(hmt)(H2O)2]1/2·2H2O}n (2) (H2dbsa=meso-2,3-dibromosuccinic acid, hmt=hexamethylenetetramine) have been synthesized and characterized by X-ray structral analyses. The metal ions have two kinds of coordination fashion in one unit, and bridged by carboxylate and hmt ligands along with weak interactions existing in the solid structure, forming a 3-D supramolecular network. Variable-temperature magnetic property studies reveal the existence of antiferromagnetic interactions in 1 and 2 with g=2.2, J1=-3.5 cm-1, J2=-2.8 cm-1 for 1, and g=2.1, J=-3.5 cm-1 for 2.

  6. EDITORIAL: New materials with high spin polarization: half-metallic Heusler compounds (United States)

    Felser, Claudia; Hillebrands, Burkard


    The development of magnetic Heusler compounds, specifically designed as materials for spintronic applications, has made tremendous progress in the very recent past [1-21]. Heusler compounds can be made as half-metals, showing a high spin polarization of the conduction electrons of up to 100% [1]. These materials are exceptionally well suited for applications in magnetic tunnel junctions acting, for example, as sensors for magnetic fields. The tunnelling magneto-resistance (TMR) effect is the relative change in the electrical resistance upon application of a small magnetic field. Tunnel junctions with a TMR effect of 580% at 4 K were reported by the group of Miyazaki and Ando [1], consisting of two Co2MnSi Heusler electrodes. High Curie temperatures were found in Co2 Heusler compounds with values up to 1120 K in Co2FeSi [2]. The latest results are for a TMR device made from the Co2FeAl0.5Si0.5 Heusler compound and working at room temperature with a TMR effect of 174% [3]. The first significant magneto-resistance effect was discovered in Co2Cr0.6Fe0.4Al (CCFA) in Mainz [4]. With the classical Heusler compound CCFA as one electrode, the record TMR effect at 4 K is 240% [5]. Positive and negative TMR values at room temperature utilizing magnetic tunnel junctions with one Heusler compound electrode render magnetic logic possible [6]. Research efforts exist, in particular, in Japan and in Germany. The status of research as of winter 2005 was compiled in a recent special volume of Journal of Physics D: Applied Physics [7-20]. Since then specific progress has been made on the issues of (i) new advanced Heusler materials, (ii) advanced characterization, and (iii) advanced devices using the new materials. In Germany, the Mainz and Kaiserslautern based Research Unit 559 `New Materials with High Spin Polarization', funded since 2004 by the Deutsche Forschungsgemeinschaft, is a basic science approach to Heusler compounds, and it addresses the first two topics in particular

  7. Application of humic compounds for remediation of soils contaminated with heavy metals: the benefits and risks (United States)

    Motuzova, Galina; Barsova, Natalia; Stepanov, Andrey; Kiseleva, Violetta; Kolchanova, Ksenia; Starkova, Irina; Karpukhin, Mikhail


    found to contain only 3-9% of copper. The content of free Cu2+ ions in the sample extract was negligible. The samples used for field experiments were tested in laboratory to estimate their sorption capacity for Cu. For this purpose, 300 g of substrate (loam and mixed organic substrate) with addition of water (control) and humic preparation (same dose as in the field experiment) were kept in the laboratory for 1 week. Soil samples were then dried and brought into equilibrium with the solution of copper sulfate at concentration of 50 mg/l. The concentration of copper in the solution in equilibrium with HC was 2.5-4 times higher than in the control variant; absorption of copper by solid phase decreased by 5-6%. Results of the laboratory study were in good agreement with the results of the field experiment. Addition of HC increased the content of soluble organic matter and copper complexation by an order of magnitude and thus reduced the activity of copper ions in the liquid phase that was treated as a possible remediation effect of the humic compound for plants and biota. However the increased total metal content mainly in a migration-capable form (negatively charged complexes with organic matter) may increase the risk of contaminating ground waters with heavy metals. Therefore, application of the artificial humic compounds for remediation of soils contaminated with heavy metals requires monitoring and further development of means to prevent their migration.

  8. Silicic Large Igneous Provinces

    Institute of Scientific and Technical Information of China (English)

    Scott Bryan


    @@ Large Igneous Provinces (LIPs) are the end-product of huge additions of magma to the continental crust both at the surface and at depth. Since the first categorisation of LIPs by Coffin & Eldholm (1994), it has been recognised that LIPs are more varied inform, age and character, and this includes the recognition of Silicic LIPs. Silicic LIPs are the largest accumulations of primary volcaniclastic rocks at the Earth's surface with areal extents >0.1 Mkm2 and extrusive and subvolcanic intrusive volumes >0.25 Mkm3. The Late Palaeozoic to Cenozoic Silicic LIP events are the best recognised and are similar in terms of their dimension, crustal setting, volcanic architecture and geochemistry.

  9. [Evaluation of compounding EDTA and citric acid on remediation of heavy metals contaminated soil]. (United States)

    Yin, Xue; Chen, Jia-Jun; Cai, Wen-Min


    As commonly used eluents, Na2EDTA (EDTA) and citric acid (CA) have been widely applied in remediation of soil contaminated by heavy metals. In order to evaluate the removal of arsenic, cadmium, copper, and lead in the contaminated soil collected in a chemical plant by compounding EDTA and CA, a series of stirring experiments were conducted. Furthermore, the changes in speciation distribution of heavy metals before and after washing were studied. The results showed that, adopting the optimal molar ratio of EDTA/CA (1:1), when the pH of the solution was 3, the stirring time was 30 min, the stirring rate was 150 r x min(-1) and the L/S was 5:1, the removal rates of arsenic, cadmium, copper and lead could reach 11.72%, 43.39%, 24.36% and 27.17%, respectively. And it was found that after washing, for arsenic and copper, the content of acid dissolved fraction rose which increased the percentage of available contents. Fe-Mn oxide fraction mainly contributed to the removal of copper. As for cadmium, the percentages of acid dissolved fraction, Fe-Mn oxide fraction and organic fraction also decreased. In practical projects, speciation changes would pose certain environmental risk after soil washing, which should be taken into consideration.

  10. Electronic Structures of Square Planar Coordinated Transition Metal Ions in Compounds with Gillespite Structure

    Institute of Scientific and Technical Information of China (English)



    Electronic structures of square planar coordinated transition metal ions in BaCuSi4O10 and CaCrSi4O10 are investigated using the ligand-field theory(LFT),angular overlap model(AOM) and iterative extended Hueckel molecular orbital theory(IET).The electronic energy levels of the natural mineral dioptase are also investigated,in which the Cu2+ ions occupy the sites of pseudo D4h symmetry,Both LFT and AOM predict that the crystal-field levels of transition metal ions in these compounds follow such an order that E(2B1g)

  11. Adsorptive removal of nitrogen-containing compounds from fuel by metal-organic frameworks

    Institute of Scientific and Technical Information of China (English)

    Zhaoyang; Wang; Zhiguo; Sun; Linghao; Kong; Gang; Li


    The adsorptive denitrogenation from fuels over three metal-organic frameworks(MIL-96(Al),MIL-53(Al)and MIL-101(Cr))was studied by batch adsorption experiments.Four nitrogen-containing compounds(NCCs)pyridine,pyrrole,quinoline and indole were used as model NCCs in fuels to study the adsorption mechanism.The physicochemical properties of the adsorbents were characterized by XRD,N2physical adsorption,FT-IR spectrum and Hammett indicator method.The metal-organic frameworks(MOFs),especially the MIL-101(Cr)containing Lewis acid sites as well as high specific surface area,can adsorb large quantities of NCCs from fuels.In addition,the adsorptive capacity over MIL-101(Cr)will be different for NCCs with different basicity.The stronger basicity of the NCC is,the more it can be absorbed over MIL-101(Cr).Furthermore,pore size and shape also affect the adsorption capacity for a given adsorbate,which can be proved by the adsorption over MIL-53(Al)and MIL-96(Al).The pseudo-second-order kinetic model and Langmuir equation can be used to describe kinetics and thermodynamics of the adsorption process,respectively.Finally,the regeneration of the used adsorbent has been conducted successfully by just washing it with ethanol.

  12. Adsorption on Mesoporous Metal-Organic Frameworks in Solution: Aromatic and Heterocyclic Compounds. (United States)

    Samokhvalov, Alexander


    Adsorption and desorption play major roles in separations, purification of water, waste streams, liquid fuels, catalysis, biomedicine and chromatography. Mesoporous metal-organic frameworks (MOFs) with pore sizes 2-50 nm are particularly suitable for adsorption of organic compounds in solution. Tens of thousands of aromatic and heterocyclic compounds are major components of liquid fuels, feedstock for industrial synthesis, solvents, dyestuffs, agricultural chemicals, medicinal drugs, food additives, and so forth. This Review provides a systematization and analysis of studies on adsorption/desorption on mesoporous MOFs in solution and their underlying chemical mechanisms. The (in)stability of mesoporous MOFs in water is critically discussed. Adsorption capacity and selectivity are covered for organic dyes, medicinal drugs, major components of liquid fuels, and miscellaneous industrial chemicals. Ionic interactions, Brønsted acid-base interactions, hydrogen bonding, coordination bonding, π-π interactions, and non-specific interactions are covered amongst adsorption mechanisms. The effects of post-synthetic modifications of mesoporous MOFs on their stability, adsorption capacity, selectivity, and mechanisms of adsorption and desorption are analyzed. To encourage research in this quickly growing field, we identify "niches" for which no application-oriented and/or mechanistic studies were reported. Perspectives and limitations of a wide use of mesoporous MOFs as industrial sorbents are discussed.

  13. Study of Recycled and Virgin Compounded Metal Injection Moulded Feedstock for Stainless Steel 630 (United States)

    Manonukul, Anchalee; Likityingwara, Warakij; Rungkiatnawin, Phataraporn; Muenya, Nattapol; Amoranan, Suttha; Kittinantapol, Witoo; Surapunt, Suphachai

    Fine rounded powders preferable for metal injection moulding (MIM) are expensive. This forces MIM makers to recycle green scraps, for example, the runner system and defected green parts. This is particularly necessary for injection moulded small parts where parts are only a small portion of the injection short size. There is very little published data, although recycling feedstock has been practise throughout the industry. This work aims at investigating the effects of recycled stainless steel 630 feedstock content on the density, mechanical properties, dimensional changes and microstructure. Five batches of compounded virgin and recycled feedstock were studies from 0% to 100% recycled feedstock with the increment of 25%. Homogenously compounded feedstock was injected using the same injection condition. Subsequently, green parts were debinded and sintered at 1325°C for 2 hours in argon atmosphere. The results suggest that the green density increases linearly with increasing percentage of recycled feedstock because the polymeric binder was broken down during previous process. However, the sintered density remains nominally constant. As a result, the mechanical properties and microstructure of sintered parts are independent of recycled feedstock content. However, the volumetric and linear shrinkage decreases linearly with the increase in percentage of recycled feedstock. The difference in shrinkage is vital to dimensional control during commercial production. For example, only 4.5% of recycled feedstock can be added to virgin feedstock if a tolerance of ±0.3 mm is required for a 25 mm MIM part.

  14. The heavy metal ions (Cu2+, Zn2+, Cd+) toxic compounds influence on triticale plants growth (United States)

    Brezoczki, V. M.; Filip, G. M.


    The presence of the heavy metals toxic compounds (CuSO4 · 5H2O, ZnSO4 · 7H2O and 3CdSO4·8H2O) in water and soil can be observed by their negative effects on the germination and growth process for different vegetable (barley, oat, maize) who are used for human and animal consumption. This paper it aims the determination of germination and growth inhibition negative effects for triticale plants in the heavy metals ions presence by ecotoxicological laboratory tests. The triticale plants was chosen for their different characteristics to the other grasses respectively: a very good resistance for a wide range of diseases, an accelerated growth and a very good tolerance for aluminum ions presents in acid soils. The determinations were conducted step by step, first, we put the triticale grains in contact with the heavy metal solutions with different concentration then for 3 days we noticed the triticale germination inhibition effects and finally we noticed the growth inhibition process for triticale plants respectively in 7th and 9th day from the start of the experiment. At the end of the tests we can conclude that the triticale roots have a very great sensibility to a CuSO4 solutions compared to the effects for their stalks. A positive effect for triticale stalks we can see for low CuSO4 solution concentrations thus for 5 mg Cu/l the growth is 19,44%. A positive effect for triticale roots it can see for low ZnSO4 solution concentrations so for 5 - 15 mg Zn/l the growth is 24,4%. In the presence of the CdSO4 solution all the processes are inhibited (germination and growth for triticale plants) even for a low concentrations for this toxic.

  15. Serum heavy metals and hemoglobin related compounds in Saudi Arabia firefighters

    Directory of Open Access Journals (Sweden)

    Al-Malki Abdulrahman L


    Full Text Available Abstract Background Firefighters are frequently exposed to significant concentrations of hazardous materials including heavy metals, aldehydes, hydrogen chloride, dichlorofluoromethane and some particulates. Many of these materials have been implicated in the triggering of several diseases. The aim of the present study is to investigate the effect of fire smoke exposure on serum heavy metals and possible affection on iron functions compounds (total iron binding capacity, transferrin saturation percent, ferritin, unsaturated iron-binding capacity blood hemoglobin and carboxyhemoglobin,. Subjects and methods Two groups of male firefighter volunteers were included; the first included 28 firefighters from Jeddah city, while the second included 21 firefighters from Yanbu city with an overall age rang of 20–48 years. An additional group of 23 male non-firefighters volunteered from both cities as normal control subjects. Blood samples were collected from all volunteer subjects and investigated for relevant parameters. Results The results obtained showed that there were no statistically significant changes in the levels of serum heavy metals in firefighters as compared to normal control subjects. Blood carboxyhemoglobin and serum ferritin were statistically increased in Jeddah firefighters, (p Conclusion Such results might point to the need for more health protective and prophylactic measures to avoid such hazardous health effects (elevated Blood carboxyhemoglobin and serum ferritin and decreased serum TIBC and UIBC that might endanger firefighters working under dangerous conditions. Firefighters must be under regular medical follow-up through standard timetabled medical laboratory investigations to allow for early detection of any serum biochemical or blood hematological changes.

  16. First principles study on half-metallic properties of Heusler compounds Ti2VZ (Z=Al, Ga, and In) (United States)

    Galehgirian, S.; Ahmadian, F.


    First principles calculations using the self-consistent full-potential linearized augmented plane wave (FPLAPW) method in the framework of density functional theory (DFT) were performed to study the electronic structures and magnetic properties of new full-Heusler compounds Ti2VZ (Z=Al, Ga, and In). Electronic structure calculations showed that Ti2VZ (Z=Al, Ga, and In) compounds in AlCu2Mn-type are conventional ferrimagnets. The Ti2VAl, Ti2VGa, and Ti2VIn compounds in the CuHg2Ti-type structure have half-metallic characteristics with a respective majority band gap of 0.52, 0.51, and 0.59 eV at the equilibrium lattice parameter. The origin of half-metallicity in these compounds was also discussed. The total magnetic moments of Ti2VZ (Z=Al, Ga, and In) compounds in the CuHg2Ti-type structures were 2 μB per formula unit which were in agreement with Slater-Pauling rule (Mtot=18-Ztot). The Ti2VAl, Ti2VGa, and Ti2VIn compounds in the CuHg2Ti-type structure respectively showed half-metallic characteristics at lattice constants ranges of 6.12-7.17 Å, 5.99-7.12 Å, and 6.31-7.06 Å, indicating the lattice distortion did not affect the half-metallic properties of these compounds which makes them interesting materials in the spintronics field.

  17. Bioavailability of heavy metals in soil: impact on microbial biodegradation of organic compounds and possible improvement strategies. (United States)

    Olaniran, Ademola O; Balgobind, Adhika; Pillay, Balakrishna


    Co-contamination of the environment with toxic chlorinated organic and heavy metal pollutants is one of the major problems facing industrialized nations today. Heavy metals may inhibit biodegradation of chlorinated organics by interacting with enzymes directly involved in biodegradation or those involved in general metabolism. Predictions of metal toxicity effects on organic pollutant biodegradation in co-contaminated soil and water environments is difficult since heavy metals may be present in a variety of chemical and physical forms. Recent advances in bioremediation of co-contaminated environments have focussed on the use of metal-resistant bacteria (cell and gene bioaugmentation), treatment amendments, clay minerals and chelating agents to reduce bioavailable heavy metal concentrations. Phytoremediation has also shown promise as an emerging alternative clean-up technology for co-contaminated environments. However, despite various investigations, in both aerobic and anaerobic systems, demonstrating that metal toxicity hampers the biodegradation of the organic component, a paucity of information exists in this area of research. Therefore, in this review, we discuss the problems associated with the degradation of chlorinated organics in co-contaminated environments, owing to metal toxicity and shed light on possible improvement strategies for effective bioremediation of sites co-contaminated with chlorinated organic compounds and heavy metals.

  18. Bioavailability of Heavy Metals in Soil: Impact on Microbial Biodegradation of Organic Compounds and Possible Improvement Strategies

    Directory of Open Access Journals (Sweden)

    Balakrishna Pillay


    Full Text Available Co-contamination of the environment with toxic chlorinated organic and heavy metal pollutants is one of the major problems facing industrialized nations today. Heavy metals may inhibit biodegradation of chlorinated organics by interacting with enzymes directly involved in biodegradation or those involved in general metabolism. Predictions of metal toxicity effects on organic pollutant biodegradation in co-contaminated soil and water environments is difficult since heavy metals may be present in a variety of chemical and physical forms. Recent advances in bioremediation of co-contaminated environments have focussed on the use of metal-resistant bacteria (cell and gene bioaugmentation, treatment amendments, clay minerals and chelating agents to reduce bioavailable heavy metal concentrations. Phytoremediation has also shown promise as an emerging alternative clean-up technology for co-contaminated environments. However, despite various investigations, in both aerobic and anaerobic systems, demonstrating that metal toxicity hampers the biodegradation of the organic component, a paucity of information exists in this area of research. Therefore, in this review, we discuss the problems associated with the degradation of chlorinated organics in co-contaminated environments, owing to metal toxicity and shed light on possible improvement strategies for effective bioremediation of sites co-contaminated with chlorinated organic compounds and heavy metals.

  19. Semivolatile organic compounds, organochlorine pesticides and heavy metals in sediments and risk assessment in Huaihe River of China

    Institute of Scientific and Technical Information of China (English)


    The concentrations of semivolatile organic compounds, organochlorine pesticides and heavy metals in sediments from Jiangsu reach of Huaihe River, China, were presented. The organic compounds were extracted by acetone: n-hexane using a Soxhlet apparatus and concentrations were performed using HP6890 gas chromatography coupled by FID and ECD detector. The total contents of 8 heavy metals by inductively coupled plasma atomic emission spectrometry or cold-vapor/atomic absorption spectrometry were developed. 30 semivolatile organic compounds were detected, including substituted benzenes, phenols, phthalates and polycyclic aromatic hydrocarbons, from 0.01 to 3.01 mg/kg. 16 organochlorine pesticides were almost detected and from 0.010 to 2.339 μg/kg.Concentrations of major metals were 50 mg/kg or less, mean level of mercury was only 0.055 mg/kg. Compared to sediment quality guidelines (SQGs), concentrations of some semivolatile organic compounds were high enough to cause possible toxic effects to living resources. The organochlorine pesticides presented relatively low, lower than threshold effect concentrations (TECs), harmful effects on sediment-dwelling organisms were not expected. Chromium posed probable toxic effects to the living resources, other heavy metals had no threat temporarily according to SQGs.

  20. Glutathione-dependent interaction of heavy metal compounds with multidrug resistance proteins MRP1 and MRP2

    NARCIS (Netherlands)

    Wortelboer, H.M.; Balvers, M.G.J.; Usta, M.; Bladeren, P.J. van; Cnubben, N.H.P.


    The interactions of three heavy metal-containing compounds, cisplatin (CDDP), arsenic trioxide (As2O3), and mercury dichloride (HgCl2), with the multidrug resistance transporters MRP1 and MRP2 and the involvement of glutathione (GSH)-related processes herein were investigated. In Madin-Darby canine

  1. Glutathione-dependent interaction of heavy metal compounds with multidrug resistance proteins MRP1 and MRP2

    NARCIS (Netherlands)

    Wortelboer, H.M.; Balvers, M.G.J.; Usta, M.; Bladeren, van P.J.; Cnubben, N.H.P.


    The interactions of three heavy metal-containing compounds, cisplatin (CDDP), arsenic trioxide (AS(2)O(3)), and mercury dichloride (HgCl2), with the multidrug resistance transporters MRP1 and MRP2 and the involvement of glutathione (GSH)-related processes herein were investigated. In Madin-Darby can

  2. New organic-inorganic hybrid compounds constructed from polyoxometalates and transition metal mixed-organic-ligand complexes. (United States)

    Hu, Yang-Yang; Zhang, Ting-Ting; Zhang, Xiao; Zhao, De-Chuan; Cui, Xiao-Bing; Huo, Qi-Sheng; Xu, Ji-Qing


    Five new organic-inorganic hybrid compounds based on different polyoxoanions [HxGeW12O40](n-) or [H3As2W18O62](3-) (x = 0, 2; n = 4, 2), namely [Cu3(2,2'-bpy)3(inic)(OH)(H2O)][GeW12O40]·1.5H2O (1), [Cu2(phen)2(μ2-Cl)2(inic)]2[H2GeW12O40]·2H2O (2), [Cu2(phen)2(μ2-Cl)Cl(nic)]2[H2GeW12O40] (3), [Cu2(2,2'-bpy)2(hnic)Cl]2[H2GeW12O40] (4), [Cu(phen)(inic)H2O][Cu2(phen)2(inic)2(H2O)][H3As2W18O62]·3H2O (5) (inic = isonicotinic acid, nic = nicotinic acid, hnic = 2-hydroxy-nicotinic acid, 2,2'-bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline), have been synthesized and characterized by IR, UV-Vis, XRD, cyclic voltammetric measurements and single crystal X-ray diffraction analysis. Single crystal X-ray analysis reveals that compound 1 is isomorphous and isostructural with a compound reported by us recently, the main difference between the two is the heteroatom of the polyoxoanions in the two compounds. Compound 2 is a supramolecular structure constructed from polyoxoanions and transition metal mixed-organic-ligand complexes. Compound 3 is a novel polyoxoanion bi-supported transition metal mixed-organic-ligand complex. Compound 4 is a 1-D chain structure constructed from polyoxoanions and transition metal mixed-organic-ligand complexes. The photodegradation properties of compounds 1-5 have been analyzed.

  3. Flexible metal-organic framework compounds: In situ studies for selective CO{sub 2} capture

    Energy Technology Data Exchange (ETDEWEB)

    Allen, A.J., E-mail: [Material Measurement Laboratory, National Institute of Standards and Technology (NIST), Gaithersburg, MD 20899-8520 (United States); Espinal, L.; Wong-Ng, W. [Material Measurement Laboratory, National Institute of Standards and Technology (NIST), Gaithersburg, MD 20899-8520 (United States); Queen, W.L. [NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (United States); The Molecular Foundry, Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA 94720 (United States); Brown, C.M. [NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (United States); Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE 19716 (United States); Kline, S.R. [NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (United States); Kauffman, K.L. [National Energy Technology Laboratory (NETL), US Department of Energy, Pittsburgh, PA 15236 (United States); Culp, J.T. [National Energy Technology Laboratory (NETL), US Department of Energy, Pittsburgh, PA 15236 (United States); URS Corporation, South Park, PA 15219 (United States); Matranga, C. [National Energy Technology Laboratory (NETL), US Department of Energy, Pittsburgh, PA 15236 (United States)


    Results are presented that explore the dynamic structural changes occurring in two highly flexible nanocrystalline metal-organic framework (MOF) compounds during the adsorption and desorption of pure gases and binary mixtures. The Ni(1,2-bis(4-pyridyl)ethylene)[Ni(CN){sub 4}] and catena-bis(dibenzoylmethanato)-(4,4′-bipyridyl)nickel(II) chosen for this study are 3-D and 1-D porous coordination polymers (PCP) with a similar gate opening pressure response for CO{sub 2} isotherms at 303 K, but with differing degrees of flexibility for structural change to accommodate guest molecules. As such, they serve as a potential model system for evaluating the complex kinetics associated with dynamic structure changes occurring in response to gas adsorption in flexible MOF systems. Insights into the crystallographic changes occurring as the MOF pore structure expands and contracts in response to interactions with CO{sub 2}, N{sub 2}, and CO{sub 2}/N{sub 2} mixtures have been obtained from in situ small-angle neutron scattering and neutron diffraction, combined with ex situ X-ray diffraction structure measurements. The role of structure in carbon capture functionality is discussed with reference to the ongoing characterization challenges and a possible materials-by-design approach. - Graphical abstract: We present in situ small-angle neutron scattering results for two flexible metal-organic frameworks (MOFs). The figure shows that for one (NiBpene, high CO{sub 2} adsorption) the intensity of the Bragg peak for the expandable d-spacing most associated with CO{sub 2} adsorption varies approximately with the isotherm, while for the other (NiDBM-Bpy, high CO{sub 2} selectivity) the d-spacing, itself, varies with the isotherm. The cartoons show the proposed modes of structural change. - Highlights: • Dynamic structures of two flexible MOF CO{sub 2} sorbent compounds are compared in situ. • These porous solid sorbents serve as models for pure & dual gas adsorption. • Different

  4. A DFT study of volatile organic compounds adsorption on transition metal deposited graphene (United States)

    Kunaseth, Manaschai; Poldorn, Preeyaporn; Junkeaw, Anchalee; Meeprasert, Jittima; Rungnim, Chompoonut; Namuangruk, Supawadee; Kungwan, Nawee; Inntam, Chan; Jungsuttiwong, Siriporn


    Recently, elevated global emission of volatile organic compounds (VOCs) was associated to the acceleration and increasing severity of climate change worldwide. In this work, we investigated the performance of VOCs removal via modified carbon-based adsorbent using density functional theory. Here, four transition metals (TMs) including Pd, Pt, Ag, and Au were deposited onto single-vacancy defective graphene (SDG) surface to increase the adsorption efficiency. Five prototypical VOCs including benzene, furan, pyrrole, pyridine, and thiophene were used to study the adsorption capability of metal-deposited graphene adsorbent. Calculation results revealed that Pd, Pt, Au, and Ag atoms and nanoclusters bind strongly onto the SDG surface. In this study, benzene, furan and pyrrole bind in the π-interaction mode using delocalized π-electron in aromatic ring, while pyridine and thiophene favor X- interaction mode, donating lone pair electron from heteroatom. In terms of adsorption, pyridine VOC adsorption strengths to the TM-cluster doped SDG surfaces are Pt4 (-2.11 eV) > Pd4 (-2.05 eV) > Ag4 (-1.53 eV) > Au4 (-1.87 eV). Our findings indicate that TM-doped SDG is a suitable adsorbent material for VOC removal. In addition, partial density of states analysis suggests that benzene, furan, and pyrrole interactions with TM cluster are based on p-orbitals of carbon atoms, while pyridine and thiophene interactions are facilitated by hybridized sp2-orbitals of heteroatoms. This work provides a key insight into the fundamentals of VOCs adsorption on carbon-based adsorbent.

  5. NMR shielding calculations across the periodic table: diamagnetic uranium compounds. 2. Ligand and metal NMR. (United States)

    Schreckenbach, Georg


    In this and a previous article (J. Phys. Chem. A 2000, 104, 8244), the range of application for relativistic density functional theory (DFT) is extended to the calculation of nuclear magnetic resonance (NMR) shieldings and chemical shifts in diamagnetic actinide compounds. Two relativistic DFT methods are used, ZORA ("zeroth-order regular approximation") and the quasirelativistic (QR) method. In the given second paper, NMR shieldings and chemical shifts are calculated and discussed for a wide range of compounds. The molecules studied comprise uranyl complexes, [UO(2)L(n)](+/-)(q); UF(6); inorganic UF(6) derivatives, UF(6-n)Cl(n), n = 0-6; and organometallic UF(6) derivatives, UF(6-n)(OCH(3))(n), n = 0-5. Uranyl complexes include [UO(2)F(4)](2-), [UO(2)Cl(4)](2-), [UO(2)(OH)(4)](2-), [UO(2)(CO(3))(3)](4-), and [UO(2)(H(2)O)(5)](2+). For the ligand NMR, moderate (e.g., (19)F NMR chemical shifts in UF(6-n)Cl(n)) to excellent agreement [e.g., (19)F chemical shift tensor in UF(6) or (1)H NMR in UF(6-n)(OCH(3))(n)] has been found between theory and experiment. The methods have been used to calculate the experimentally unknown (235)U NMR chemical shifts. A large chemical shift range of at least 21,000 ppm has been predicted for the (235)U nucleus. ZORA spin-orbit appears to be the most accurate method for predicting actinide metal chemical shifts. Trends in the (235)U NMR chemical shifts of UF(6-n)L(n) molecules are analyzed and explained in terms of the calculated electronic structure. It is argued that the energy separation and interaction between occupied and virtual orbitals with f-character are the determining factors.

  6. Skyrmion crystal and topological Hall effect in B20-type transition-metal compounds (United States)

    Onose, Yoshinori


    Topological objects in solids such as domain walls and vortices have been attracting much attention for long. Among them the spin texture called skyrmion is an unusual topological object, in which the spins point in all the directions wrapping a sphere. The skyrmion hosts finite spin chirality, and therefore is anticipated to induce novel electromagnetic phenomena such as topological Hall effect. In B20-type transition metal compounds MnSi and Fe 1-x Co x Si, the crystallization of skyrmions was observed by the neutron diffraction studies. , . Recently, we have observed the real-space images of skyrmion crystal in thin films of related compounds (Fe 0.5 Co 0.5 Si and FeGe) using Lorentz transmission electron spectroscopy., Nature material, inpress.} We have observed the hexagonal arrangement of skyrmions including the topological defects (chiral domains and dislocations) under the magnetic field normal to the films, and found that the two dimensional skyrmion crystal phase is fairly stabilized by the thin film form of the samples. We have also studied the topological Hall effect caused by the spin chirality of the skyrmion crystal in a related material MnGe. In terms of the Hall measurement, they have shown the real space nature of the fictitious magnetic field caused by the magnetic configuration of the skyrmion crystal, in contrast with the momentum-space fictitious field in another spin chirality system, Nd 2 Mo 2 O7 . This work was done in collaboration with X. Z. Yu, N. Kanazawa, J. H. Park, J. H. Han, K. Kimoto, W. Z. Zhang, S. Ishiwata, Y. Matsui, N. Nagaosa, and Y. Tokura. S. Mühlbauer et al. Science 323, 915 (2009).}

  7. Effects of heavy metals and nitroaromatic compounds on horseradish glutathione S-transferase and peroxidase. (United States)

    Nepovím, Ales; Podlipná, Radka; Soudek, Petr; Schröder, Peter; Vanek, Tomás


    Glutathione S-transferase (GST) and peroxidase (POX) activities have a direct relation to the effect of stress on plant metabolism. Changes in the activities of the enzymes were therefore studied. Horseradish hairy roots were treated by selected bivalent ions of heavy metals (HMs) and nitroaromatic compounds (NACs). We have shown differences in GST activity when assayed with substrates 1-chloro-2,4-dinitrobenzene (CDNB) and 1,2-dichloro-4-nitrobenzene (DCNB). The conjugation of DCNB catalysed by GST was inhibited in all roots treated with HMs as compared to non-treated roots, whereas NACs caused induction of the activity in dependence on the exposition time and concentration of compounds. The conjugation of CDNB by GST was not affected to the same extent. The increase of GST activity was determined in cultures treated by nickel (0.1 mM) and diaminonitrotoluenes (DANTs, 0.1 mM) for 6 h, whereas the roots treated by 2,4,6-trinitrotoluene (TNT), 4-amino-2,6-dinitrotoluene (ADNT) and dinitrotoluene (DNT, 1.0 mM) needed 27 h treatment to induce the activity. The POX activity of cultures treated by HMs was inhibited to 17-35% in comparison to non-treated cultures. The POX activity of roots treated by TNT (0.1 and 1.0 mM) for 6 and 27 h and by ADNT (0.1 and 1.0 mM) for 6 h was inhibited. A partial increase of POX activity was measured in roots treated by all NACs for 27 h. The content of oxidized glutathione (GSSG) and reduced glutathione (GSH) in the roots differed significantly. It was followed as a symptom of the stress reaction of the plant metabolism to the effect of NACs and HMs.

  8. Solid-phase extraction with metal-organic frameworks for the analysis of chiral compounds. (United States)

    Tang, Bo; Zhang, Jun-Hui; Zi, Min; Chen, Xue-Xian; Yuan, Li-Ming


    Metal-organic frameworks (MOFs) are excellent porous materials with nanoscale cavities and high surface areas, which make them promising as novel adsorbents in solid-phase extraction (SPE). In this article we report a new application of the chiral MOF [Zn2 (D-Cam)2 (4,4'-bpy)]n in SPE used for the measurement of the enantiomeric excess (ee) of (±)-1,1'-bi-2-naphthol. Several important experimental parameters that may influence the extraction efficiency were investigated and optimized. Under the optimum conditions, a good linearity (R(2)  > 0.999) was found between the ee value and the reciprocal of the peak areas. When compared with the actual ee measured using chiral HPLC, the SPE-based assay also showed good accuracy and precision. The results showed that SPE based on chiral MOFs as adsorbents is a simple and effective method for the determination of the ee values of chiral compounds. © 2016 Wiley Periodicals, Inc.

  9. Spiral magnetic order and pressure-induced superconductivity in transition metal compounds (United States)

    Wang, Yishu; Feng, Yejun; Cheng, J.-G.; Wu, W.; Luo, J. L.; Rosenbaum, T. F.


    Magnetic and superconducting ground states can compete, cooperate and coexist. MnP provides a compelling and potentially generalizable example of a material where superconductivity and magnetism may be intertwined. Using a synchrotron-based non-resonant X-ray magnetic diffraction technique, we reveal a spiral spin order in MnP and trace its pressure evolution towards superconducting order via measurements in a diamond anvil cell. Judging from the magnetostriction, ordered moments vanish at the quantum phase transition as pressure increases the electron kinetic energy. Spins remain local in the disordered phase, and the promotion of superconductivity is likely to emerge from an enhanced coupling to residual spiral spin fluctuations and their concomitant suppression of phonon-mediated superconductivity. As the pitch of the spiral order varies across the 3d transition metal compounds in the MnP family, the magnetic ground state switches between antiferromagnet and ferromagnet, providing an additional tuning parameter in probing spin-fluctuation-induced superconductivity.

  10. Spiral magnetic order and pressure-induced superconductivity in transition metal compounds (United States)

    Wang, Yishu; Feng, Yejun; Cheng, J.-G.; Wu, W.; Luo, J. L.; Rosenbaum, T. F.


    Magnetic and superconducting ground states can compete, cooperate and coexist. MnP provides a compelling and potentially generalizable example of a material where superconductivity and magnetism may be intertwined. Using a synchrotron-based non-resonant X-ray magnetic diffraction technique, we reveal a spiral spin order in MnP and trace its pressure evolution towards superconducting order via measurements in a diamond anvil cell. Judging from the magnetostriction, ordered moments vanish at the quantum phase transition as pressure increases the electron kinetic energy. Spins remain local in the disordered phase, and the promotion of superconductivity is likely to emerge from an enhanced coupling to residual spiral spin fluctuations and their concomitant suppression of phonon-mediated superconductivity. As the pitch of the spiral order varies across the 3d transition metal compounds in the MnP family, the magnetic ground state switches between antiferromagnet and ferromagnet, providing an additional tuning parameter in probing spin-fluctuation-induced superconductivity. PMID:27708255

  11. Silicates in Alien Asteroids (United States)


    This plot of data from NASA's Spitzer Space Telescopes shows that asteroid dust around a dead 'white dwarf' star contains silicates a common mineral on Earth. The data were taken primarily by Spitzer's infrared spectrograph, an instrument that breaks light apart into its basic constituents. The yellow dots show averaged data from the spectrograph, while the orange triangles show older data from Spitzer's infrared array camera. The white dwarf is called GD 40.

  12. Silicates in Alien Asteroids (United States)


    This plot of data from NASA's Spitzer Space Telescopes shows that asteroid dust around a dead 'white dwarf' star contains silicates a common mineral on Earth. The data were taken primarily by Spitzer's infrared spectrograph, an instrument that breaks light apart into its basic constituents. The yellow dots show averaged data from the spectrograph, while the orange triangles show older data from Spitzer's infrared array camera. The white dwarf is called GD 40.

  13. Thermochemistry of Silicates (United States)

    Costa, Gustavo; Jacobson, Nathan


    The thermodynamic properties of vapor and condensed phases of silicates are crucial in many fields of science. These quantities address fundamental questions on the formation, stability, transformation, and physical properties of silicate minerals and silicate coating compositions. Here the thermodynamic activities of silica and other species in solid solution have been measured by the analysis of the corresponding high temperature vapors using Knudsen Effusion Mass Spectrometry (KEMS). In first set of experiments KEMS has been used to examine the volatility sequence of species (Fe, SiO, Mg, O2 and O) present in the vapor phase during heating of fosterite-rich olivine (Fo93Fa7) up to 2400 C and to measure the Fe, SiO and Mg activities in its solid solution. The data of fosterite-rich olivine are essential for thermochemical equilibrium models to predict the atmospheric and surface composition of hot, rocky exoplanets (Lava Planets). In the second set of experiments the measured thermodynamic activities of the silica in Y2O3-SiO2 and Yb2O3-SiO2 systems are used to assess their reactivity and degradation recession as environmental barrier coatings (EBCs) in combustion environments (e.g. non-moveable parts of gas turbine engine).

  14. Compound surface-plasmon-polariton waves guided by a thin metal layer sandwiched between a homogeneous isotropic dielectric material and a structurally chiral material

    CERN Document Server

    Chiadini, Francesco; Scaglione, Antonio; Lakhtakia, Akhlesh


    Multiple compound surface plasmon-polariton (SPP) waves can be guided by a structure consisting of a sufficiently thick layer of metal sandwiched between a homogeneous isotropic dielectric (HID) material and a dielectric structurally chiral material (SCM). The compound SPP waves are strongly bound to both metal/dielectric interfaces when the thickness of the metal layer is comparable to the skin depth but just to one of the two interfaces when the thickness is much larger. The compound SPP waves differ in phase speed, attenuation rate, and field profile, even though all are excitable at the same frequency. Some compound SPP waves are not greatly affected by the choice of the direction of propagation in the transverse plane but others are, depending on metal thickness. For fixed metal thickness, the number of compound SPP waves depends on the relative permittivity of the HID material, which can be useful for sensing applications.

  15. Diarylplatinum(II Compounds as Versatile Metallating Agents in the Synthesis of Cyclometallated Platinum Compounds with N-Donor Ligands

    Directory of Open Access Journals (Sweden)

    Margarita Crespo


    Full Text Available This review deals with the reactions of diarylplatinum(II complexes with N-donor ligands to produce a variety of cycloplatinated compounds including endo-five-, endo-seven-, endo-six- or exo-five-membered platinacycles. The observed reactions result from a series of oxidative addition/reductive elimination processes taking place at platinum(II/platinum(IV species and involving C–X (X = H, Cl, Br bond activation, arene elimination, and, in some cases, Caryl–Caryl bond formation.

  16. Biological Role of Cobalt(II), Copper(II) and Nickel(II) Metal Ions on the Antibacterial Properties of Some Nicotinoyl-Hydrazine Derived Compounds


    Chohan, Zahid H.; Sherazi, Syed K. A.


    Several cobalt(II), copper(II) and nickel(II) complexes of nicotinoylhydrazine-derived compounds were prepared and characterised by physical, spectral and analytical data. These compounds and their complexes have proven to be antibacterial. The screening data show the metal complexes to be more potential/bactericidal than the uncomplexed compounds against one or more bacterial species.

  17. New pathway for the formation of metallic cubic phase Ge-Sb-Te compounds induced by an electric current


    Yong-Jin Park; Ju-Young Cho; Min-Woo Jeong; Sekwon Na; Young-Chang Joo


    The novel discovery of a current-induced transition from insulator to metal in the crystalline phase of Ge2Sb2Te5 and GeSb4Te7 have been studied by means of a model using line-patterned samples. The resistivity of cubic phase Ge-Sb-Te compound was reduced by an electrical current (~1 MA/cm2), and the final resistivity was determined based on the stress current density, regardless of the initial resistivity and temperature, which indicates that the conductivity of Ge-Sb-Te compound can be modu...

  18. Carcinogenicity studies on fibres, metal compounds, and some other dusts in rats. (United States)

    Pott, F; Ziem, U; Reiffer, F J; Huth, F; Ernst, H; Mohr, U


    About 50 dusts were examined on their carcinogenicity in rats mainly after intraperitoneal injection and some after intratracheal instillation. In the i.p. test, very low doses between 0.05 and 0.5 mg asbestos led to tumour incidences of about 20 to 80%. Polyvinyl-pyridine-N-oxide prolonged the tumour latency after injection of actinolite. 60 mg attapulgite from three sources with short fibre lengths were not shown to be carcinogenic but an attapulgite sample with longer fibres had a moderate effect. Relatively thick rock and ceramic fibres (median greater than 1 micron) induced tumours, but slag and wollastonite fibres did not, probably because of their better solubility. Intratracheal instillations of glass microfibres (20 X 0.5 mg) led to lung tumours in 5 of 34 rats (0 in control). The carcinogenic potency of an inorganic fibre depends on its size and persistency, and possibly also on other properties, especially on the surface. Nickel powder, nickel oxide, nickel subsulfide and cadmium sulfide were all found to be carcinogenic in the two tests. Cadmium chloride and cadmium oxide could only be administered in very low doses because of their high acute toxicity. A high amount of magnetite (15 X 15 mg led to an unexpected lung tumour incidence of 69%. The i.p. test in rats proved to be very sensitive for detecting the carcinogenic potency of non-acute toxic natural and man-made mineral dusts as well as metal compounds. This means that, if a high dose of one of these dusts does not induce tumours in this test, no suspicion of carcinogenic potency can be substantiated.

  19. Polyphenolic compounds and essential oil analysis of selected species of the genus Thymus / Analýza fenolových zložiek a analýza silice vybraných druhov rodu Thymus

    Directory of Open Access Journals (Sweden)

    Kameníková M.


    Full Text Available Predložena praca bola zamerana na stanovenie obsahu vybranych fenolovych zlučenin (celkove fenoly, triesloviny, flavonoidy a antokyany troch roznych druhov rodu Thymus (T. pulegioides, T. pannonicus, T. praecox s rozdielnym povodom (Českomoravska vrchovina, Křivoklat a Považsky Inovec. Na stanovenie tychto zložiek boli využite spektrofotometricke metody Europskeho liekopisu, 8. vydanie. Zaroveň bol stanoveny aj obsah silice a bola vykonana analyza jej zložiek. Obsah celkovych polyfenolov bol stanoveny spektrofotometrickou metodou s využitim Folin-Ciocalteovho činidla. Obsah kolisal od 3.87 % do 8,86 %. Obsah trieslovin bol realizovany na zaklade predošleho stanovenia obsahu celkovych fenolov, a to adsorpciou trieslovin na kožny prašok. Ich obsah sa pohyboval v rozmedzi 1,96 % do 5,65 %. Na stanovenie obsahu flavonoidov bola využita spektrofotometricka metoda s chloridom hlinitym. Obsah flavonoidov vyjadrenych ako luteolin-7-O-glukozid (λ = 392 nm kolisal od 0,59 % do 1,52 % a obsah flavonoidov vyjadrenych ako rutin (λ = 420 nm sa pohyboval v rozmedzi od 0,41 % do 1,12 %. Antokyany zaberaju v ramci fenolovych zložiek rodu Thymus len minimalny podiel. V našich vzorkach bol obsah antokyanov vyjadreny ako cyanidin-3- O-glukozid a kolisal od 0,02 % do 0,1 %. Na stanovenie obsahu silice bola využita metoda Europskeho liekopisu, 8.vydanie. Obsah silice sa pohyboval v rozmedzi od 0,2 % do 0,75 %. Na analyzu silice bola nasledne využita metoda plynovej chromatografie s hmotnostnou spektrometriou. Na zaklade tejto analyzy bola zistena pritomnosť troch chemotypov silice, a to tymoloveho, karvakroloveho a linalooloveho chemotypu. Vďaka variaciami chemickeho zloženia silice, bolo možne pozorovať vzťah medzi pritomnosťou určiteho chemotypu a povodom vzorky. Rozdiely v stanoveni obsahu flavonoidov nepreukazali žiadny vyrazny vzťah k lokalite povodu.

  20. Design, selection, and characterization of thioflavin-based intercalation compounds with metal chelating properties for application in Alzheimer's disease. (United States)

    Rodríguez-Rodríguez, Cristina; Sánchez de Groot, Natalia; Rimola, Albert; Alvarez-Larena, Angel; Lloveras, Vega; Vidal-Gancedo, José; Ventura, Salvador; Vendrell, Josep; Sodupe, Mariona; González-Duarte, Pilar


    Metal chelation is considered a rational therapeutic approach for interdicting Alzheimer's amyloid pathogenesis. At present, enhancing the targeting and efficacy of metal-ion chelating agents through ligand design is a main strategy in the development of the next generation of metal chelators. Inspired by the traditional dye Thioflavin-T, we have designed new multifunctional molecules that contain both amyloid binding and metal chelating properties. In silico techniques have enabled us to identify commercial compounds that enclose the designed molecular framework (M1), include potential antioxidant properties, facilitate the formation of iodine-labeled derivatives, and can be permeable through the blood-brain barrier. Iodination reactions of the selected compounds, 2-(2-hydroxyphenyl)benzoxazole (HBX), 2-(2-hydroxyphenyl)benzothiazole (HBT), and 2-(2-aminophenyl)-1H-benzimidazole (BM), have led to the corresponding iodinated derivatives HBXI, HBTI, and BMI, which have been characterized by X-ray diffraction. The chelating properties of the latter compounds toward Cu(II) and Zn(II) have been examined in the solid phase and in solution. The acidity constants of HBXI, HBTI, and BMI and the formation constants of the corresponding ML and ML2 complexes [M = Cu(II), Zn(II)] have been determined by UV-vis pH titrations. The calculated values for the overall formation constants for the ML2 complexes indicate the suitability of the HBXI, HBTI, and BMI ligands for sequestering Cu(II) and Zn(II) metal ions present in freshly prepared solutions of beta-amyloid (Abeta) peptide. This was confirmed by Abeta aggregation studies showing that these compounds are able to arrest the metal-promoted increase in amyloid fibril buildup. The fluorescence features of HBX, HBT, BM, and the corresponding iodinated derivatives, together with fluorescence microscopy studies on two types of pregrown fibrils, have shown that HBX and HBT compounds could behave as potential markers for the presence

  1. Heteroepitaxial growth of 3-5 semiconductor compounds by metal-organic chemical vapor deposition for device applications (United States)

    Collis, Ward J.; Abul-Fadl, Ali


    The purpose of this research is to design, install and operate a metal-organic chemical vapor deposition system which is to be used for the epitaxial growth of 3-5 semiconductor binary compounds, and ternary and quaternary alloys. The long-term goal is to utilize this vapor phase deposition in conjunction with existing current controlled liquid phase epitaxy facilities to perform hybrid growth sequences for fabricating integrated optoelectronic devices.

  2. Investigation of spin-gapless semiconductivity and half-metallicity in Ti{sub 2}MnAl-based compounds

    Energy Technology Data Exchange (ETDEWEB)

    Lukashev, P., E-mail:; Staten, B.; Hurley, N. [Department of Physics, University of Northern Iowa, Cedar Falls, Iowa 50614 (United States); Kharel, P., E-mail: [Department of Physics, South Dakota State University, Brookings, South Dakota 57007 (United States); Nebraska Center for Materials and Nanoscience, University of Nebraska, Lincoln, Nebraska 68588 (United States); Gilbert, S.; Fuglsby, R.; Huh, Y. [Department of Physics, South Dakota State University, Brookings, South Dakota 57007 (United States); Valloppilly, S. [Nebraska Center for Materials and Nanoscience, University of Nebraska, Lincoln, Nebraska 68588 (United States); Zhang, W.; Skomski, R.; Sellmyer, D. J. [Nebraska Center for Materials and Nanoscience, University of Nebraska, Lincoln, Nebraska 68588 (United States); Department of Physics and Astronomy, University of Nebraska, Lincoln, Nebraska 68588 (United States); Yang, K. [Department of Physics, South Dakota State University, Brookings, South Dakota 57007 (United States); College of Mechanical and Electrical Engineering, Hohai University, Changzhou, Jiangsu 213022 (China)


    The increasing interest in spin-based electronics has led to a vigorous search for new materials that can provide a high degree of spin polarization in electron transport. An ideal candidate would act as an insulator for one spin channel and a conductor or semiconductor for the opposite spin channel, corresponding to the respective cases of half-metallicity and spin-gapless semiconductivity. Our first-principle electronic-structure calculations indicate that the metallic Heusler compound Ti{sub 2}MnAl becomes half-metallic and spin-gapless semiconducting if half of the Al atoms are replaced by Sn and In, respectively. These electronic structures are associated with structural transitions from the regular cubic Heusler structure to the inverted cubic Heusler structure.

  3. An expert system for process planning of sheet metal parts produced on compound die for use in stamping industries

    Indian Academy of Sciences (India)



    Process planning of sheet metal part is an important activity in the design of compound die. Traditional methods of carrying out this task are manual, tedious, time-consuming, error-prone and experiencebased. This paper describes the research work involved in the development of an expert system for process planning of sheet metal parts produced on compound die. The proposed system is organized in six modules. For development of system modules, domain knowledge acquired from various sources of knowledge acquisition is refined and then framed in form of ‘IF-Then’ variety of production rules. System modules are coded in AutoLISP language and user interface is created using visual basic (VB). The system is capable to automate various activities of process planning including blank modeling, blank nesting, determining punch force required, election of clearance between punch and die, identifying sheet metal operations, and determining proper sequence of operations for manufacturing the part. The proposed system can be implemented on a PC having VB and AutoCAD software, therefore its low cost of implementation makes it affordable even for small scale sheet metal industries.

  4. Exchange bias in a mixed metal oxide based magnetocaloric compound YFe0.5Cr0.5O3 (United States)

    Sharma, Mohit K.; Singh, Karan; Mukherjee, K.


    We report a detailed investigation of magnetization, magnetocaloric effect and exchange bias studies on a mixed metal oxide YFe0.5Cr0.5O3 belonging to perovskite family. Our results reveal that the compound is in canted magnetic state (CMS) where ferromagnetic correlations are present in an antiferromagnetic state. Magnetic entropy change of this compound follows a power law (∆SM∼Hm) dependence of magnetic field. In this compound, inverse magnetocaloric effect (IMCE) is observed below 260 K while conventional magnetocaloric effect (CMCE) above it. The exponent 'm' is found to be independent of temperature and field only in the IMCE region. Investigation of temperature and magnetic field dependence studies of exchange bias, reveal a competition between effective Zeeman energy of the ferromagnetic regions and anisotropic exchange energy at the interface between ferromagnetic and antiferromagnetic regions. Variation of exchange bias due to temperature and field cycling is also investigated.

  5. First-principles study of new quaternary Heusler compounds without 3d transition metal elements: ZrRhHfZ (Z = Al, Ga, In)

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaotian [School of Material Sciences and Engineering, Hebei University of Technology, Tianjin 300130 (China); Institute for Superconducting & Electronic Materials (ISEM), University of Wollongong, Wollongong 2500 (Australia); Cheng, Zhenxiang, E-mail: [Institute for Superconducting & Electronic Materials (ISEM), University of Wollongong, Wollongong 2500 (Australia); Guo, Ruikang [School of Material Sciences and Engineering, Hebei University of Technology, Tianjin 300130 (China); Wang, Jianli [Institute for Superconducting & Electronic Materials (ISEM), University of Wollongong, Wollongong 2500 (Australia); Rozale, Habib [Condensed Matter and Sustainable Development Laboratory, Physics Department, University of Sidi-Bel-Abbès, 22000 Sidi-Bel-Abbès (Algeria); Wang, Liying [Department of Physics, Tianjin University, Tianjin 300350 (China); Yu, Zheyin [Institute for Superconducting & Electronic Materials (ISEM), University of Wollongong, Wollongong 2500 (Australia); Liu, Guodong, E-mail: [School of Material Sciences and Engineering, Hebei University of Technology, Tianjin 300130 (China)


    Plane-wave pseudo-potential methods based on density functional theory are employed to investigate the electronic structures, and the magnetic and half-metallic properties of the newly designed quaternary Heusler compounds ZrRhHfZ (Z = Al, Ga, In) without 3d transition metal elements. The calculated results show that ZrRhHfZ (Z = Al, Ga, In) compounds are half-metallic, with 100% spin polarization around the Fermi level. The structural stability of these compounds has been tested from the aspects of their cohesion energy and formation. The spin-flip/half-metallic gaps of ZrRhHfZ (Z = Al, Ga, In) compounds are quite large, with values of 0.2548 eV, 0.3483 eV, and 0.2866 eV, respectively. These compounds show Slater-Pauling behavior, and the total spin magnetic moment per unit cell (M{sub t}) scales with the total number of valence electrons (Z{sub t}) following the rule: M{sub t} = Z{sub t} - 18. The magnetization of ZrRhHfZ (Z = Al, Ga, In) compounds mainly comes from the 4d electrons of the Zr atoms and the 5d electrons of the Hf atoms. Furthermore, the effects of uniform strain and tetragonal deformation on the half metallicity has been investigated in detail, which is important for practical application. Finally, we reveal that the half-metallicity can be maintained when the Coulomb interactions are considered. - Highlights: • New quaternary compounds without 3d transition metal elements have been designed. • The electronic structures and magnetism of the ZrRhHfZ compounds have been studied. • The effect of strain on the half-metallic behavior has been tested. • The effect of the Coulomb interactions on the half-metallicity has been investigated.

  6. Facile synthesis of magnetic hierarchical copper silicate hollow nanotubes for efficient adsorption and removal of hemoglobin. (United States)

    Zhang, Min; Wang, Baoyu; Zhang, Yanwei; Li, Weizhen; Gan, Wenjun; Xu, Jingli


    This study reports the fabrication of magnetic copper silicate hierarchical hollow nanotubes, which are featured by a tailored complex wall structure and high surface area. Moreover, they exhibit excellent performance as an easily recycled adsorbent for protein separation. Particularly, this strategy can be extended as a general method to prepare other magnetic metal silicate hollow nanotubes.

  7. Effects of metal compounds with distinct physicochemical properties on iron homeostasis and antibacterial activity in the lungs: chromium and vanadium. (United States)

    Cohen, Mitchell D; Sisco, Maureen; Prophete, Colette; Yoshida, Kotaro; Chen, Lung-chi; Zelikoff, Judith T; Smee, Jason; Holder, Alvin A; Stonehuerner, Jacqueline; Crans, Debbie C; Ghio, Andrew J


    In situ reactions of metal ions or their compounds are important mechanisms by which particles alter lung immune responses. The authors hypothesized that major determinants of the immunomodulatory effect of any metal include its redox behavior/properties, oxidation state, and/or solubility, and that the toxicities arising from differences in physicochemical parameters are manifest, in part, via differential shifts in lung iron (Fe) homeostasis. To test the hypotheses, immunomodulatory potentials for both pentavalent vanadium (VV; as soluble metavanadate or insoluble vanadium pentoxide) and hexavalent chromium (CrVI; as soluble sodium chromate or insoluble calcium chromate) were quantified in rats after inhalation (5h/day for 5 days) of each at 100 microg metal/m3. Differences in effects on local bacterial resistance between the two VV, and between each CrVI, agents suggested that solubility might be a determinant of in situ immunotoxicity. For the soluble forms, VV had a greater impact on resistance than CrVI, indicating that redox behavior/properties was likely also a determinant. The soluble VV agent was the strongest immunomodulant. Regarding Fe homeostasis, both VV agents had dramatic effects on airway Fe levels. Both also impacted local immune/airway epithelial cell Fe levels in that there were significant increases in production of select cytokines/chemokines whose genes are subject to regulation by HIF-1 (whose intracellular longevity is related to cell Fe status). Our findings contribute to a better understanding of the role that metal compound properties play in respiratory disease pathogenesis and provide a rationale for differing pulmonary immunotoxicities of commonly encountered ambient metal pollutants.

  8. Effect of central metal ions of analogous metal-organic frameworks on adsorption of organoarsenic compounds from water: plausible mechanism of adsorption and water purification. (United States)

    Jun, Jong Won; Tong, Minman; Jung, Beom K; Hasan, Zubair; Zhong, Chongli; Jhung, Sung Hwa


    The adsorptive removal of organoarsenic compounds such as p-arsanilic acid (ASA) and roxarsone (ROX) from water using metal-organic frameworks (MOFs) has been investigated for the first time. A MOF, iron benzenetricarboxylate (also called MIL-100-Fe) exhibits a much higher adsorption capacity for ASA and ROX than activated carbon, zeolite (HY), goethite, and other MOFs. The adsorption of ASA and ROX over MIL-100-Fe is also much more rapid than that over activated carbon. Moreover, the used MIL-100-Fe can be recycled by simply washing with acidic ethanol. Therefore, it is determined that a MOF such as MIL-100-Fe can be used to remove organoarsenic compounds from contaminated water because of its high adsorption capacity, rapid adsorption, and ready regeneration. Moreover, only one of three analogous MIL-100 species (MIL-100-Fe, rather than MIL-100-Al or MIL-100-Cr) can effectively remove the organoarsenic compounds. This selective and high adsorption over MIL-100-Fe, different from other analogous MIL-100 species, can be explained (through calculations) by the facile desorption of water from MIL-100-Fe as well as the large (absolute value) replacement energy (difference between the adsorption energies of the organoarsenic compounds and water) exhibited by MIL-100-Fe. A plausible adsorption/desorption mechanism is proposed based on the surface charge of the MOFs, FTIR results, calculations, and the reactivation results with respect to the solvents used in the experiments.

  9. Radionuclides, Trace Metals, and Organic Compounds in Shells of Native Freshwater Mussels Along the Hanford Reach of the Columbia River: 6000 Years Before Present to Current Times

    Energy Technology Data Exchange (ETDEWEB)

    B. L. Tiller; T. E. Marceau


    This report documents concentrations of radionuclides, trace metals, and semivolatile organic compounds measured in shell samples of the western pearl shell mussel collected along the Hanford Reach of the Columbia River.

  10. Toxicity assessment of heavy metals and organic compounds using CellSense biosensor with E.coli

    Institute of Scientific and Technical Information of China (English)

    Hong Wang; Xue Jiang Wang; Jian Fu Zhao; Ling Chen


    A new strategy using an amperometric biosensor with Escherichia coli(E.coli)that provides a rapid toxicity determination of chemical compounds is described.The CellSense biosensor system comprises a biological component immobilized in intimate contact with a transducer which converts the biochemical signal into a quantifiable electrical signal.Toxicity assessment of heavy metals using E.coli biosensors could be finished within 30 min and the 50% effective concentrations(EC50)values of four heavy metals were determined.The results shows that inhibitory effects of four heavy metals to E.coli can be ranked in a decreasing order of Hg2+>Cu2+>Zn2+>Ni2+,which accords to the results of conventional bacterial counting method.The toxicity test of organic compounds by using CellSense biosensor was also demonstrated.The CellSense biosensor with E.coli shows a good,reproducible behavior and can be used for reproducible measurements.

  11. Review of magnetic properties and magnetocaloric effect in the intermetallic compounds of rare earth with low boiling point metals (United States)

    Ling-Wei, Li


    The magnetocaloric effect (MCE) in many rare earth (RE) based intermetallic compounds has been extensively investigated during the last two decades, not only due to their potential applications for magnetic refrigeration but also for better understanding of the fundamental problems of the materials. This paper reviews our recent progress on studying the magnetic properties and MCE in some binary or ternary intermetallic compounds of RE with low boiling point metal(s) (Zn, Mg, and Cd). Some of them exhibit promising MCE properties, which make them attractive for low temperature magnetic refrigeration. Characteristics of the magnetic transition, origin of large MCE, as well as the potential application of these compounds are thoroughly discussed. Additionally, a brief review of the magnetic and magnetocaloric properties in the quaternary rare earth nickel boroncarbides RENi2B2C superconductors is also presented. Project supported by the National Natural Science Foundation of China (Grant Nos. 11374081 and 11004044), the Fundamental Research Funds for the Central Universities, China (Grant Nos. N150905001, L1509006, and N140901001), the Japan Society for the Promotion of Science Postdoctoral Fellowships for Foreign Researchers (Grant No. P10060), and the Alexander von Humboldt (AvH) Foundation (Research stipend to L. Li).

  12. Pressure-Induced Metallization in Iron-Based Ladder Compounds Ba1-xCsxFe2Se3 (United States)

    Hawai, Takafumi; Kawashima, Chizuru; Ohgushi, Kenya; Matsubayashi, Kazuyuki; Nambu, Yusuke; Uwatoko, Yoshiya; Sato, Taku J.; Takahashi, Hiroki


    Electrical resistivity measurements have been performed on the iron-based ladder compounds Ba1-xCsxFe2Se3 (x = 0, 0.25, 0.65, and 1) under high pressure. A cubic anvil press was used up to 8.0 GPa, whereas further higher pressure was applied using a diamond anvil cell up to 30.0 GPa. Metallic behavior of the electrical conductivity was confirmed in the x = 0.25 and 0.65 samples for pressures greater than 11.3 and 14.4 GPa, respectively, with the low-temperature log T upturn being consistent with weak localization of 2D electrons due to random potential. At pressures higher than 23.8 GPa, three-dimensional Fermi-liquid-like behavior was observed in the latter sample. No metallic conductivity was observed in the parent compounds BaFe2Se3 (x = 0) up to 30.0 GPa and CsFe2Se3 (x = 1) up to 17.0 GPa. The present results indicate that the origins of the insulating ground states in the parent and intermediate compounds are intrinsically different; the former is a Mott insulator, whereas the latter is an Anderson insulator owing to the random substitution of Cs for Ba.

  13. Thermochemistry and Dynamics of Reactive Species: Nitrogen-rich Compounds, Metals and SiC Clusters in Free and Solvated Environment (United States)


    of Reactive Species : Nitrogen-rich F49620-02-1-0371 Compounds, Metals and SiC clusters in Free and Solvated Environments Sb. GRANT NUMBER 5c. PROGRAM...F49620-02-1-0371 Thermochemistry and Dynamics of Reactive Species : Nitrogen-rich Compounds, Metals, and SiC clusters in Free and Solvated Environments...research program remain the same as before: obtaining fundamental thermochemical and dynamical data on reactive species Status of Effort This report

  14. Thin films of metal-organic compounds and metal nanoparticle-embedded polymers for nonlinear optical applications

    Indian Academy of Sciences (India)

    S Philip Anthony; Shatabdi Porel; D Narayana Rao; T P Radhakrishnan


    Thin films based on two very different metal-organic systems are developed and some nonlinear optical applications are explored. A family of zinc complexes which form perfectly polar assemblies in their crystalline state are found to organize as uniaxially oriented crystallites in vapor deposited thin films on glass substrate. Optical second harmonic generation from these films is investigated. A simple protocol is developed for the in-situ fabrication of highly monodisperse silver nanoparticles in a polymer film matrix. The methodology can be used to produce free-standing films. Optical limiting capability of the nanoparticle-embedded polymer film is demonstrated.

  15. Fundamental Studies of the Reforming of Oxygenated Compounds over Supported Metal Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Dumesic, James A. [Univ. of Wisconsin, Madison, WI (United States)


    The main objective of our research has been to elucidate fundamental concepts associated with controlling the activity, selectivity, and stability of bifunctional, metal-based heterogeneous catalysts for tandem reactions, such as liquid-phase conversion of oxygenated hydrocarbons derived from biomass. We have shown that bimetallic catalysts that combine a highly-reducible metal (e.g., platinum) with an oxygen-containing metal promoter (e.g., molybdenum) are promising materials for conversion of oxygenated hydrocarbons because of their high activity for selective cleavage for carbon-oxygen bonds. We have developed methods to stabilize metal nanoparticles against leaching and sintering under liquid-phase reaction conditions by using atomic layer deposition (ALD) to apply oxide overcoat layers. We have used controlled surface reactions to produce bimetallic catalysts with controlled particle size and controlled composition, with an important application being the selective conversion of biomass-derived molecules. The synthesis of catalysts by traditional methods may produce a wide distribution of metal particle sizes and compositions; and thus, results from spectroscopic and reactions kinetics measurements have contributions from a distribution of active sites, making it difficult to assess how the size and composition of the metal particles affect the nature of the surface, the active sites, and the catalytic behavior. Thus, we have developed methods to synthesize bimetallic nanoparticles with controlled particle size and controlled composition to achieve an effective link between characterization and reactivity, and between theory and experiment. We have also used ALD to modify supported metal catalysts by addition of promoters with atomic-level precision, to produce new bifunctional sites for selective catalytic transformations. We have used a variety of techniques to characterize the metal nanoparticles in our catalysts, including scanning transmission electron

  16. Surface protected lithium-metal-oxide electrodes (United States)

    Thackeray, Michael M.; Kang, Sun-Ho


    A lithium-metal-oxide positive electrode having a layered or spinel structure for a non-aqueous lithium electrochemical cell and battery is disclosed comprising electrode particles that are protected at the surface from undesirable effects, such as electrolyte oxidation, oxygen loss or dissolution by one or more lithium-metal-polyanionic compounds, such as a lithium-metal-phosphate or a lithium-metal-silicate material that can act as a solid electrolyte at or above the operating potential of the lithium-metal-oxide electrode. The surface protection significantly enhances the surface stability, rate capability and cycling stability of the lithium-metal-oxide electrodes, particularly when charged to high potentials.

  17. Porphyrin-Embedded Silicate Materials for Detection of Hydrocarbon Solvents (United States)


    are naturally occurring in petroleum products . The individual compounds are also used in a range of manufacturing and production processes. The BTEX...478-483. 17. Ueno, Y.; Tate, A.; Niwa, O.; Zhou, H.-S.; Yamada, T.; Honma, I. High benzene selectivity of mesoporous silicate for BTX gas sensing

  18. DFT and post-DFT studies of metallic MXY3-type compounds for low temperature TE applications (United States)

    Bilal, M.; Saifullah; Ahmad, Iftikhar; Jalali-Asadabadi, S.; Ahmad, Rashid; Shafiq, M.


    In this paper, thermoelectric properties of carbon and nitrogen based twenty metallic antiperovskites MXY3 (M=Al, Ga, Ir, Mg, Pd, Pt, Rh; X=C, N; Y=Mn, Ni, Sc, Ti, Cr, Fe) using ab-initio density functional theory and post-DFT Boltzmann's techniques are investigated. The electronic properties of these compounds are also discussed. We find high values of Seebeck coefficient and small values of electronic thermal conductivity for AlCTi3, AlNSc3, AlCNi3, AlNTi3, GaCCr3 and MgCNi3 between -0.25 and 0.25 eV chemical potential. These results show high dimensionless figure of merit in metallic materials and therefore, we predict these materials can be potential candidates for low temperature thermoelectric applications.

  19. Organic acid compounds in root exudation of Moso Bamboo (Phyllostachys pubescens) and its bioactivity as affected by heavy metals. (United States)

    Chen, Junren; Shafi, Mohammad; Wang, Ying; Wu, Jiasen; Ye, Zhengqian; Liu, Chen; Zhong, Bin; Guo, Hua; He, Lizhi; Liu, Dan


    Moso bamboo (Phyllostachys pubescens) has great potential as phytoremediation material in soil contaminated by heavy metals. A hydroponics experiment was conducted to determine organic acid compounds of root exudates of lead- (Pb), zinc- (Zn), copper- (Cu), and cadmium (Cd)-tolerant of Moso bamboo. Plants were grown in nutrients solution which included Pb, Zn, Cu, and Cd applied as Pb(NO3)2 (200 μM), ZnSO4·7H2O (100 μM), CuSO4·5H2O (25 μM), and CdCl2 (10 μM), respectively. Oxalic acid and malic acid were detected in all treatments. Lactic acid was observed in Cu, Cd, and control treatments. The oxalic was the main organic acid exudated by Moso bamboo. In the sand culture experiment, the Moso bamboo significantly activated carbonate heavy metals under activation of roots. The concentration of water-soluble metals (except Pb) in sand were significantly increased as compared with control. Organic acids (1 mM mixed) were used due to its effect on the soil adsorption of heavy metals. After adding mixed organic acids, the Cu and Zn sorption capacity in soils was decreased markedly compared with enhanced Pb and Cd sorption capacity in soils. The sorption was analyzed using Langmuir and Freundlich equations with R (2) values that ranged from 0.956 to 0.999 and 0.919 to 0.997, respectively.

  20. Graphene-Based Materials as Solid Phase Extraction Sorbent for Trace Metal Ions, Organic Compounds, and Biological Sample Preparation. (United States)

    Ibrahim, Wan Aini Wan; Nodeh, Hamid Rashidi; Sanagi, Mohd Marsin


    Graphene is a new carbon-based material that is of interest in separation science. Graphene has extraordinary properties including nano size, high surface area, thermal and chemical stability, and excellent adsorption affinity to pollutants. Its adsorption mechanisms are through non-covalent interactions (π-π stacking, electrostatic interactions, and H-bonding) for organic compounds and covalent interactions for metal ions. These properties have led to graphene-based material becoming a desirable adsorbent in a popular sample preparation technique known as solid phase extraction (SPE). Numerous studies have been published on graphene applications in recent years, but few review papers have focused on its applications in analytical chemistry. This article focuses on recent preconcentration of trace elements, organic compounds, and biological species using SPE-based graphene, graphene oxide, and their modified forms. Solid phase microextraction and micro SPE (µSPE) methods based on graphene are discussed.

  1. Compound surface-plasmon-polariton waves guided by a thin metal layer sandwiched between a homogeneous isotropic dielectric material and a periodically multilayered isotropic dielectric material

    CERN Document Server

    Chiadini, Francesco; Scaglione, Antonio; Lakhtakia, Akhlesh


    Multiple p- and s-polarized compound surface plasmon-polariton (SPP) waves at a fixed frequency can be guided by a structure consisting of a metal layer sandwiched between a homogeneous isotropic dielectric (HID) material and a periodic multilayered isotropic dielectric (PMLID) material. For any thickness of the metal layer, at least one compound SPP wave must exist. It possesses the p-polarization state, is strongly bound to the metal/HID interface when the metal thickness is large but to both metal/dielectric interfaces when the metal thickness is small. When the metal layer vanishes, this compound SPP wave transmutes into a Tamm wave. Additional compound SPP waves exist, depending on the thickness of the metal layer, the relative permittivity of the HID material, and the period and the composition of the PMLID material. Some of these are p polarized, the others being s polarized. All of them differ in phase speed, attenuation rate, and field profile, even though all are excitable at the same frequency. The...

  2. Development of Silicate Polymers

    DEFF Research Database (Denmark)

    Søgaard, Erik Gydesen; Simonsen, Morten Enggrob

      The development of inorganic polymers is a new promising technology that may be used in many applications. The syntheses of inorganic polymers are normally carried out either by mixing an amorphous material for example silicium dioxide with a mineral base or dissolving metal oxids or metal...... hydroxide in acid and increase pH to saturation of the metal hydroxide. It is assumed that the syntheses of the inorganic polymer are carried out through polymerisation of oligomers (dimer, trimer) which provide the actual unit structures of the three dimensional macromolecular structure. In this work...

  3. Volatile organic compounds and metal leaching from composite products made from fiberglass-resin portion of printed circuit board waste. (United States)

    Guo, Jie; Jiang, Ying; Hu, Xiaofang; Xu, Zhenming


    This study focused on the volatile organic compounds (VOCs) and metal leaching from three kinds of composite products made from fiberglass-resin portion (FRP) of crushed printed circuit board (PCB) waste, including phenolic molding compound (PMC), wood plastic composite (WPC), and nonmetallic plate (NMP). Released VOCs from the composite products were quantified by air sampling on adsorbent followed by thermal desorption and GC-MS analysis. The results showed that VOCs emitted from composite products originated from the added organic components during manufacturing process. Phenol in PMC panels came primarily from phenolic resin, and the airborne concentration of phenol emitted from PMC product was 59.4 ± 6.1 μg/m(3), which was lower than odor threshold of 100% response for phenol (180 μg/m(3)). VOCs from WPC product mainly originated from wood flour, e.g., benzaldehyde, octanal, and d-limonene were emitted in relatively low concentrations. For VOCs emitted from NMP product, the airborne concentration of styrene was the highest (633 ± 67 μg/m(3)). Leaching characteristics of metal ions from composite products were tested using acetic acid buffer solution and sulphuric acid and nitric acid solution. Then the metal concentrations in the leachates were tested by ICP-AES. The results showed that only the concentration of Cu (average = 893 mg/L; limit = 100 mg/L) in the leachate solution of the FRP using acetic acid buffer solution exceeded the standard limit. However, concentrations of other metal ions (Pb, Cd, Cr, Ba, and Ni) were within the standard limit. All the results indicated that the FRP in composite products was not a major concern in terms of environmental assessment based upon VOCs tests and leaching characteristics.

  4. Ionothermal synthesis and structural transformation targeted by ion exchange in metal-1,3,5-benzenetricarboxylate compounds (United States)

    Xu, Qing-Qing; Liu, Bing; Xu, Ling; Jiao, Huan


    Ionothermal reactions of 1,3,5-benzenetricarboxylate acid (H3BTC) and Ni(NO3)2, Co(NO3)2 and Cu(NO3)2 gave two discrete 32-membered ring-like allomers, [M2(HBTC)2(NH2CONH2)2(H2O)4]·3H2O (M=Ni(1), Co(2)) and one layered [Cu2(BTC)Cl(H2O)4] (3). The weak interactions in 1 can be deconstructed to some degree in ion exchange by exploring the factors of divalent and trivalent metal species, metal concentration and soaking time, which are demonstrated by PXRD and N2 absorption. Cu2+ has the highest N2 adsorbance when soaking with 1, and 1 can keep structure stable when Cu2+ below 0.16 mol L-1 and the soaking time within 24d. As Cu2+ beyond 0.16 mol L-1 and the soaking time beyond 24d, the structure of compound 1 starts to transform with the crystal morphology from clear pale green to opaque blue. Ionothermal reactions of compound 1 with different Cu2+ amounts obtained Ni2+-Cu2+ hetero complexes, whose PXRD patterns are similar to that of 3 and EDS indicates Cu2+% increases with Cu2+ additions and close to 100% as Cu2+ being 1.6 mmol. It suggests that 3 is a controlled product and Cu2+ can transform discrete compound 1 into 2D compound 3.

  5. Mineral stimulation of subsurface microorganisms: release of limiting nutrients from silicates (United States)

    Roger, Jennifer Roberts; Bennett, Philip C.


    Microorganisms play an important role in the weathering of silicate minerals in many subsurface environments, but an unanswered question is whether the mineral plays an important role in the microbial ecology. Silicate minerals often contain nutrients necessary for microbial growth, but whether the microbial community benefits from their release during weathering is unclear. In this study, we used field and laboratory approaches to investigate microbial interactions with minerals and glasses containing beneficial nutrients and metals. Field experiments from a petroleum-contaminated aquifer, where silicate weathering is substantially accelerated in the contaminated zone, revealed that phosphorus (P) and iron (Fe)-bearing silicate glasses were preferentially colonized and weathered, while glasses without these elements were typically barren of colonizing microorganisms, corroborating previous studies using feldspars. In laboratory studies, we investigated microbial weathering of silicates and the release of nutrients using a model ligand-promoted pathway. A metal-chelating organic ligand 3,4 dihydroxybenzoic acid (3,4 DHBA) was used as a source of chelated ferric iron, and a carbon source, to investigate mineral weathering rate and microbial metabolism.In the investigated aquifer, we hypothesize that microbes produce organic ligands to chelate metals, particularly Fe, for metabolic processes and also form stable complexes with Al and occasionally with Si. Further, the concentration of these ligands is apparently sufficient near an attached microorganism to destroy the silicate framework while releasing the nutrient of interest. In microcosms containing silicates and glasses with trace phosphate mineral inclusions, microbial biomass increased, indicating that the microbial community can use silicate-bound phosphate inclusions. The addition of a native microbial consortium to microcosms containing silicates or glasses with iron oxide inclusions correlated to

  6. Solving the problem of structure determination in 3d transition metal based Heusler compounds

    Energy Technology Data Exchange (ETDEWEB)

    Balke, Benjamin; Fecher, Gerhard H.; Blum, Christian; Basit, Lubna; Felser, Claudia [Institute of Inorganic and Analytical Chemistry, Johannes Gutenberg - University, Mainz (Germany)


    This work reports on the structural investigation of Fe-containing, Co{sub 2}-based Heusler compounds (Co{sub 2}FeZ with Z=Al, Si, Ga, Ge) using anomalous X-ray diffraction (XRD) and extended X-ray absorption fine structure spectroscopy (EXAFS). Using XRD, it was shown that Co{sub 2}FeAl crystallizes in the B2 structure whereas Co{sub 2}FeSi crystallizes in the L2{sub 1} structure. For compounds containing Ga or Ge, the XRD technique with regular laboratory sources for excitation can not be used easily to distinguish the two structures. For this reason, EXAFS was used to elucidate the structure of these two compounds. The absorption experiments close to the K-edges of Co, Fe, Ga, and Ge indicated that both compounds crystallize in the L2{sub 1} structure. Exciting the XRD at the K-edges of Co and Fe leads to anomalous X-ray scattering. The dependence of the scattering parameters on the energy close to the absorption edges was used to identify the L2{sub 1} structure of the Ga and Ge containing compounds unambiguously. The applicability of the techniques on nano-scaled materials is demonstrated for the example of Co{sub 2}FeGa nano-particles with sizes of below 25 nm.

  7. Trends in air concentration and deposition at background monitoring sites in Sweden - major inorganic compounds, heavy metals and ozone

    Energy Technology Data Exchange (ETDEWEB)

    Kindbom, K.; Svensson, Annika; Sjoeberg, K.; Pihl Karlsson, G.


    This report describes concentrations in air of sulphur compounds, soot, nitrogen compounds and ozone in Sweden between 1985-1998. Time trends of concentration in precipitation and deposition of sulphate, nitrate, ammonium, acidity, base cations and chloride in six different regions covering Sweden are evaluated during the period 1983-1998. Trends of heavy metals in precipitation have been analysed for the period 1983-1998 and the change in heavy metal concentration, 1975-1995, in mosses is described. Data used in the trend analyses originates from measurements performed at six Swedish EMEP stations and from approximately 25 stations within the national Precipitation Chemistry Network. Two different statistical methods, linear regression and the non-parametric Mann Kendall test, have been used to evaluate changes in annual mean values. Time trends of concentration of sulphur dioxide, particulate sulphate, soot, nitrogen dioxide, total nitrate and total ammonium in air show highly significant decreasing trends, except for soot at one station in northern Sweden. Concentrations of ozone have a strong seasonal variation with a peak occurring in spring every year. However, annual ozone concentrations show no obvious trends in spite of decreasing emissions of the precursors NOx and VOC. A slight indication of a decreasing trend in the number of ozone episodes might be seen from 1990 to 1998. Sulphate concentrations in precipitation and deposition show strongly significant decreasing trends in the whole country. Concentrations and deposition of nitrate and ammonium have been decreasing in all areas except for nitrate at stations in south-west and north-west Sweden and ammonium in south-west Sweden. Acidity has decreased in all areas since 1989, resulting in increasing pH values in Sweden. The interannual variations of concentration and deposition of base cations and chloride are large and few general trends can be seen during 1983-1997. Time trends of four heavy metals in

  8. New electrolyte systems for capillary zone electrophoresis of metal cations and non-ionic organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Y.


    Excellent separations of metal ions can be obtained very quickly by capillary electrophoresis provided a weak complexing reagent is incorporated into the electrolyte to alter the effective mobilities of the sample ions. Indirect photometric detection is possible by also adding a UV-sensitive ion to the electrolyte. Separations are described using phthalate, tartrate, lactate or hydroxyisobutyrate as the complexing reagent. A separation of twenty-seven metal ions was achieved in only 6 min using a lactate system. A mechanism for the separation of lanthanides is proposed for the hydroxyisobutyrate system.

  9. Environmental silicate nano-biocomposites

    CERN Document Server

    Pollet, Eric


    Environmental Silicate Nano-Biocomposites focuses on nano-biocomposites, which are obtained by the association of silicates such as bioclays with biopolymers. By highlighting recent developments and findings, green and biodegradable nano-composites from both renewable and biodegradable polymers are explored. This includes coverage of potential markets such as packaging, agricultures, leisure and the fast food industry. The knowledge and experience of more than twenty international experts in diverse fields, from chemical and biochemical engineering to applications, is brought together in four different sections covering: Biodegradable polymers and Silicates, Clay/Polyesters Nano-biocomposites, Clay/Agropolymers Nano-biocomposites, and Applications and biodegradation of Nano-biocomposites. By exploring the relationships between the biopolymer structures, the processes, and the final properties Environmental Silicate Nano-Biocomposites explains how to design nano-materials to develop new, valuable, environmenta...

  10. Rapid growth of FeAl inter-metallic compound under high undercooling conditions

    Institute of Scientific and Technical Information of China (English)

    L(U) Yongjun; WEI Bingbo


    Fe-58at%Al alloy is undercooled up to 222 K(0.15TL) with the drop tube technique. It is found that there exists a critical undercooling about 185 K, beyond which a "dendrite-equiaxed" growth morphology transition occurs in FeAI intermetallic compound. This transition is characterized by sharp decrease of its grain size. Once the undercooling exceeds 215 K, the peritectic transformation is suppressed completely and a fibrous structure is formed, which results from the cooperative growth of FeAI and FeAl2 compounds.

  11. [Development of novel methods for synthesis of heterocyclic compounds catalyzed by transition metals in fluorinated alcohols]. (United States)

    Saito, Akio


    New possibilities for catalytic syntheses of lactone derivatives and nitrogen-containing heterocyclic compounds in fluorinated alcohols are described. The cationic Rh(I) catalyst in fluorinated alcohol solvents (hexafluoroisopropanol: HFIP, trifluoroethanol: TFE) brought about not only mild cycloaddition reactions of ester-tethered compounds but also a facile formation of indole derivatives by the aromatic amino-Claisen rearrangement of N-propargyl aniline derivatives. The use of HFIP as an additive exerted a remarkable effect on the Pictet-Spengler reaction catalyzed by the fluorinated surfactant-combined Brønsted acid catalyst in water.

  12. Discovery of ancient silicate stardust in a meteorite. (United States)

    Nguyen, Ann N; Zinner, Ernst


    We have discovered nine presolar silicate grains from the carbonaceous chondrite Acfer 094. Their anomalous oxygen isotopic compositions indicate formation in the atmospheres of evolved stars. Two grains are identified as pyroxene, two as olivine, one as a glass with embedded metal and sulfides (GEMS), and one as an Al-rich silicate. One grain is enriched in 26Mg, which is attributed to the radioactive decay of 26Al and provides information about mixing processes in the parent star. This discovery opens new means for studying stellar processes and conditions in various solar system environments.

  13. Depolymerization of organosolv lignin to aromatic compounds over Cu-doped porous metal oxides

    NARCIS (Netherlands)

    Barta, Katalin; Warner, Genoa R.; Beach, Evan S.; Anastas, Paul T.


    Isolated, solvent-extracted lignin from candlenut (Aleurites moluccana) biomass was subjected to catalytic depolymerization in methanol with an added pressure of H-2, using a porous metal oxide catalyst (PMO) derived from a Cu-doped hydrotalcite-like precursor. The Cu-PMO was effective in converting

  14. Tunable hydrogen storage in magnesium-transition metal compounds: first-principles calculations

    NARCIS (Netherlands)

    Er, S.; Tiwari, Dhirendra; Tiwari, D.; de Wijs, Gilles A.; Brocks, G.


    Magnesium dihydride (MgH2) stores 7.7 wt % hydrogen but it suffers from a high thermodynamic stability and slow (de)hydrogenation kinetics. Alloying Mg with lightweight transition metals (TM) (=Sc,Ti,V,Cr) aims at improving the thermodynamic and kinetic properties. We study the structure and

  15. Depolymerization of organosolv lignin to aromatic compounds over Cu-doped porous metal oxides

    NARCIS (Netherlands)

    Barta, Katalin; Warner, Genoa R.; Beach, Evan S.; Anastas, Paul T.


    Isolated, solvent-extracted lignin from candlenut (Aleurites moluccana) biomass was subjected to catalytic depolymerization in methanol with an added pressure of H-2, using a porous metal oxide catalyst (PMO) derived from a Cu-doped hydrotalcite-like precursor. The Cu-PMO was effective in converting

  16. Effects of Ga substitution on the structural and magnetic properties of half metallic Fe{sub 2}MnSi Heusler compound

    Energy Technology Data Exchange (ETDEWEB)

    Pedro, S. S., E-mail:; Caraballo Vivas, R. J.; Andrade, V. M.; Cruz, C.; Paixão, L. S.; Contreras, C.; Costa-Soares, T.; Rocco, D. L.; Reis, M. S. [Instituto de Física, Universidade Federal Fluminense, Niterói-RJ (Brazil); Caldeira, L. [IF Sudeste MG, Campus Juiz de Fora - Núcleo de Física, Juiz de Fora-MG (Brazil); Coelho, A. A. [Instituto de Física Gleb Wataghin, Universidade Estadual de Campinas - Unicamp, Campinas-SP (Brazil); Carvalho, A. Magnus G. [Laboratório Nacional de Luz Sincrotron, CNPEM, Campinas-SP (Brazil)


    The so-called half-metallic magnets have been proposed as good candidates for spintronic applications due to the feature of exhibiting a hundred percent spin polarization at the Fermi level. Such materials follow the Slater-Pauling rule, which relates the magnetic moment with the valence electrons in the system. In this paper, we study the bulk polycrystalline half-metallic Fe{sub 2}MnSi Heusler compound replacing Si by Ga to determine how the Ga addition changes the magnetic, the structural, and the half-metal properties of this compound. The material does not follow the Slater-Pauling rule, probably due to a minor structural disorder degree in the system, but a linear dependence on the magnetic transition temperature with the valence electron number points to the half-metallic behavior of this compound.

  17. Structure of metal-rich (001) surfaces of III-V compound semiconductors

    DEFF Research Database (Denmark)

    Kumpf, C.; Smilgies, D.; Landemark, E.


    feature of the structure is accompanied by linear arrays of atoms on nonbulklike sites at the surface which, depending on the compounds, exhibit a certain degree of disorder. A tendency to group-III-dimer formation within these chains increases when descending the periodic table. We propose that all the c...

  18. Transition metal catalyzed oxidation of Alcell lignin, soda lignin, and lignin model compounds in ionic liquids

    NARCIS (Netherlands)

    Zakzeski, J.|info:eu-repo/dai/nl/326160256; Jongerius, A.L.|info:eu-repo/dai/nl/325840202; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397


    Lignin is a component of lignocellulosic biomass from which important aromatic compounds can potentially be obtained. In the present work, Alcell and soda lignin were dissolved in the ionic liquid 1-ethyl-3-methylimidazolium diethylphosphate (EMIM DEP) and subsequently oxidized using several transit

  19. Electron Correlations on a Mesoscopic Scale : Magnetic Properties of Transition Metal Telluride Cluster Compounds

    NARCIS (Netherlands)

    Palstra, T.T.M.; Steigerwald, M.L.; Ramirez, A.P.; Kwon, Y.-U.; Stuczynski, S.M.; Schneemeyer, L.F.; Waszczak, J.V.; Zaanen, J.


    We report the magnetic properties of a new class of materials: Ni9Te6n+ and Co6Te8n+ with n=0,1,2. These cluster compounds, which can be charged by chemical means from neutral to 2+, provide a unique and novel way to change the Fermi level. For most charge states we observe quenching of the spin and

  20. Transition metal catalyzed oxidation of Alcell lignin, soda lignin, and lignin model compounds in ionic liquids

    NARCIS (Netherlands)

    Zakzeski, J.|info:eu-repo/dai/nl/326160256; Jongerius, A.L.|info:eu-repo/dai/nl/325840202; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397


    Lignin is a component of lignocellulosic biomass from which important aromatic compounds can potentially be obtained. In the present work, Alcell and soda lignin were dissolved in the ionic liquid 1-ethyl-3-methylimidazolium diethylphosphate (EMIM DEP) and subsequently oxidized using several

  1. Effects of metallic nanoparticle doped flux on the interfacial intermetallic compounds between lead-free solder ball and copper substrate

    Energy Technology Data Exchange (ETDEWEB)

    Sujan, G.K., E-mail:; Haseeb, A.S.M.A., E-mail:; Afifi, A.B.M., E-mail:


    Lead free solders currently in use are prone to develop thick interfacial intermetallic compound layers with rough morphology which are detrimental to the long term solder joint reliability. A novel method has been developed to control the morphology and growth of intermetallic compound layers between lead-free Sn–3.0Ag–0.5Cu solder ball and copper substrate by doping a water soluble flux with metallic nanoparticles. Four types of metallic nanoparticles (nickel, cobalt, molybdenum and titanium) were used to investigate their effects on the wetting behavior and interfacial microstructural evaluations after reflow. Nanoparticles were dispersed manually with a water soluble flux and the resulting nanoparticle doped flux was placed on copper substrate. Lead-free Sn–3.0Ag–0.5Cu solder balls of diameter 0.45 mm were placed on top of the flux and were reflowed at a peak temperature of 240 °C for 45 s. Angle of contact, wetting area and interfacial microstructure were studied by optical microscopy, field emission scanning electron microscopy and energy-dispersive X-ray spectroscopy. It was observed that the angle of contact increased and wetting area decreased with the addition of cobalt, molybdenum and titanium nanoparticles to flux. On the other hand, wettability improved with the addition of nickel nanoparticles. Cross-sectional micrographs revealed that both nickel and cobalt nanoparticle doping transformed the morphology of Cu{sub 6}Sn{sub 5} from a typical scallop type to a planer one and reduced the intermetallic compound thickness under optimum condition. These effects were suggested to be related to in-situ interfacial alloying at the interface during reflow. The minimum amount of nanoparticles required to produce the planer morphology was found to be 0.1 wt.% for both nickel and cobalt. Molybdenum and titanium nanoparticles neither appear to undergo alloying during reflow nor have any influence at the solder/substrate interfacial reaction. Thus, doping

  2. Large scale simulations of the mechanical properties of layered transition metal ternary compounds for fossil energy power system applications

    Energy Technology Data Exchange (ETDEWEB)

    Ching, Wai-Yim [Univ. of Missouri, Kansas City, MO (United States)


    Advanced materials with applications in extreme conditions such as high temperature, high pressure, and corrosive environments play a critical role in the development of new technologies to significantly improve the performance of different types of power plants. Materials that are currently employed in fossil energy conversion systems are typically the Ni-based alloys and stainless steels that have already reached their ultimate performance limits. Incremental improvements are unlikely to meet the more stringent requirements aimed at increased efficiency and reduce risks while addressing environmental concerns and keeping costs low. Computational studies can lead the way in the search for novel materials or for significant improvements in existing materials that can meet such requirements. Detailed computational studies with sufficient predictive power can provide an atomistic level understanding of the key characteristics that lead to desirable properties. This project focuses on the comprehensive study of a new class of materials called MAX phases, or Mn+1AXn (M = a transition metal, A = Al or other group III, IV, and V elements, X = C or N). The MAX phases are layered transition metal carbides or nitrides with a rare combination of metallic and ceramic properties. Due to their unique structural arrangements and special types of bonding, these thermodynamically stable alloys possess some of the most outstanding properties. We used a genomic approach in screening a large number of potential MAX phases and established a database for 665 viable MAX compounds on the structure, mechanical and electronic properties and investigated the correlations between them. This database if then used as a tool for materials informatics for further exploration of this class of intermetallic compounds.

  3. In vitro susceptibility of the oomycete Pythium insidiosum to metallic compounds containing cadmium, lead, copper, manganese or zinc. (United States)

    Ribeiro, Tatiana Corrêa; Weiblen, Carla; Botton, Sônia de Avila; Pereira, Daniela Isabel Brayer; de Jesus, Francielli Pantella Kunz; Verdi, Camila Marina; Gressler, Leticia Trevisan; Sangioni, Luís Antonio; Santurio, Janio Morais


    Pythium insidiosum is an aquatic oomycete that causes pythiosis, an important and severe disease of difficult treatment that affects humans, domestic and wild animals. This infection is often described in horses in Brazil and humans in Thailand. In clinical practice, we have observed many cases that do not respond to available therapies, indicating the need to explore alternative therapeutic approaches. In this sense, studies using metal compounds in conjunction with available antimicrobial agents have been demonstrated greater antimicrobial activity. Thus, in this research, we tested in vitro activities of metallic compounds containing cadmium, lead, copper, manganese, or zinc against 23 isolates of P. insidiosum. The assays were performed by broth microdilution based on CLSI M38-A2 document. The minimum inhibitory and fungicidal concentrations were established for all isolates. Copper acetate and cadmium acetate showed the highest inhibitory effects, with minimal inhibitory concentration ranging from 4-64 μg/ml and 16-256 μg/ml, respectively. The mean geometric for minimal fungicidal concentrations were, respectively, 26 μg/ml and 111.43 μg/ml for copper acetate and cadmium acetate. These results suggest that copper and cadmium can inhibit P. insidiosum growth, highlighting the greater inhibitory activity of copper acetate. In addition, our results propose that copper and/or cadmium compounds can be used in upcoming researches to formulate effective new complexed drugs against P. insidiosum in in vitro and in vivo experimental models. © The Author 2016. Published by Oxford University Press on behalf of The International Society for Human and Animal Mycology. All rights reserved. For permissions, please e-mail:

  4. A Stable, Magnetic, and Metallic Li3O4 Compound as a Discharge Product in a Li-Air Battery. (United States)

    Yang, Guochun; Wang, Yanchao; Ma, Yanming


    The Li-air battery with the specific energy exceeding that of a Li ion battery has been aimed as the next-generation battery. The improvement of the performance of the Li-air battery needs a full resolution of the actual discharge products. Li2O2 has been long recognized as the main discharge product, with which, however, there are obvious failures on the understanding of various experimental observations (e.g., magnetism, oxygen K-edge spectrum, etc.) on discharge products. There is a possibility of the existence of other Li-O compounds unknown thus far. Here, a hitherto unknown Li3O4 compound as a discharge product of the Li-air battery was predicted through first-principles swarm structure searching calculations. The new compound has a unique structure featuring the mixture of superoxide O2(-) and peroxide O2(2-), the first such example in the Li-O system. The existence of superoxide O2(-) creates magnetism and hole-doped metallicity. Findings of Li3O4 gave rise to direct explanations of the unresolved experimental magnetism, triple peaks of oxygen K-edge spectra, and the Raman peak at 1125 cm(-1) of the discharge products. Our work enables an opportunity for the performance of capacity, charge overpotential, and round-trip efficiency of the Li-air battery.

  5. Creep of metal-type organic compounds. 4: Application to hot isostatic pressing

    Energy Technology Data Exchange (ETDEWEB)

    Davies, G.C.; Jones, D.R.H. [Univ. of Cambridge (United Kingdom). Engineering Dept.


    Hot isostatic pressing (HIP) experiments using the metal analogue materials camphene and succinonitrile are described. Data obtained previously from uniaxial creep experiments are used in densification rate equations for HIP taken from the literature, and the predicted densification behavior is compared with experimental data. The HIP equations are then modified to include two different representations of the friction stress arising from a dispersed phase of fine, hard particles. In each case the modified theory adequately describes the experimental data.

  6. The role of iron compounds and hydrogen peroxideon the oxidation of metallic mercury


    "愛甲, 博美"


    The uptake of metallic mercury with ferric and ferrous ions was studied. The results were; (1) Mercury uptake of free ferric ion increased with hydrogen peroxide, the maximum uptake was 1.0 mM. However, ferric ion was not taken up without hydrogen peroxide. (2) In the presence of ferric and ferrous ions with hydrogen peroxide, mercury uptake was maximum when the mole ratio (Fe(3+)/Fe(2+)) was 0.1.

  7. The different poisoning behaviors of various alkali metal containing compounds on SCR catalyst (United States)

    Du, Xuesen; Yang, Guangpeng; Chen, Yanrong; Ran, Jingyu; Zhang, Li


    Alkali metals are poisonous to the metal oxide catalyst for NO removal. The chemical configuration of alkali containing substance and interacting temperature can affect the poisoning profile. A computational method based on Frontier Molecular Orbital analysis was proposed to determine the reacting behavior of various alkali-containing substances with SCR catalyst. The results reveal that the poisoning reactivities of various substances can be ranked as: E (MOH) > E (M2SO4) > E(MCl) > E(MNO3) > E(MHSO4). The experimental activity tests of the catalysts calcined at stepped temperatures show that NaOH can react with the catalyst below 200 °C. NaCl and NaNO3 start to react with the catalyst at a temperature between 300 and 400 °C. Unlike MOH, MCl and MNO3, which can produce volatile or decomposable species for the anions after reacting with the catalyst, M2SO4 and MHSO4 will leave both cations and anions on the catalyst surface. The sulfate ions left on the catalyst can generate active acid sites for NH3 adsorption. The experimental results also show that Na2SO4 and NaHSO4 will not lower the NO conversion. The after-reaction influences of various alkali metals were studied using theoretical and experimental methods. The theoretical results show that the acidity decreases with doping of alkali metal. Experiments show a consistent result that the NO conversion decreases as undoped >LiCl > NaCl > KCl.

  8. Exploring the DNA binding mode of transition metal based biologically active compounds (United States)

    Raman, N.; Sobha, S.


    Few novel 4-aminoantipyrine derived Schiff bases and their metal complexes were synthesized and characterized. Their structural features and other properties were deduced from the elemental analysis, magnetic susceptibility and molar conductivity as well as from mass, IR, UV-vis, 1H NMR and EPR spectral studies. The binding of the complexes with CT-DNA was analyzed by electronic absorption spectroscopy, viscosity measurement, and cyclic voltammetry. The interaction of the metal complexes with DNA was also studied by molecular modeling with special reference to docking. The experimental and docking results revealed that the complexes have the ability of interaction with DNA of minor groove binding mode. The intrinsic binding constants ( Kb) of the complexes with CT-DNA were found out which show that they are minor groove binders. Gel electrophoresis assay demonstrated the ability of the complexes to cleave the pUC19 DNA in the presence of AH 2 (ascorbic acid). Moreover, the oxidative cleavage studies using distamycin revealed the minor groove binding for the newly synthesized 4-aminoantipyrine derived Schiff bases and their metal complexes. Evaluation of antibacterial activity of the complexes against Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Staphylococcus epidermidis, and Klebsiella pneumoniae exhibited that the complexes have potent biocidal activity than the free ligands.

  9. Are cadmium and other heavy metal compounds acting as endocrine disrupters? (United States)

    Kortenkamp, Andreas


    Observations of specific interactions of the heavy metal cadmium with the estrogen receptor have spawned a series of studies to investigate the propensity of this and other heavy metals to act as estrogen mimicks. There is good evidence that Cd has the ability to produce estrogenic effects in rodents, including proliferation of the uterine and mammary tissues. These effects could be suppressed by cotreatment with specific estrogen receptor antagonists, suggesting mediation via the estrogen receptor. Epidemiological studies have provided some support for the idea that Cd poses cancer risks for hormone sensitive tissues, such as the breast and the endometrium. Strikingly, attempts to demonstrate estrogenic effects of Cd in in vitro assay systems have produced mixed results. Mitogenic effects on estrogen receptor-competent cells, activation of estrogen receptor-dependent gene transcription and signalling events associated with the estrogen receptor were observed in cellular models, but could not be reproduced by others. Despite these inconsistencies, the available evidence forces the conclusion that Cd and certain other heavy metals should be regarded as estrogen mimicks. In the context of deterministic risk assessment, this should lend further support for risk reduction measures by controlling exposure to Cd. However, data suitable for the quantitation of estrogenic risks, especially in comparison with the established health risks of Cd, are not yet available. It is recommended to close this knowledge gap with urgency.

  10. Volatile organic compounds and trace metal level in some beers collected from Romanian market (United States)

    Voica, Cezara; Kovacs, Melinda; Vadan, Marius


    Beer is one of the most popular beverages at worldwide level. Through this study fifteen different types of beer collected from Romanian market were analysed in order to evaluate their mineral, trace element as well the their organic content. Importance of such characterization of beer samples is supported by the fact that their chemical composition can affect both taste and stability of beer, as well the consumer health. Minerals and trace elements analysis were performed on ICP-MS while organic compounds analysis was done through GC-MS. Through ICP-MS analysis, elements as Ca, Na, K and Mg were evidenced at mgṡkg-1 order while elements as Cr, Ba, Co, Ni were detected at lower level. After GC-MS analysis the major volatile compounds that were detected belong to alcohols namely ethanol, propanol, isobutanol, isoamyl alcohol and linalool. Selected fatty acids and esters were evidenced also in the studied beer samples.

  11. Evaporation of hydrocarbon compounds, including gasoline and diesel fuel, on heated metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Fardad, D.; Ladommatos, N. [Brunel Univ., Dept. of Mechanical Engineering, Uxbridge (United Kingdom)


    An investigation was carried out on the evaporation of various hydrocarbon liquids on heated surfaces. Single and multicomponent hydrocarbon compounds were used, including hexane, heptane, octane, a hexane-octane mixture, gasoline and diesel fuel. The heated surface included aluminium, mild steel, cast iron and copper. Tests were also carried out with different surface textures and surface coatings. The motivation for this work was a desire to improve understanding of the evaporation processes taking place in the inlet port and, to a lesser extent, within the combustion chamber of internal combustion engines. The hydrocarbon compounds were released on the heated surfaces as individual small droplets, and the subsequent evaporation was recorded using a CCD (charge coupled device) camera. These observations were then used to ascertain the effects of material, surface temperature, surface textures, surface coating and liquid composition on the heat flux and other aspects of droplet behaviour. (Author)

  12. Catalytic Addition of Simple Alkenes to Carbonyl Compounds Using Group 10 Metals. (United States)

    Ho, Chun-Yu; Schleicher, Kristin D; Jamison, Timothy F


    Recent advances using nickel complexes in the activation of unactivated monosubstituted olefins for catalytic intermolecular carbon-carbon bond-forming reactions with carbonyl compounds, such as simple aldehydes, isocyanates, and conjugated aldehydes and ketones, are discussed. In these reactions, the olefins function as vinyl- and allylmetal equivalents, providing a new strategy for organic synthesis. Current limitations and the outlook for this new strategy are also discussed.


    Directory of Open Access Journals (Sweden)



    Full Text Available The objective of the submitted work was to prepare and to characterize two types of silicate coatings prepared by the sol-gel method using the dip-coating technique on a titanium substrate. Efforts have been made to use mechanical properties of bio-inert titanium and bioactive properties of a silicate layer enriched with an admixture of compounds identified below. The first group consisted of silicate coatings containing silver, brushite and monetite. The other group of silicate coatings contained calcium nitrate and triethyl phosphate. Mechanically and chemically treated titanium substrates were dipped into sols and dried and fired. Silicate coatings from the first group were also chemically treated in 10 mol.l-1 solution of sodium hydroxide. All coatings were measured to determine their adhesive and bioactive properties and furthermore the antibacterial properties were tested in the case of first group. Surfaces of the coated substrates were investigated after the firing and after the individual tests with optical and electron microscopy and X-ray microdiffraction. A tape test demonstrated excellent adhesive property of all coatings to the substrate, classified with degree 5. A static in vitro test demonstrated bioactivity of nearly all the coatings. The basic silicate coating from the first group and one type of coating from the second group were identified as inert. Antibacterial properties of silicate coatings containing silver showed to be different when tested against Escherichia coli bacteria. A complete inhibition of the growth of bacteria under our experimental conditions was observed for the coating containing silver and monetite and a partial inhibition of the growth of bacteria for coatings containing silver and silver in combination with brushite.

  14. A hidden reservoir of Fe/FeS in interstellar silicates?

    CERN Document Server

    Köhler, M; Ysard, N


    The depletion of iron and sulphur into dust in the interstellar medium and the exact nature of interstellar amorphous silicate grains is still an open question. We study the incorporation of iron and sulphur into amorphous silicates of olivine- and pyroxene-type and their effects on the dust spectroscopy and thermal emission. We used the Maxwell-Garnett effective-medium theory to construct the optical constants for a mixture of silicates, metallic iron, and iron sulphide. We also studied the effects of iron and iron sulphide in aggregate grains. Iron sulphide inclusions within amorphous silicates that contain iron metal inclusions shows no strong differences in the optical properties of the grains. A mix of amorphous olivine- and pyroxene-type silicate broadens the silicate features. An amorphous carbon mantle with a thickness of 10 nm on the silicate grains leads to an increase in absorption on the short-wavelength side of the 10 $\\mu$m silicate band. The assumption of amorphous olivine-type and pyroxene-typ...

  15. Optical Properties of Astronomical Silicates with Infrared Techniques (OPASI-T) (United States)

    Rinehart, Stephen


    Astronomical dust is observed in a variety of astrophysical environments and plays an important role in radiative processes and chemical evolution in the galaxy. Depending upon the environment, dust can be either carbon-rich or oxygen-rich (silicate grains). Both astronomical observations and ground-based data show that the optical properties of silicates can change dramatically with the crystallinity of the material, and recent laboratory research provides evidence that the optical properties of silicate dust vary as a function of temperature as well. Therefore, correct interpretation of a vast array of astronomical data relies on the understanding of the properties of silicate dust as functions of wavelength, temperature, and crystallinity. The OPASI-T (Optical Properties of Astronomical Silicates with Infrared Techniques) project addresses the need for high quality optical characterization of metal-enriched silicate condensates using a variety of techniques. A combination of both new and established experiments are used to measure the extinction, reflection, and emission properties of amorphous silicates across the infrared (near infrared to millimeter wavelengths), providing a comprehensive data set characterizing the optical parameters of dust samples. We present room temperature measurements and the experimental apparatus to be used to investigate and characterize additional metal-silicate materials.

  16. Investigation of synthesized Be-bearing silicate glass as laboratory reference sample at X-ray electron probe microanalysis of silicates (United States)

    Belozerova, Olga Yu.; Mikhailov, Mikhail A.; Demina, Tamara V.


    The article discusses estimates of the stability and homogeneity in Be-Mg-Al-silicate glass produced by the authors and its applicability as a laboratory reference sample for X-ray electron probe microanalysis (EPMA) of Be-bearing silicate matters: crystals and quenching melt (glasses), silicates and oxides. The results were obtained using Superprobe-733 and Superprobe JXA-8200 (JEOL Ltd, Japan) devices. The sample homogeneity was studied on macro (10-100 μm) and micro (1-10 μm) levels and was evaluated by the scheme of dispersion analysis. The applicability of Be-bearing silicate glass as a reference sample for Mg, Al, Si determinations was tested on the international certified reference glasses and laboratory reference samples of minerals with a known composition. The obtained experimental metrological characteristics correspond to the "applied geochemistry" type of analysis (second category) and suggest that Be-bearing silicate glass is appropriate as a laboratory reference sample for EPMA of Be-bearing silicate matters, silicates and oxides. Using Be-Mg-Al-silicate glass as a reference sample we obtained satisfactory data on the composition of both some minerals including cordierite and beryllium cordierite, beryllium indialite, beryl and metastable phases (chrysoberyl, compounds with structure of β-quartz and petalite).

  17. High-performance ab initio density matrix renormalization group method: Applicability to large-scale multireference problems for metal compounds (United States)

    Kurashige, Yuki; Yanai, Takeshi


    This article presents an efficient and parallelized implementation of the density matrix renormalization group (DMRG) algorithm for quantum chemistry calculations. The DMRG method as a large-scale multireference electronic structure model is by nature particularly efficient for one-dimensionally correlated systems, while the present development is oriented toward applications for polynuclear transition metal compounds, in which the macroscopic one-dimensional structure of electron correlation is absent. A straightforward extension of the DMRG algorithm is proposed with further improvements and aggressive optimizations to allow its application with large multireference active space, which is often demanded for metal compound calculations. Special efficiency is achieved by making better use of sparsity and symmetry in the operator and wave function representations. By accomplishing computationally intensive DMRG calculations, the authors have found that a large number of renormalized basis states are required to represent high entanglement of the electron correlation for metal compound applications, and it is crucial to adopt auxiliary perturbative correction to the projected density matrix during the DMRG sweep optimization in order to attain proper convergence to the solution. Potential energy curve calculations for the Cr2 molecule near the known equilibrium precisely predicted the full configuration interaction energies with a correlation space of 24 electrons in 30 orbitals [denoted by (24e,30o)]. The energies are demonstrated to be accurate to 0.6mEh (the error from the extrapolated best value) when as many as 10 000 renormalized basis states are employed for the left and right DMRG block representations. The relative energy curves for [Cu2O2]2+ along the isomerization coordinate were obtained from DMRG and other correlated calculations, for which a fairly large orbital space (32e,62o) is modeled as a full correlation space. The DMRG prediction nearly overlaps

  18. Electronic, thermal, and superconducting properties of metal nitrides (MN) and metal carbides (MC) (M=V, Nb, Ta) compounds by first principles studies

    Energy Technology Data Exchange (ETDEWEB)

    Subhashree, G.; Sankar, S.; Krithiga, R. [Anna Univ., Chennai, Tamil Nadu (India). Condensed Matter Lab.


    Structural, electronic, and superconducting properties of carbides and nitrides of vanadium (V), niobium (Nb), and tantalum (Ta) (group V transition elements) have been studied by computing their electronic band structure characteristics. The electronic band structure calculations have been carried out based on the density functional theory (DFT) within the local density approximation (LDA) by using the tight binding linear muffin tin orbital method. The NaCl-type cubic structures of MN and MC (M=V, Nb, Ta) compounds have been confirmed from the electronic total energy minimum of these compounds. The ground state properties, such as equilibrium lattice constant (a{sub 0}), bulk modulus (B), and Wigner-Seitz radius (S{sub 0}) are determined and compared with available data. The electronic density of states reveals the metallic nature of the chosen materials. The electronic specific heat coefficient, Debye temperature, and superconducting transition temperature obtained from the band structure results are found to agree well with the earlier reported literature.

  19. Metal Atom Dynamics and Spin-Lattice Relaxation in Multilayer Sandwich Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Nowik, Israel; Herber, Rolfe H., E-mail: [Hebrew University of Jerusalem, Racah Institute of Physics (Israel)


    Temperature-dependent {sup 57}Fe Moessbauer spectroscopy has been used to elucidate the hyperfine parameters and dynamical behavior of the metal atom in several organo-iron complexes which have one or more {eta}{sup 5} P{sub 5} ring structures as ligated groups. The spin-lattice relaxation of the (paramagnetic) one-electron oxidation products occurs on a time scale fast compared to {tau}{sub 1/2} (ME) at temperatures in the range 85 < T < 320 K.

  20. Theoretical modelling of intermediate band solar cell materials based on metal-doped chalcopyrite compounds

    Energy Technology Data Exchange (ETDEWEB)

    Palacios, P. [Instituto de Energia Solar and Dpt. de Tecnologias Especiales, ETSI de Telecomunicacion, UPM, Ciudad Universitaria s/n, 28040 Madrid (Spain)]. E-mail:; Sanchez, K. [Instituto de Energia Solar and Dpt. de Tecnologias Especiales, ETSI de Telecomunicacion, UPM, Ciudad Universitaria s/n, 28040 Madrid (Spain); Conesa, J.C. [Instituto de Catalisis y Petroleoquimica, CSIC, Marie Curie 2, Cantoblanco, 28049 Madrid (Spain); Fernandez, J.J. [Dpt. de Fisica Fundamental, Universidad Nacional de Educacion a Distancia, 28080, Madrid (Spain); Wahnon, P. [Instituto de Energia Solar and Dpt. de Tecnologias Especiales, ETSI de Telecomunicacion, UPM, Ciudad Universitaria s/n, 28040 Madrid (Spain)


    Electronic structure calculations are carried out for CuGaS{sub 2} partially substituted with Ti, V, Cr or Mn to ascertain if some of these systems could provide an intermediate band material able to give a high efficiency photovoltaic cell. Trends in electronic level positions are analyzed and more accurate advanced theory levels (exact exchange or Hubbard-type methods) are used in some cases. The Ti-substituted system seems more likely to yield an intermediate band material with the desired properties, and furthermore seems realizable from the thermodynamic point of view, while those with Cr and Mn might give half-metal structures with applications in spintronics.

  1. Synchrotron Diffraction Studies of Spontaneous Magnetostriction in Rare Earth Transition Metal Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ning [Iowa State Univ., Ames, IA (United States)


    Thermal expansion anomalies of R2Fe14B and R2Fe17Cx (x = 0,2) (R = Y, Nd, Gd, Tb, Er) stoichiometric compounds are studied with high-energy synchrotron X-ray powder diffraction using Debye-Schemer geometry in temperature range 10K to 1000K. Large spontaneous magnetostriction up to their Curie temperatures (Tc) is observed. The a-axes show relatively larger invar effects than c-axes in the R2Fe14B compounds whereas the R2Fe17Cx show the contrary anisotropies. The iron sub-lattice is shown to dominate the spontaneous magnetostriction of the compounds. The contribution of the rare earth sublattice is roughly proportional to the spin magnetic moment of the rare earth in the R2Fe14B compounds but in R2Fe17Cx, the rare earth sub-lattice contribution appears more likely to be dominated by the local bonding. The calculation of spontaneous magnetostrain of bonds shows that the bonds associated with Fe(j2) sites in R2Fe14B and the dumbbell sites in R2Fe17Cx have larger values, which is strongly related to their largest magnetic moment and Wigner-Seitz atomic cell volume. The roles of the carbon atoms in increasing the Curie temperatures of the R2Fe17 compounds are attributed to the increased separation of Fe hexagons. The R2Fe17 and R2Fe14B phases with magnetic rare earth ions also show anisotropies of thermal expansion above c. For R2Fe17 and R2Fe14B the a a/a c > 1 whereas the anisotropy is reversed with the interstitial carbon in R2Fe17. The average bond magnetostrain is shown to be a possible predictor of the magnetic moment of Fe sites in the compounds. Both of the theoretical and

  2. Perturbed Angular Correlation (PAC)/NMR spectroscopic properties and dynamics of compounds containing metal ions

    DEFF Research Database (Denmark)

    Arcisauskaité, Vaida

    computationally demanding Coupled Cluster results. We also determined to what degree the computationally cheaper approximate relativistic methods ZORA(-4) and SR-ZORA-4 at the DFT level can reproduce fully-relativistic results. As a result, we proposed reliable computational methods applicable to Hg binding sites...... compounds in terms of the atomic constituents. The analysis provided a chemophysical interpretation of changes in Vzz upon structural distortions and ligand exchange. The gained insights can be useful when predicting and understanding changes in Q values for Hg binding sites in proteins. One of the first...

  3. Stardust silicates from primitive meteorites. (United States)

    Nagashima, Kazuhide; Krot, Alexander N; Yurimoto, Hisayoshi


    Primitive chondritic meteorites contain material (presolar grains), at the level of a few parts per million, that predates the formation of our Solar System. Astronomical observations and the chemical composition of the Sun both suggest that silicates must have been the dominant solids in the protoplanetary disk from which the planets of the Solar System formed, but no presolar silicates have been identified in chondrites. Here we report the in situ discovery of presolar silicate grains 0.1-1 microm in size in the matrices of two primitive carbonaceous chondrites. These grains are highly enriched in 17O (delta17O(SMOW) > 100-400 per thousand ), but have solar silicon isotopic compositions within analytical uncertainties, suggesting an origin in an oxygen-rich red giant or an asymptotic giant branch star. The estimated abundance of these presolar silicates (3-30 parts per million) is higher than reported for other types of presolar grains in meteorites, consistent with their ubiquity in the early Solar System, but is about two orders of magnitude lower than their abundance in anhydrous interplanetary dust particles. This result is best explained by the destruction of silicates during high-temperature processing in the solar nebula.

  4. Heavy metals and polycyclic hydrocarbon compounds in benthic organisms of the Upper Gulf of Thailand

    Energy Technology Data Exchange (ETDEWEB)

    Hungspreugs, M.; Silpipat, S.; Tonapong, C.; Lee, R.F.; Windom, H.L.; Tenore, K.R.


    Concentrations of heavy metals and polycyclic aromatic hydrocarbons (PAHs) were measured in bivalves collected in the Upper Gulf of Thailand. PAHs detected included acenaphthene, acenaphthylene, benzo(a)pyrene, fluoranthene, methylphenanthrene, phenanthrene and triphenylene. Benzol(a)pyrene was detected in all species at concentrations varying from 1.0 to 8.2 ng.g/sup -1/. Concentrations of cadmium, cobalt, copper, lead, and nickel were significantly lower in bivalves from the Gulf than in green mussels collected from the mouth of the Chao Phraya River. No correlation was found between metal concentrations in animals and sediment, with the exception of copper. Copper concentrations in polychaetes and clams appeared to correlate with the copper:iron ratio of sediments. High rates of degradation were observed when radiolabelled chlorobenzene, phenanthrene and chrysene were added to water and sediment of the Chao Phraya River. Rates were lower in the waters and sediment of the Gulf of Thailand. The calculated half-lives of chlorobenzene in the Gulf of Thailand and the Chao Phraya River were about 130 and 68 days, respectively. 32 references, 3 figures, 3 tables.

  5. Preparation of solid-state samples of a transition metal coordination compound for synchrotron radiation photoemission studies

    CERN Document Server

    Crotti, C; Celestino, T; Fontana, S


    The aim of this research was to identify a sample preparation method suitable for the study of transition metal complexes by photoemission spectroscopy with synchrotron radiation as the X-ray source, even in the case where the compound is not evaporable. Solid-phase samples of W(CO) sub 4 (dppe) [dppe=1,2-bis(diphenylphosphino)ethane] were prepared according to different methods and their synchrotron radiation XPS spectra measured. The spectra acquired from samples prepared by spin coating show core level peaks only slightly broader than the spectrum recorded from UHV evaporated samples. Moreover, for these samples the reproducibility of the binding energy values is excellent. The dependence of the spin coating technique on parameters such as solvent and solution concentration, spinning speed and support material was studied. The same preparation method also allowed the acquisition of valence band spectra, the main peaks of which were clearly resolved. The results suggest that use of the spin coating techniqu...

  6. Core formation in silicate bodies (United States)

    Nimmo, F.; O'Brien, D. P.; Kleine, T.


    Differentiation of a body into a metallic core and silicate mantle occurs most efficiently if temperatures are high enough to allow at least the metal to melt [1], and is enhanced if matrix deformation occurs [2]. Elevated temperatures may occur due to either decay of short-lived radio-isotopes, or gravitational energy release during accretion [3]. For bodies smaller than the Moon, core formation happens primarily due to radioactive decay. The Hf-W isotopic system may be used to date core formation; cores in some iron meteorites and the eucrite parent body (probably Vesta) formed within 1 My and 1-4~My of solar system formation, respectively [4]. These formation times are early enough to ensure widespread melting and differentiation by 26Al decay. Incorporation of Fe60 into the core, together with rapid early mantle solidification and cooling, may have driven early dynamo activity on some bodies [5]. Iron meteorites are typically depleted in sulphur relative to chondrites, for unknown reasons [6]. This depletion contrasts with the apparently higher sulphur contents of cores in larger planetary bodies, such as Mars [7], and also has a significant effect on the timing of core solidification. For bodies of Moon-size and larger, gravitational energy released during accretion is probably the primary cause of core formation [3]. The final stages of accretion involve large, stochastic collisions [8] between objects which are already differentiated. During each collision, the metallic cores of the colliding objects merge on timescales of a few hours [9]. Each collision will reset the Hf-W isotopic signature of both mantle and core, depending on the degree to which the impactor core re-equilibrates with the mantle of the target [10]. The re-equilibration efficiency depends mainly on the degree to which the impactor emulsifies [11], which is very uncertain. Results from N-body simulations [8,12] suggest that significant degrees of re- equilibration are required [4,10]. Re

  7. Ferromagnetism in half-metallic quaternary FeVTiAl Heusler compound (United States)

    Bhat, Tahir Mohiuddin; Bhat, Idris Hamid; Yousuf, Saleem; Gupta, Dinesh C.


    The electronic structure and magnetic properties of FeVTiAl quaternary Heusler alloy have been investigated within the density functional theory framework. The material was found completely spin-polarized half-metallic Ferromagnet in the ground state with F-43m structure. The structural stability was further confirmed by calculating different elastic constants in the cubic phase. Present study predicts an energy band gap of 0.72 eV calculated in localized minority spin channel at an equilibrium lattice parameter of 6.0Å. The calculated total spin magnetic moment of 2 µB/f.u. is in agreement with the Slater-Pauling rule for full Heusler alloys.

  8. On the nature of actinide- and lanthanide-metal bonds in heterobimetallic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Vlaisavljevich, Bess; Miro, P.; Cramer, C. J.; Gagliardi, Laura; Infante, I.; Liddle, S. T.


    Eleven experimentally characterized complexes containing heterobimetallic bonds between elements of the f-block and other elements were examined by quantum chemical methods: [(η⁵-C₅H₅)₂(THF)LuRu(η⁵-C₅H₅) (CO)₂], [(η⁵-C₅Me₅)₂(I)ThRu(η⁵-C₅H₅) (CO)₂], [(η⁵-C₅H₅)₂YRe(η⁵-C₅H₅)₂], [{N(CH₂CH₂NSiMe₃)₃}URe(η⁵-C₅H₅)₂], [Y{Ga(NArCh)₂}{C(PPh₂NSiH₃)₂}(CH₃OCH₃)₂], [{N(CH₂CH₂NSiMe₃)₃}U{Ga(NArCH)₂}(THF)], [(η⁵-C₅H₅)₃UGa(η⁵-C₅Me₅)], [Yb(η⁵-C₅H₅){Si(SiMe₃)₃(THF)₂}], [(η⁵-C₅H₅)₃U(SnPh₃)], [(η⁵-C₅H₅)₃U(SiPh₃)], and (Ph[Me]N)₃USi(SiMe₃)₃. Geometries in good agreement with experiment were obtained at the density functional level of theory. The multiconfigurational complete active space self-consistent field method (CASSCF) and subsequent corrections with second order perturbation theory (CASPT2) were applied to further understand the electronic structure of the lanthanide/actinide–metal (or metal–metalloid) bonds. Fragment calculations and energy-decomposition analyses were also performed and indicate that charge transfer occurs from one supported metal fragment to the other, while the bonding itself is always dominated by ionic character.

  9. Perturbed Angular Correlation (PAC)/NMR spectroscopic properties and dynamics of compounds containing metal ions

    DEFF Research Database (Denmark)

    Arcisauskaité, Vaida

    steps towards understanding how Zn(II) reaches its target position in biological systems in vivo and in vitro experiments in aqueous solution, is the detailed investigation of water exchange reactions for Zn(II)(aq). A very advanced (albeit not complete) picture of structure and dynamics of solvated Zn......199mHg PAC and 199Hg NMR spectroscopic properties, nuclear quadrupole coupling constants, Q, asymmetry parameters, , and chemical shifts, , respectively, are the fingerprint of the local molecular and electronic structure, at the probed Hg nuclei. For this reason, these spectroscopic techniques...... compounds in terms of the atomic constituents. The analysis provided a chemophysical interpretation of changes in Vzz upon structural distortions and ligand exchange. The gained insights can be useful when predicting and understanding changes in Q values for Hg binding sites in proteins. One of the first...

  10. Titanium coordination compounds: from discrete metal complexes to metal–organic frameworks

    KAUST Repository

    Assi, Hala


    Owing to their promise in photocatalysis and optoelectronics, titanium based metal–organic frameworks (MOFs) are one of the most appealing classes of MOFs reported to date. Nevertheless, Ti-MOFs are still very scarce because of their challenging synthesis associated with a poor degree of control of their chemistry and crystallization. This review aims at giving an overview of the recent progress in this field focusing on the most relevant existing titanium coordination compounds as well as their promising photoredox properties. Not only Ti-MOFs but also Ti-oxo-clusters will be discussed and particular interest will be dedicated to highlight the different successful synthetic strategies allowing to overcome the still “unpredictable” reactivity of titanium ions, particularly to afford crystalline porous coordination polymers.

  11. Immiscible silicate liquids and phosphoran olivine in Netschaëvo IIE silicate: Analogue for planetesimal core-mantle boundaries (United States)

    Van Roosbroek, Nadia; Hamann, Christopher; McKibbin, Seann; Greshake, Ansgar; Wirth, Richard; Pittarello, Lidia; Hecht, Lutz; Claeys, Philippe; Debaille, Vinciane


    We have investigated a piece of the Netschaëvo IIE iron meteorite containing a silicate inclusion by means of electron microprobe analysis (EMPA) and transmission electron microscopy (TEM). Netschaëvo contains chondrule-bearing clasts and impact melt rock clasts were also recently found. The examined inclusion belongs to the latter and is characterized by a porphyritic texture dominated by clusters of coarse-grained olivine and pyroxene, set in a fine-grained groundmass that consists of new crystals of olivine and a hyaline matrix. This matrix material has a quasi-basaltic composition in the inner part of the inclusion, whereas the edge of the inclusion has a lower SiO2 concentration and is enriched in MgO, P2O5, CaO, and FeO. Close to the metal host, the inclusion also contains euhedral Mg-chromite crystals and small (olivine crystallites containing up to 14 wt% P2O5, amorphous material, and interstitial Cl-apatite crystals. The Si-rich silicate glass globules show a second population of Fe-rich silicate glass droplets, indicating they formed by silicate liquid immiscibility. Together with the presence of phosphoran olivine and quenched Cl-apatite, these textures suggest rapid cooling and quenching as a consequence of an impact event. Moreover, the enrichment of phosphorus in the silicate inclusion close to the metal host (phosphoran olivine and Cl-apatite) indicates that phosphorus re-partitioned from the metal into the silicate phase upon cooling. This probably also took place in pallasite meteorites that contain late-crystallizing phases rich in phosphorus. Accordingly, our findings suggest that oxidation of phosphorus might be a general process in core-mantle environments, bearing on our understanding of planetesimal evolution. Thus, the Netschaëvo sample serves as a natural planetesimal core-mantle boundary experiment and based on our temperature estimates, the following sequence of events takes place: (i) precipitation of olivine (1400-1360 °C), (ii) re

  12. Mbosi: An anomalous iron with unique silicate inclusions (United States)

    Olsen, Edward J.; Clayton, Robert N.; Mayeda, Toshiko K.; Davis, Andrew M.; Clarke, Roy S., Jr.; Wasson, John T.


    The Mbosi iron meteorite contains millimeter size silicate inclusions. Mbosi is an ungrouped iron meteorite with a Ge/Ga ratio >10, which is an anomalous property shared with the five-member IIF iron group, the Eagle Station pallasites and four other ungrouped irons. Neither the IIF group nor the four other ungrouped irons are known to have silicate inclusions. Chips from three Mbosi inclusions were studied, but most of the work concentrated on a whole 3.1 mm circular inclusion. This inclusion consists of a mantle and a central core of different mineralogies. The mantle is partially devitrified quartz-normative glass, consisting of microscopic crystallites of two pyroxenes and plagioclase, which are crystalline enough to give an x-ray powder diffraction pattern but not coarse enough to permit analyses of individual minerals. The core consists of silica. The bulk composition does not match any known meteorite type, although there is a similarity in mode of occurrence to quartz-normative silicate inclusions in some HE irons. Mbosi silicate appears to be unique. The bulk rare earth element (REE) pattern of the mantle is flat at ≅ 7×C1; the core is depleted in REE but shows a small positive Eu anomaly. The O-isotope composition of bulk silicate lies on a unit slope mixing line (parallel and close to the C3 mixing line) that includes the Eagle Station pallasites and the iron Bocaiuva (related to the IIF irons); all of these share the property of having Ge/Ga ratios >10. It is concluded that Mbosi silicate represents a silica-bearing source rock that was melted and injected into metal. Melting occurred early in the history of the parent body because the metal now shows a normal Widmanstätten structure with only minor distortion that was caused when the parent body broke up and released meteorites into interplanetary space. The cause of Ge/Ga ratios being >10 in these irons is unknown. The fact that silicates in Mbosi, Bocaiuva (related to IIF irons) and the Eagle

  13. Steam reforming of biomass gasification tar using benzene as a model compound over various Ni supported metal oxide catalysts. (United States)

    Park, Hyun Ju; Park, Sung Hoon; Sohn, Jung Min; Park, Junhong; Jeon, Jong-Ki; Kim, Seung-Soo; Park, Young-Kwon


    The steam reforming of benzene as a model compound of biomass gasification tar was carried out over various Ni/metal oxide catalysts. The effects of the support, temperature, Ni-precursor, Ni loading and reaction time were examined, and their catalytic performance was compared with that of a commercial Ni catalyst. Among the Ni/metal oxide catalysts used, 15 wt% Ni/CeO(2)(75%)-ZrO(2)(25%) showed the highest catalytic performance owing to its greater redox characteristics and increased surface area, irrespective of the reaction temperature. The catalytic activity of 15 wt% Ni/CeO(2)(75%)-ZrO(2)(25%) was higher than that of the commercial Ni catalyst. Moreover, the catalyst activity was retained due to its excellent resistance to coke deposition even after 5h. The Ni-precursor played a critical role in the catalytic activity. With the exception of nickel nitrate, all the Ni-precursors (chloride and sulfate) caused deactivation of the catalyst.

  14. Bioactivity studies of calcium magnesium silicate prepared from eggshell waste by sol–gel combustion synthesis

    Directory of Open Access Journals (Sweden)

    Rajan Choudhary


    Full Text Available The present study focused on the synthesis of calcium magnesium silicate (akermanite, Ca2MgSi2O7 using eggshell biowaste (as calcium source, magnesium nitrate and tetraethyl orthosilicate (TEOS as starting materials. Sol–gel combustion method was adopted to obtain calcium magnesium silicate. Citric acid was used as a fuel (reducing agent and nitrate ions present in the metal nitrates acts as an oxidizing agent during combustion process. The characterization of synthesized calcium magnesium silicate was carried out by powder X-ray diffraction (XRD, Fourier transform infrared (FTIR and scanning electron microscopy (SEM techniques. Calcium magnesium silicate crystallite size was observed in nano regime which can effectively mimic natural bone apatite composition. In-vitro bioactivity was investigated by immersing calcium magnesium silicate pellet in simulated body fluid (SBF for three weeks. Results show effective deposition of crystallized hydroxyapatite (HAP layer on its surface and predicting its possibilities for applications in hard tissue regeneration.

  15. Toxicity testing of heavy metals with the Rhizobium-legume symbiosis: High sensitivity to cadmium and arsenic compounds. (United States)

    Neumann, H; Bode-Kirchhoff, A; Madeheim, A; Wetzel, A


    Legume root nodules are the site of biological nitrogen fixation in the Rhizobium-legume symbiosis. Nodules are structures unique to this symbiosis and they are morphologically as well as physiologically distinct from other plant organs. Organic substances affecting the macro- or microsymbionts vitality, such as PAHs (WETZEL: et al., 1991), reduce nodulation even before visible damage to the plant can be detected. We present data that the formation of nodules (nodulation) may also serve for ecotoxicological evaluation of heavy metals in different binding states. Tests were performed in petri dishes with alfalfa (lucerne) seedlings inoculated with Rhizobium meliloti. Cultivation took place in growth cabinets with carefully standardized and documented growth conditions. Data from stressed plants was recorded after 14 days of cultivation on contaminated substrate. A dose responsive decrease in nodulation was found after application of cadmium acetate, cadmium iodide, cadmium chloride, sodium salts of arsenate and arsenite, arsenic pentoxide, and lead nitrate, whereas lead acetate showed no effect up to a concentration of 3 microM. The dose response curves were used to calculate EC10, EC50 and EC90 values. EC50 values for cadmium compounds range from 1.5 to 9.5 pM. Testing different arsenic compounds results in EC50 from 2.6 to 20.1 microM. EC50 of lead nitrate is 2.2 microM. The sensitivity, reproducibility and reliability of this test system is discussed compared to established biotests.

  16. Preparation of calcium silicate?chitosan polymer and the adsorptive removal of heavy metals in wastewater%硅酸钙?壳聚糖聚合物制备及其对重金属废水的吸附特性

    Institute of Scientific and Technical Information of China (English)

    吴亚琪; 徐畅; 赵越; 严群


    A solution blending method was adopted to prepare calcium silicate?chitosan polymer in this study, and FT?IR and XRD were used to characterize the polymer adsorbent. In addition, a preliminary study was carried on the adsorbent abilities of chitosan, calcium silicate and calcium silicate?chitosan polymer for heavy metal ions in wastewater. The characterization indicated that crystal structure of the polymer changed and crystallinity decreased during the synthesis process. Adsorbent ability of the polymer was the highest among the three adsorbents and the maximum adsorbent ability for Ni2+, Cu2+, Pb2+, Zn2+and Cr3+reached 167.01, 192.30, 232.47, 174.71 and 162.33 mg·g-1 , respectively. Moreover, it was noteworthy that calcium silicate?chitosan polymer showed a stronger acid resistance for removal of heavy metal ions in wastewater.%使用溶液共混法制备出硅酸钙?壳聚糖聚合物,同时采用FT?IR、XRD等方法对制备的硅酸钙?壳聚糖聚合物进行表征,并分别对壳聚糖、硅酸钙、硅酸钙?壳聚糖聚合物吸附去除重金属废水的特性进行了初步研究.结果表明,硅酸钙?壳聚糖聚合物在制备过程中晶型发生变化,结晶度降低;硅酸钙?壳聚糖聚合物对各重金属离子的吸附能力最强,其对Ni2+、Cu2+、Pb2+、Zn2+、Cr3+的最大吸附量分别为167.01、192.30、232.47、174.71、162.33 mg·g-1;重要的是,硅酸钙?壳聚糖聚合物可在酸性环境下更有效吸附去除废水中重金属离子.

  17. Solvent exfoliation of transition metal dichalcogenides: dispersibility of exfoliated nanosheets varies only weakly between compounds. (United States)

    Cunningham, Graeme; Lotya, Mustafa; Cucinotta, Clotilde S; Sanvito, Stefano; Bergin, Shane D; Menzel, Robert; Shaffer, Milo S P; Coleman, Jonathan N


    We have studied the dispersion and exfoliation of four inorganic layered compounds, WS(2), MoS(2), MoSe(2), and MoTe(2), in a range of organic solvents. The aim was to explore the relationship between the chemical structure of the exfoliated nanosheets and their dispersibility. Sonication of the layered compounds in solvents generally gave few-layer nanosheets with lateral dimensions of a few hundred nanometers. However, the dispersed concentration varied greatly from solvent to solvent. For all four materials, the concentration peaked for solvents with surface energy close to 70 mJ/m(2), implying that all four have surface energy close to this value. Inverse gas chromatography measurements showed MoS(2) and MoSe(2) to have surface energies of ∼75 mJ/m(2), in good agreement with dispersibility measurements. However, this method suggested MoTe(2) to have a considerably larger surface energy (∼120 mJ/m(2)). While surface-energy-based solubility parameters are perhaps more intuitive for two-dimensional materials, Hansen solubility parameters are probably more useful. Our analysis shows the dispersed concentration of all four layered materials to show well-defined peaks when plotted as a function of Hansen's dispersive, polar, and H-bonding solubility parameters. This suggests that we can associate Hansen solubility parameters of δ(D) ∼ 18 MPa(1/2), δ(P) ∼ 8.5 MPa(1/2), and δ(H) ∼ 7 MPa(1/2) with all four types of layered material. Knowledge of these properties allows the estimation of the Flory-Huggins parameter, χ, for each combination of nanosheet and solvent. We found that the dispersed concentration of each material falls exponentially with χ as predicted by solution thermodynamics. This work shows that solution thermodynamics and specifically solubility parameter analysis can be used as a framework to understand the dispersion of two-dimensional materials. Finally, we note that in good solvents, such as cyclohexylpyrrolidone, the dispersions are

  18. Co-transport of metals and organic compounds in geochemical, biochemical and environmental processes

    Energy Technology Data Exchange (ETDEWEB)

    Shock, E.L. [GEOPIG, St. Louis, Washington Univ., MO (United States). Dept. of Earth and Planetary Sciences


    If the environment is defined as consisting of the interdependent processes that enable life to persist, then environmental science begins where geology and biology overlap. It follows that the environmental chemistry emerges from the confluence of geochemistry and biochemistry. With increasing evidence that the biosphere extends well into what has traditionally been considered the sterile geosphere, perhaps even to thousands of meters of the crust (Ghiorse and Wilson, 1988; Pedersen and Ekendahl, 1990; Stevens and McKinley, 1995; Boone et al., 1995), many crustal geochemical processes are being re-evaluated in terms of their potential for supporting life, and microorganisms are increasingly invoked to explain the rates and mechanisms of reactions in geochemical processes (Banfield and Hamers, 1997; Barker et al.,1997; Bazylinski and Moskowitz, 1997; Fortin et al., 1997; Little et al., 1997; McCollom and Shock, 1997; Nordstrom and Southam, 1997; Tebo et al., 1997). Elemental mobility from the geosphere to the hydrosphere, biosphere and atmosphere occurs in surface reactions that are often mediated by microorganisms that actively uptake metals and other nutrients from their surrounding geochemical environments.

  19. Thermal, structural, and magnetic studies of metals and intermetallic compounds. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Wallace, W.E.; Craig, R.S.; Rao, V.U.S.


    The powerful magnetism of certain intermetallics, e.g., SmCo/sub 5/, has been established to originate with the powerful magnetic anisotropy of SmCo/sub 5/, not its large magnetization. The anisotropy is, in turn, a crystal field effect. The crystal field interaction has been elucidated by the method of quantum mechanics. Studies of the systems RFe/sub 2/, RFe/sub 3/, RCo/sub 3/, and R/sub 2/Co/sub 7/ (R = a rare earth, Y or Th) reveals them to be important for hydrogen storage. In addition, important effects associated with hydrogenation of metals have been found--great enhancement of magnetization of certain systems (e.g., ErFe/sub 2/) and substantial increase in superconducting transition temperatures (e.g., Zr/sub .5/H/sub .5/V/sub 2/). Results of studies suggest that the surfaces of rare earth intermetallics are atypical. The spectrum of properties exhibited by the rare earth intermetallics suggests their utility in the efficient capture and storage of solar energy and the use of it for powering a vehicle. These aspects of the systems warrant further attention.

  20. Monitoring of metals, organic compounds and coliforms in water catchment points from the Sinos River basin. (United States)

    Nascimento, C A; Staggemeier, R; Bianchi, E; Rodrigues, M T; Fabres, R; Soliman, M C; Bortoluzzi, M; Luz, R B; Heinzelmann, L S; Santos, E L; Fleck, J D; Spilki, F R


    Unplanned use and occupation of the land without respecting its capacity of assimilation and environmental purification leads to the degradation of the environment and of water used for human consumption. Agricultural areas, industrial plants and urban centres developed without planning and the control of effluent discharges are the main causes of water pollution in river basins that receive all the liquid effluents produced in those places. Over the last decades, environmental management has become part of governmental agendas in search of solutions for the preservation of water quality and the restoration of already degraded resources. This study evaluated the conditions of the main watercourse of the Sinos River basin by monitoring the main physical, chemical and microbiological parameters described in the CONAMA Resolution no. 357/2005.The set of parameters evaluated at five catchment points of water human consumption revealed a river that has different characteristics in each reach, as the upper reach was class 1, whereas the middle and lower reaches of the basin were class 4. Monitoring pointed to households as the main sources of pollutants in those reaches, although metals used in the industrial production of the region were found in the samples analyzed.

  1. Hypervalent Compounds as Ligands: I 3 -Anion Adducts with Transition Metal Pentacarbonyls

    KAUST Repository

    Rogachev, Andrey Yu.


    Just a couple of transition metal complexes of the familiar triiodide anion are known. To investigate the bonding in these, as well as isomeric possibilities, we examined theoretically adducts of I3 - with model organometallic fragments, [Cr(CO)5] and [Mn(CO) 5]+. Bonding energy computations were augmented by a Natural Bond Orbital (NBO) perturbation theory analysis and Energy Decomposition Analysis (EDA). The bonding between I3 - and the organometallic fragment is substantial, especially for the electrostatically driven anion-cation case. "End-on" coordination is favored by 5-13 kcal/mol over "side-on" (to the central I of I3 -), with a ∼10 kcal/mol barrier for isomerization. A developing asymmetry in the I-I bonding of "end-on" coordinated I 3 - led us to consider in some detail the obvious fragmentation to a coordinated I- and free I2. While the signs of incipient fragmentation in that direction are there, these is a definite advantage to maintaining some I- to I2 bonding in triiodide complexes. © 2013 American Chemical Society.

  2. Radioactive and stable metal bioaccumulation, crystalline compound and siderophore detection in Clavariadelphus truncatus

    Energy Technology Data Exchange (ETDEWEB)

    Gaso, M.I. [ININ, Ap. Post. 18-1027, C.P. 11801, Mexico D.F. (Mexico)], E-mail:; Segovia, N. [Instituto de Geofisica, UNAM, Ciudad Universitaria, 04510 Mexico, D.F. (Mexico)], E-mail:; Morton, O. [Instituto de Geofisica, UNAM, Ciudad Universitaria, 04510 Mexico, D.F. (Mexico)], E-mail:; Lopez, J.L. [Instituto de Geografia, UNAM, Ciudad Universitaria, 04510 Mexico, D.F. (Mexico)], E-mail:; Machuca, A. [Departmento Forestal, Universidad de Concepcion, Los Angeles (Chile)], E-mail:; Hernandez, E. [Instituto de Geofisica, UNAM, Ciudad Universitaria, 04510 Mexico, D.F. (Mexico)], E-mail:


    {sup 137}Cs and {sup 40}K activity concentrations and stable elements have been measured in Clavariadelphus truncatus collected in Mexico. Iron-chelating compounds of siderophore-type was also studied in the species. {sup 137}Cs and {sup 40}K were determined in soil and mushroom samples with HpGe gamma-ray spectrometry. Macro- and micro-elemental concentrations were determined by XRF and ICP-MS. Siderophore detection was obtained with a colorimetric assay and X-ray diffraction analysis was performed using a Siemens D5000 diffractometer. {sup 137}Cs geometric mean concentration in C. truncatus was 26 times higher as compared with other Mexican edible mushroom species, while {sup 40}K showed stability. Soil-C. truncatus concentration ratio for {sup 137}Cs and other micro-elements such as Cs, Rb and Pb were also higher than other Mexican edible species. The {sup 137}Cs committed effective dose due to the ingestion of C. truncatus was 8 x 10{sup -6} Sv year{sup -1}. The main crystalline structure found in C. truncatus was D-Mannitol.

  3. 21 CFR 872.6670 - Silicate protector. (United States)


    ... DEVICES DENTAL DEVICES Miscellaneous Devices § 872.6670 Silicate protector. (a) Identification. A silicate protector is a device made of silicone intended to be applied with an absorbent tipped applicator to...

  4. Antibacterial Activity of Silicate Bioceramics

    Institute of Scientific and Technical Information of China (English)

    HU Sheng; NING Congqin; ZHOU Yue; CHEN Lei; LIN Kaili; CHANG Jiang


    Four kinds of pure silicate ceramic particles, CaSiO3, Ca3SiO5, bredigite and akermanite were prepared and their bactericidal effects were systematically investigated. The phase compositions of these silicate ceramics were characterized by XRD. The ionic concentration meas urement revealed that the Calcium (Ca) ion concentration were relatively higher in Ca3SiO5 and bredigite, and much lower in CaSiO3 and akermanite. Accordingly, the pH values of the four silicate ceramics extracts showed a positive correlation with the particle concentrations. Meanwhile, by decreasing the particle size, higher Ca ion concentrations can be achieved, leading to the increase of aqueous pH value as well. In summary, all of the four silicate ceramics tested in our study showed antibacterial effect in a dose-dependent manner. Generally, the order of their antibacterial activity against E.coli from strong to weak is Ca3SiO5, bredigite, CaSiO3 and akermanite.

  5. Rapid and efficient synthesis of alkali metal-C[sub 60] compounds in liquid ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Buffinger, D.R.; Ziebarth, R.P.; Stenger, V.A.; Recchia, C.; Pennington, C.H. (Ohio State Univ., Columbus, OH (United States))


    The reaction of stoichiometric amounts of alkali metals with C[sub 60] in liquid ammonia provides a rapid and quantitative route to M[sub x]C[sub 60] superconductors (M[sub x] = K[sub 3]/, Rb[sub 3]/, CsRb[sub 2], RbCs[sub 2], KRbCs). Annealing of the samples for 24-48 h at 375[degrees]C is required to obtain large superconducting fractions. [sup 13]C and [sup 87]Rb NMR line shapes are reported for Rb[sub 3]C[sub 60]. The [sup 13]C line shapes show the degree of rotational motion of the C[sub 60] ions varies considerably from sample to sample and is dependent on the method of preparation and subsequent heat treatment. A correlation between the degree of rotational motion and the superconducting fraction is noted and attributed to the amount of disorder in the sample. [sup 87]Rb NMR shows three peaks indicating that Rb[sub 3]C[sub 60] actually contains three different cation sites, rather than the two suggested by X-ray powder diffraction data. The third site is occupied by approximately 15% of the Rb ions in Rb[sub 3]C[sub 60] and is shown to be a subset of the tetrahedral sites in the cubic close-packed C[sub 60] lattice. Although the exact nature of the distortion required to produce the third site is unknown, it appears to be unrelated to the orientations of the C[sub 60] ions creating the site. 18 refs., 2 figs.

  6. Synthesis of nanoporous carbohydrate metal-organic framework and encapsulation of selected organic compounds (United States)

    Al-Ghamdi, Saleh

    Cyclodextrin metal organic frameworks (CDMOFs) with different types of cyclodextrins (CDs) (i.e., Alpha, Beta and Gamma-CD) and coordination potassium ion sources (KOH) CDMOF-a and (C7H5KO2) CDMOF-b were synthesized and fully characterized. The physical and thermal properties of the successfully produced CDMOFs were evaluated using N2 gas sorption, thermal gravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The N2 gas sorption isotherm revealed high uptake into the micropores (330 cm3.g -1 for Gamma-CDMOF-a) to macropore (125 cm3.g -1 for Gamma-CDMOF-b) structures with isotherm types I and II for Gamma-CDMOFs and Alpha-CDMOFs, respectively. The Langmuir specific surface area (SSA) of Gamma-CDMOF-a (1376 m2.g-1) was significantly higher than the SSA of Alpha-CDMOF-a (289 m2.g -1) and Beta-CDMOF-a (54 m2.g-1). The TGA of dehydrated CDMOF crystals showed the structures were thermally stable up to 300 °C. The XRD of the Gamma-CDMOFs and Alpha-CDMOFs showed a highly face-centered-cubic symmetrical structure. An Aldol condensation reaction occurred during the encapsulation of acetaldehyde, hexanal, trans-2-hexenal, and ethanol into Gamma-CDMOF-a, with a SSA of 1416 m2.g -1. However, Gamma-CDMOF-b with a SSA of 499 m2.g -1 was successfully used to encapsulate acetaldehyde. The maximum release of acetaldehyde from CDMOF-b was 53 mug of acetaldehyde per g of CDMOF, which is greater than previously reported acetaldehyde encapsulation on Beta-CD inclusion complexes.

  7. Cu-based metal-organic framework/activated carbon composites for sulfur compounds removal (United States)

    Shi, Rui-Hua; Zhang, Zhen-Rong; Fan, Hui-Ling; Zhen, Tian; Shangguan, Ju; Mi, Jie


    MOF-199 was modified by incorporating activated carbon (AC) during its synthesis under hydrothermal conditions to improve its performance in the removal of hydrogen sulfide (H2S) and dimethyl sulfide (CH3SCH3). A variety of different characterization techniques including X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, nitrogen adsorption/desorption isotherms, scanning electron microscopy (SEM), pyridine adsorption infrared spectroscopy (Py-IR), thermogravimetric- mass spectroscopy (TG-MS) and X-ray photoelectron spectroscopy (XPS) were used to analyze the fresh and exhausted composites. It was found that the composites, which have an amount of AC of less than 2%, had the same morphology as those of pristine MOF-199, but exhibited a more ordered crystallinity structure as well as higher surface area. The composite with 2% AC incorporation showed highest sulfur capacity of 8.46 and 8.53% for H2S and CH3SCH3, respectively, which increased by 51 and 41% compared to that of MOF-199. This improvement was attributed to the formation of more micropores and especially the increased number of unsaturated copper metal sites, as revealed by Py-IR. It is suggested the chemical reaction was apparent during adsorption of H2S, which resulted in the formation of CuS and the collapse of the MOF structure. Whereas reversible chemisorption was found for CH3SCH3 adsorption, as testified by TG-MS and fixed-bed regeneration. Exhausted MAC-2 can be almost totally regenerated by high temperature 180 °C nitrogen purge, indicating a promising adsorbent for CH3SCH3 removal.

  8. Complexation by natural heterogeneous compounds: Site occupation distribution functions, a normalized description of metal complexation (United States)

    Buffle, J.; Altmann, R. S.; Filella, M.; Tessier, A.


    This paper presents a new conceptual approach to interpreting titration curves of metal complexation by physically and chemically heterogeneous natural complexants such as humic acids, clays, complete soils, or sediments. The physico-chemical and analytical difficulties encountered with such systems are reviewed by comparison with a system containing only a few simple ligands, followed by discussion of the new approach on the same basis. It is shown that interpretation of heterogeneous complexant properties necessitates a preliminary transformation of experimental raw data into a function sufficiently normalized so as to allow comparison of results obtained under different conditions. A normalized function called a Site Occupation Distribution Function (SODF) and its potential usefulness is described here. The SODF is a readily computable function which relates the complexation buffer intensity of the system to the differential free energy of the complexation sites present. Its major interest is that it enables one to obtain both a rigorous mathematical description of the complexant properties (even when highly heterogeneous) at the macroscopic level and, in certain cases, an estimation of the molecular-scale behavior of particular site types. The relationship of the SODF to other distribution functions proposed in the literature is discussed and applications are exemplified using simulated and real natural systems. In particular, its utility is discussed in detail for (1) discriminating between different site types (major, minor, dominant, background), (2) evaluating the degree of heterogeneity of an unknown complexant system, (3) estimating the nature and true thermodynamic constants of complexes, and (4) yielding a rigorous definition of "complexation capacity."

  9. Metals, organic compounds, and nutrients in Long Island Sound: sources, magnitudes, trends, and impacts (United States)

    Mullaney, John R.; Varekamp, J.C.; MCElroy, A.E.; Brsslin, V.T.


    Long Island Sound (LIS) is a relatively shallow estuary with a mean depth of 20 m (maximum depth 49 m) and a unique hydrology and history of pollutant loading. Those factors have contributed to a wide variety of contamination problems in its muddy sediments, aquatic life and water column. The LIS sediments are contaminated with a host of legacy and more recently released toxic compounds and elements related to past and present wastewater discharges and runoff. These include non-point and storm water runoff and groundwater discharges, whose character has changed over the years along with the evolution of its watershed and industrial history. Major impacts have resulted from the copious amounts of nutrients discharged into LIS through atmospheric deposition (N), domestic and industrial waste water flows, fertilizer releases, and urban runoff. All these sources and their effects are in essence the result of human presence and activities in the watershed, and the severity of pollutant loading and their impacts generally scales with total population in the watersheds surrounding LIS. Environmental legislation passed since the mid-to late 1900s (e.g., Clean Air Act, Clean Water Act) has had a beneficial effect, however, and contaminant loadings for many toxic organic and inorganic chemicals and nutrients have diminished over the last few decades (O’Shea and Brosnan 2000; Trench, et al, 2012; O’Connor and Lauenstein 2006; USEPA 2007). Major strides have been made in reducing the inflow of nutrients into LIS, but cultural eutrophication is still an ongoing problem and nutrient control efforts will need to continue. Nonetheless, LIS is still a heavily human impacted estuary (an ‘Urban Estuary’, as described for San Francisco Bay by Conomos, 1979), and severe changes in water quality and sediment toxicity as well as ecosystem shifts have been witnessed over the relatively short period since European colonization in the early 1600s (Koppelman et al., 1976).

  10. Amended Silicated for Mercury Control

    Energy Technology Data Exchange (ETDEWEB)

    James Butz; Thomas Broderick; Craig Turchi


    Amended Silicates{trademark}, a powdered, noncarbon mercury-control sorbent, was tested at Duke Energy's Miami Fort Station, Unit 6 during the first quarter of 2006. Unit 6 is a 175-MW boiler with a cold-side electrostatic precipitator (ESP). The plant burns run-of-the-river eastern bituminous coal with typical ash contents ranging from 8-15% and sulfur contents from 1.6-2.6% on an as-received basis. The performance of the Amended Silicates sorbent was compared with that for powdered activated carbon (PAC). The trial began with a period of baseline monitoring during which no sorbent was injected. Sampling during this and subsequent periods indicated mercury capture by the native fly ash was less than 10%. After the baseline period, Amended Silicates sorbent was injected at several different ratios, followed by a 30-day trial at a fixed injection ratio of 5-6 lb/MMACF. After this period, PAC was injected to provide a comparison. Approximately 40% mercury control was achieved for both the Amended Silicates sorbent and PAC at injection ratios of 5-6 lbs/MMACF. Higher injection ratios did not achieve significantly increased removal. Similar removal efficiencies have been reported for PAC injection trials at other plants with cold-side ESPs, most notably for plants using medium to high sulfur coal. Sorbent injection did not detrimentally impact plant operations and testing confirmed that the use of Amended Silicates sorbent does not degrade fly ash quality (unlike PAC). The cost for mercury control using either PAC or Amended Silicates sorbent was estimated to be equivalent if fly ash sales are not a consideration. However, if the plant did sell fly ash, the effective cost for mercury control could more than double if those sales were no longer possible, due to lost by-product sales and additional cost for waste disposal. Accordingly, the use of Amended Silicates sorbent could reduce the overall cost of mercury control by 50% or more versus PAC for locations where

  11. Sodium Silicate Behavior in Porous Media Applied for In-Depth Profile Modifications

    Directory of Open Access Journals (Sweden)

    Hossein A. Akhlaghi Amiri


    Full Text Available This paper addresses alkaline sodium silicate (Na-silicate behavior in porous media. One of the advantages of the Na-silicate system is its water-like injectivity during the placement stage. Mixing Na-silicate with saline water results in metal silicate precipitation as well as immediate gelation. This work demonstrated that low salinity water (LSW, sea water diluted 25 times could be used as a pre-flush in flooding operations. A water override phenomenon was observed during gel formation which is caused by gravity segregation. Dynamic adsorption tests in the sand-packed tubes showed inconsiderable adsorbed silicon density (about 8.5 × 10−10 kg/cm3 for a solution with 33 mg/L silicon content, which is less than the estimated mono-layer adsorption density of 1.4 × 10−8 kg/cm3. Na-silicate enhanced water sweep efficiency after application in a dual-permeability sand-pack system, without leak off into the oil-bearing low permeability (LP zone. Field-scale numerical sensitivity studies in a layered reservoir demonstrated that higher permeability and viscosity contrasts and lower vertical/horizontal permeability ratio result in lower Na-silicate leakoff into the matrix. The length of the mixing zone between reservoir water and the injected Na-silicate solution, which is formed by low salinity pre-flush, acts as a buffer zone.

  12. [Neurotoxic occupational substances: I. Metals and their compounds. A literature review of the years 1970 to 1982]. (United States)

    Triebig, G; Büttner, J


    The knowledge of the neurotoxicity to the peripheral nervous system of arsenic, lead, thallium and mercury as well as their compounds is reviewed according to the literature of the period 1970-1982. - First acute and chronic intoxications are described with special reference of the neurological symptoms. Then we review the results of electromyographic, neurophysiological and histological investigations. Field studies in occupationally exposed groups and evaluation of dose-response-relationships are specified in detail. Further the presented results are discussed according to aspects in occupational medicine. The following conclusions can be drawn: Neuropathies after arsenic intoxications are characterized by symmetric sensory symptoms as usually numbness and paresthesiae of the distal extremities, but the neurophysiological and histological studies showed a great variety of results. In a former study a significant dose-response-relationship between arsenic load and evidence of neuropathy in workers was demonstrated. The onset of impairments of the peripheral nervous system caused by chronic lead exposure is discussed controversially. Some reports showed a dose-response-relationship between a slowering of nerve conduction velocities and an increase of the lead body burden. Proposals of threshold values ranged between 50 to 80 micrograms lead/dl blood. Other authors did not confirm these results. Longitudinal studies are, with one exception, not available at present. Thus a relevant evaluation, particularly regarding relevance and prognosis of a mild slowering of nerve conduction velocity, can not be given now. The neurotoxicity of mercury and its compounds is well demonstrated. In case of the metal and the inorganic compounds a direct damage of the peripheral nerve is possible, whereas for organic compounds the pathophysiological mechanism is unclear. Studies concerning dose-response-relationships as well as evaluation of threshold values in chronically exposed

  13. Recovery of rare metal compounds from nickel-metal hydride battery waste and their application to CH4 dry reforming catalyst. (United States)

    Kanamori, Tomohiro; Matsuda, Motohide; Miyake, Michihiro


    The recovery of valuable components such as nickel from nickel-metal hydride (Ni-MH) battery waste by chemical processes and their applications to CH(4) dry reforming catalysts were investigated. Three types of compound, identified by XRD analysis as NiO, CeO(2) and LaCoO(3) phases, were successfully separated from the waste by a series of chemical processes at room temperature using aqueous solutions of HCl, NaOH and NH(3), and Ni component of approximately 70% in Ni-MH battery waste was recovered. The separated NiO, CeO(2) and LaCoO(3) showed catalytic activities for CH(4) dry reforming. In particular, the separated NiO easily reduced to Ni(0) at an initial stage, and exhibited excellent catalytic activity in terms of CH(4) conversion and stability. Furthermore, it was found that the resulting Ni from separated NiO exhibited an anomalous catalysis from the comparison with that from regent NiO.

  14. Multiplet calculations of L2,3 x-ray absorption near-edge structures for 3d transition-metal compounds

    NARCIS (Netherlands)

    de Groot, F.M.F.; Ikeno, H.; Stavitski, E.; Tanaka, I.


    The purpose of this work is to compare the two different procedures to calculate the L2,3 x-ray absorption spectra of transition-metal compounds: (1) the semi-empirical charge transfer multiplet (CTM) approach and (2) the ab initio configuration-interaction (CI) method based on molecular orbitals.

  15. Mineralogical Characterization of Fe-Bearing AGB and Supernova Silicate Grains From the Queen Alexandra Range 99177 Meteorite (United States)

    Nguyen, A. N.; Keller, L. P.; Messenger, S.; Rahman, Z.


    Spectroscopic observations of the circumstellar envelopes of evolved O-rich stars indicate the dust is mostly amorphous silicate with olivine-like compositions. Spectral modeling suggests these grains are Fe-rich [Mg/(Mg+Fe) 0.5], but it is not known whether the Fe is distributed within the silicate matrix or exists as metal inclusions. In contrast, the crystalline silicates are inferred to be extremely Mg-rich [Mg/(Mg+Fe) > 0.95]. The mineralogies and chemical compositions of dust in supernova (SN) remnants are not as well constrained, but abundant silicates of olivine-like and enstatite-like compositions have been fit to the infrared emission features. Silicates in the interstellar medium (ISM) are >99% amor-phous and Fe-bearing. The dearth of crystalline silicates in the ISM requires that some amorphization or destruction mechanisms process these grains.

  16. Effects of ionization on silicate glasses. [Silicate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Primak, W.


    This evaluation of radiation effects in silicate glasses caused by ionization is based on our own investigations, on material collected in our files (reports, articles, and notes), and on a computer literature search through recent issues of Physics Abstracts and Chemical Abstracts (and the apparently pertinent references which appeared). Some of our recent results, available heretofore only in internal correspondence, are presented in some detail. It is concluded that research into the behavior of silicate glasses generally will be required before the specific effects in the radioactive waste storage glasses can be properly understood and evaluated. Two particular neglected areas of investigation are targeted for immediate concern: a kinetic analysis of annealing data and the acquisition of data on effects of irradiation at controlled elevated temperatures.

  17. Half-metallicity and magnetism of the full-Heusler compounds KYX2 (Y=Ti, V, and Cr; X=C, N, and O) (United States)

    Dehghanzadeh, M.; Ahmadian, F.


    The electronic structure and half-metallic (HM) properties of new alloys KYX2 (Y=Ti, V, and Cr; X=C, N, and O) containing transition metals and sp elements were investigated within the density functional theory (DFT) using the self-consistent full-potential linearized augmented plane wave (FPLAPW) method. It was found that these new compounds can be experimentally synthesized because of their negative formation energies. The total energy calculations showed that in all compounds, the stable state structure was a ferromagnetic AlCu2Mn-type structure except for KTiC2 and KTiN2 which were stable in a nonmagnetic (NM) AlCu2Mn-type structure. The KTiO2 in both structures, KCrO2 in AlCu2Mn-type structure, and KVO2 in CuHg2Ti-type structure were half-metallic ferromagnets. KVO2 in AlCu2Mn-type structure was a special case with a ferromagnetic semiconducting behavior. The origin of minority band gaps for KTiO2 in both structures was also studied using the band structure calculations. The total magnetic moments of HM compounds were integer values which were in agreement with Slater-Pauling rule (Mtot=Ztot-12). Furthermore, the regions of half-metallictiy in HM compounds were considerably wider than those of Heusler compounds including transition metals, indicating the high robustness of half-metallicity with variation of lattice constants.

  18. Silicate Composition of the Interstellar Medium

    CERN Document Server

    Fogerty, Shane; Watson, Dan M; Sargent, Benjamin A; Koch, Ingrid


    The composition of silicate dust in the diffuse interstellar medium and in protoplanetary disks around young stars informs our understanding of the processing and evolution of the dust grains leading up to planet formation. Analysis of the well-known 9.7{\\mu}m feature indicates that small amorphous silicate grains represent a significant fraction of interstellar dust and are also major components of protoplanetary disks. However, this feature is typically modelled assuming amorphous silicate dust of olivine and pyroxene stoichiometries. Here, we analyze interstellar dust with models of silicate dust that include non-stoichiometric amorphous silicate grains. Modelling the optical depth along lines of sight toward the extinguished objects Cyg OB2 No. 12 and {\\zeta} Ophiuchi, we find evidence for interstellar amorphous silicate dust with stoichiometry intermediate between olivine and pyroxene, which we simply refer to as "polivene." Finally, we compare these results to models of silicate emission from the Trapez...

  19. Controllable formation of heterotrimetallic coordination compounds: systematically incorporating lanthanide and alkali metal ions into the manganese 12-metallacrown-4 framework. (United States)

    Azar, Michael R; Boron, Thaddeus T; Lutter, Jacob C; Daly, Connor I; Zegalia, Kelcie A; Nimthong, Ruthairat; Ferrence, Gregory M; Zeller, Matthias; Kampf, Jeff W; Pecoraro, Vincent L; Zaleski, Curtis M


    The inclusion of Ln(III) ions into the 12-MC-4 framework generates the first heterotrimetallic complexes of this molecular class. The controllable and deliberate preparations of these compounds are demonstrated through 12 crystal structures of the Ln(III)M(I)(OAc)4[12-MCMn(III)(N)shi-4](H2O)4·6DMF complex, where OAc(-) is acetate, shi(3-) is salicylhydroximate, and DMF is N,N-dimethylformamide. Compounds 1-12 have M(I) as Na(I), and Ln(III) can be Pr(III) (1), Nd(III) (2), Sm(III) (3), Eu(III) (4), Gd(III) (5), Tb(III) (6), Dy(III) (7), Ho(III) (8), Er(III) (9), Tm(III) (10), Yb(III) (11), and Y(III) (12). An example with M(I) = K(I) and Ln(III) = Dy(III) is also reported (Dy(III)K(OAc)4[12-MCMn(III)(N)shi-4](DMF)4·DMF (14)). When La(III), Ce(III), or Lu(III) is used as the Ln(III) ions to prepare the Ln(III)Na(I)(OAc)4[12-MCMn(III)(N)shi-4] complex, the compound Na2(OAc)2[12-MCMn(III)(N)shi-4](DMF)6·2DMF·1.60H2O (13) results. For compounds 1-12, the identity of the Ln(III) ion affects the 12-MCMn(III)(N)shi-4 framework as the largest Ln(III), Pr(III), causes an expansion of the 12-MCMn(III)(N)shi-4 framework as demonstrated by the largest metallacrown cavity radius (0.58 Å for 1 to 0.54 Å for 11), and the Pr(III) causes the 12-MCMn(III)(N)shi-4 framework to be the most domed structure as evident in the largest average angle about the axial coordination of the ring Mn(III) ions (103.95° for 1 to 101.69° for 11). For 14, the substitution of K(I) for Na(I) does not significantly affect the 12-MCMn(III)(N)shi-4 framework as many of the structural parameters such as the metallacrown cavity radius (0.56 Å) fall within the range of compounds 1-12. However, the use of the larger K(I) ion does cause the 12-MCMn(III)(N)shi-4 framework to become more planar as evident in a smaller average angle about the axial coordination of the ring Mn(III) ions (101.35°) compared to the analogous Dy(III)/Na(I) (7) complex (102.40°). In addition to broadening the range of

  20. 3D Online Submicron Scale Observation of Mixed Metal Powder's Microstructure Evolution in High Temperature and Microwave Compound Fields

    Directory of Open Access Journals (Sweden)

    Dan Kang


    Full Text Available In order to study the influence on the mechanical properties caused by microstructure evolution of metal powder in extreme environment, 3D real-time observation of the microstructure evolution of Al-Ti mixed powder in high temperature and microwave compound fields was realized by using synchrotron radiation computerized topography (SR-CT technique; the spatial resolution was enhanced to 0.37 μm/pixel through the designed equipment and the introduction of excellent reconstruction method for the first time. The process of microstructure evolution during sintering was clearly distinguished from 2D and 3D reconstructed images. Typical sintering parameters such as sintering neck size, porosity, and particle size of the sample were presented for quantitative analysis of the influence on the mechanical properties and the sintering kinetics during microwave sintering. The neck size-time curve was obtained and the neck growth exponent was 7.3, which indicated that surface diffusion was the main diffusion mechanism; the reason was the eddy current loss induced by the external microwave fields providing an additional driving force for mass diffusion on the particle surface. From the reconstructed images and the curve of porosity and average particle size versus temperature, it was believed that the presence of liquid phase aluminum accelerated the densification and particle growth.

  1. Metal organic frameworks as sorption media for volatile and semi-volatile organic compounds at ambient conditions (United States)

    Vellingiri, Kowsalya; Szulejko, Jan E.; Kumar, Pawan; Kwon, Eilhann E.; Kim, Ki-Hyun; Deep, Akash; Boukhvalov, Danil W.; Brown, Richard J. C.


    In this research, we investigated the sorptive behavior of a mixture of 14 volatile and semi-volatile organic compounds (four aromatic hydrocarbons (benzene, toluene, p-xylene, and styrene), six C2-C5 volatile fatty acids (VFAs), two phenols, and two indoles) against three metal-organic frameworks (MOFs), i.e., MOF-5, Eu-MOF, and MOF-199 at 5 to 10 mPa VOC partial pressures (25 °C). The selected MOFs exhibited the strongest affinity for semi-volatile (polar) VOC molecules (skatole), whereas the weakest affinity toward was volatile (non-polar) VOC molecules (i.e., benzene). Our experimental results were also supported through simulation analysis in which polar molecules were bound most strongly to MOF-199, reflecting the presence of strong interactions of Cu2+ with polar VOCs. In addition, the performance of selected MOFs was compared to three well-known commercial sorbents (Tenax TA, Carbopack X, and Carboxen 1000) under the same conditions. The estimated equilibrium adsorption capacity (mg.g‑1) for the all target VOCs was in the order of; MOF-199 (71.7) >Carboxen-1000 (68.4) >Eu-MOF (27.9) >Carbopack X (24.3) >MOF-5 (12.7) >Tenax TA (10.6). Hopefully, outcome of this study are expected to open a new corridor to expand the practical application of MOFs for the treatment diverse VOC mixtures.

  2. Highly selective and sensitive detection of metal ions and nitroaromatic compounds by an anionic europium(iii) coordination polymer. (United States)

    Feyisa Bogale, Raji; Ye, Junwei; Sun, Yuan; Sun, Tongxin; Zhang, Siqi; Rauf, Abdul; Hang, Cheng; Tian, Peng; Ning, Guiling


    A luminescent Eu(iii)-based coordination polymer, {[Eu(H2O)5(BTEC)][H(C5H6N2)]·3H2O} () has been synthesized under hydrothermal conditions using 1,2,4,5-benzenetetracarboxylic acid (H4BTEC) as a linker. Compound possesses an anionic zig-zag chain constructed from the BTEC ligands and [EuO4(H2O)5] nodes. The protonated 4-aminopyridine groups as guests are located between chains. exhibits the characteristic sharp emission bands of Eu(3+) at 578, 593, 615, 652 and 693 nm upon excitation at 290 nm. The strong emission of could be quenched effectively by trace amounts of Fe(3+) ions even in the presence of other metal ions including Al(3+), Ca(2+), Cd(2+), Co(2+), Cr(3+), Cu(2+), Fe(2+), K(+), Mg(2+), Mn(2+), Pd(2+) and Zn(2+). Similarly, also exhibits superior selectivity and sensitivity towards 4-nitrophenol (4-NP) compared with other competing interfering analytes, such as 2,4,6-trinitrophenol, 2,6-dinitrotolune, 4-nitrotoluene, nitrobenzene, 1,3-dinitrobenzene, o-xylene, nitromethane, nitropropane, phenol, 4-bromophenol and bromobenzene, through a fluorescence quenching mechanism. The possible fluorescence quenching mechanisms are discussed. Moreover, could be used as a visual fluorescent test paper for selectively detecting trace amounts of Fe(3+) and 4-NP.

  3. 3D online submicron scale observation of mixed metal powder's microstructure evolution in high temperature and microwave compound fields. (United States)

    Kang, Dan; Xu, Feng; Hu, Xiao-fang; Dong, Bo; Xiao, Yu; Xiao, Ti-qiao


    In order to study the influence on the mechanical properties caused by microstructure evolution of metal powder in extreme environment, 3D real-time observation of the microstructure evolution of Al-Ti mixed powder in high temperature and microwave compound fields was realized by using synchrotron radiation computerized topography (SR-CT) technique; the spatial resolution was enhanced to 0.37  μm/pixel through the designed equipment and the introduction of excellent reconstruction method for the first time. The process of microstructure evolution during sintering was clearly distinguished from 2D and 3D reconstructed images. Typical sintering parameters such as sintering neck size, porosity, and particle size of the sample were presented for quantitative analysis of the influence on the mechanical properties and the sintering kinetics during microwave sintering. The neck size-time curve was obtained and the neck growth exponent was 7.3, which indicated that surface diffusion was the main diffusion mechanism; the reason was the eddy current loss induced by the external microwave fields providing an additional driving force for mass diffusion on the particle surface. From the reconstructed images and the curve of porosity and average particle size versus temperature, it was believed that the presence of liquid phase aluminum accelerated the densification and particle growth.

  4. Adsorption of volatile organic compounds by metal-organic frameworks MIL-101: influence of molecular size and shape. (United States)

    Yang, Kun; Sun, Qian; Xue, Feng; Lin, Daohui


    Adsorption of gaseous volatile organic compounds (VOCs) on metal-organic frameworks MIL-101, a novel porous adsorbent with extremely large Langmuir surface area of 5870 m(2)/g and pore volume of 1.85 cm(3)/g, and the influence of VOC molecular size and shape on adsorption were investigated in this study. We observed that MIL-101 is a potential superior adsorbent for the sorptive removal of VOCs including polar acetone and nonpolar benzene, toluene, ethylbeznene, and xylenes. MIL-101 is of higher adsorption capacities for all selected VOCs than zeolite, activated carbon and other reported adsorbents. Adsorption of VOCs on MIL-101 is captured by a pore filling mechanism, showing the size and shape selectivity of VOC molecules. These prove to be a negative linear relationship between the volume adsorption capacities of VOCs and their molecular cross-sectional area values. Most VOC molecules, such as acetone, benzene, toluene, ethylbenzene and p-xylene, enter into MIL-101 pores with the planes having the minimum diameters. However, m-xylene and o-xylene may fill into the pores with the planes having the maximum diameters because of the preferred interaction of MIL-101 with the two methyl groups of adsorbate molecules.

  5. Surface characterization of silicate bioceramics. (United States)

    Cerruti, Marta


    The success of an implanted prosthetic material is determined by the early events occurring at the interface between the material and the body. These events depend on many surface properties, with the main ones including the surface's composition, porosity, roughness, topography, charge, functional groups and exposed area. This review will portray how our understanding of the surface reactivity of silicate bioceramics has emerged and evolved in the past four decades, owing to the adoption of many complementary surface characterization tools. The review is organized in sections dedicated to a specific surface property, each describing how the property influences the body's response to the material, and the tools that have been adopted to analyse it. The final section introduces the techniques that have yet to be applied extensively to silicate bioceramics, and the information that they could provide.

  6. Biogenic silicate accumulation in sediments, Jiaozhou Bay

    Institute of Scientific and Technical Information of China (English)

    LI Xuegang; SONG Jinming; DAI Jicui; YUAN Huamao; LI Ning; LI Fengye; SUN Song


    It has been widely recognized that low silicate content in seawater is a major limiting factor to phytoplankton primary production in Jiaozhou Bay. However the reason of Si-limitation remains poorly understood. In the present study we measured the biogenic silicate content and discussed the accumulation of silicate in Jiaozhou Bay sediment. The results show that the biogenic silica content in the sediment of the Jiaozhou Bay is obviously much higher than those in the Yellow Sea and the Bohai Sea. The BSi:TN ratios and BSi:16P ratios in the sediment are > 1 and the OC:BSi ratio in sediment is lower than these of Redfield ratio (106:16), indicating that the decomposition rate of OC is much higher than that for BSi in similar conditions. Therefore, the majority of the biogenic silicate was buried and thus did not participate in silicate recycling. Silicate accumulation in sediment may explain why Si limits the phytoplankton growth in the Jiaozhou Bay. Comparing the flux of biogenic silicate from sediments with primary production rate, it can be concluded that only 15.5% of biogenic silicate is hydrolyzed during the journey from surface to bottom in seawater, thus approximate 84.5% of biogenic silicate could reach the bottom. The silicate releasing rate from the sediment to seawater is considerably lower than that of sedimentation of biogenic silicate, indicating silicate accumulation in sediment too. In a word, the silicate accumulation in sediment is the key reason of silicate limiting to phytoplankton growth in Jiaozhou Bay.

  7. Longevity of silicate ceramic restorations. (United States)

    Beier, Ulrike Stephanie; Dumfahrt, Herbert


    The demand for esthetic restorations has resulted in an increased use of dental ceramics as a biocompatible and functionally sufficient alternative to conventional restorative materials. Silicate ceramic restorations are widely used for veneers, inlays, onlays, and crowns in dentistry. Long-term data are of crucial importance to optimize clinical practice. The purpose of the present article is to summarize data of the Innsbruck ceramic evaluation up to 261 months with the focus on longevity and failure characteristics.

  8. The stable Cr isotopic compositions of chondrites and silicate planetary reservoirs (United States)

    Schoenberg, Ronny; Merdian, Alexandra; Holmden, Chris; Kleinhanns, Ilka C.; Haßler, Kathrin; Wille, Martin; Reitter, Elmar


    The depletion of chromium in Earth's mantle (∼2700 ppm) in comparison to chondrites (∼4400 ppm) indicates significant incorporation of chromium into the core during our planet's metal-silicate differentiation, assuming that there was no significant escape of the moderately volatile element chromium during the accretionary phase of Earth. Stable Cr isotope compositions - expressed as the ‰-difference in 53Cr/52Cr from the terrestrial reference material SRM979 (δ53/52CrSRM979 values) - of planetary silicate reservoirs might thus yield information about the conditions of planetary metal segregation processes when compared to chondrites. The stable Cr isotopic compositions of 7 carbonaceous chondrites, 11 ordinary chondrites, 5 HED achondrites and 2 martian meteorites determined by a double spike MC-ICP-MS method are within uncertainties indistinguishable from each other and from the previously determined δ53/52CrSRM979 value of -0.124 ± 0.101‰ for the igneous silicate Earth. Extensive quality tests support the accuracy of the stable Cr isotope determinations of various meteorites and terrestrial silicates reported here. The uniformity in stable Cr isotope compositions of samples from planetary silicate mantles and undifferentiated meteorites indicates that metal-silicate differentiation of Earth, Mars and the HED parent body did not cause measurable stable Cr isotope fractionation between these two reservoirs. Our results also imply that the accretionary disc, at least in the inner solar system, was homogeneous in its stable Cr isotopic composition and that potential volatility loss of chromium during accretion of the terrestrial planets was not accompanied by measurable stable isotopic fractionation. Small but reproducible variations in δ53/52CrSRM979 values of terrestrial magmatic rocks point to natural stable Cr isotope variations within Earth's silicate reservoirs. Further and more detailed studies are required to investigate whether silicate

  9. Advances in Synthesis and Application of Metal Phthalocyanine Compounds%酞菁金属化合物的合成与应用进展

    Institute of Scientific and Technical Information of China (English)

    程振华; 蔡婷婷; 陈际海; 周文博; 刘咸尚; 夏道宏


    综述了主要涉及铁、钴、镍、铜和锌等过渡金属元素的酞菁金属化合物的研究进展.在单核酞菁金属合成的基础上,目前主要研究双核及多核酞菁金属的合成方法.在酞菁金属的芳环上引人种类不同、数目不同的各种取代基,能大大改善酞菁金属化合物的物理及化学性能,为酞菁金属新材料的应用提供基础.开发酞菁金属化合物的绿色化学合成路线是今后的发展方向.%Research progresses in synthesis and application of metal phthalocyanine compounds, which mainly includes transition metals, namely Fe, Co, Ni, Cu and Zn, are introduced. The synthesis methods for dinuclear and polynuclear metal phthalocyanine compounds caught more attention now than that for uninuclear one. It is demonstrated that by the introduction of different kinds and different number of substituent groups to the aromatic rings of phthalocyanines, the physical and chemical properties of the metal phthalocyanine compounds are greatly changed, which is more favorable to the application of these new materials. The review points out that the development of the metal phthalocyanine compounds is trending towards green synthetic routes.

  10. Site specific X-ray induced changes in organic and metal organic compounds and their influence on global radiation damage

    Energy Technology Data Exchange (ETDEWEB)

    Heintz, Desiree Ellen


    The aim of this work was to systematically investigate the effects of specific and global X-ray radiation damage to biological samples and obtain a conclusive model to describe the underlying principles. Based on the systematic studies performed in this work, it was possible to propose two conclusive mechanisms to describe X-ray induced photoreduction and global radiation damage. The influence of chemical composition, temperature and solvent on X-ray induced photoreduction was investigated by X-ray Absorption Near Edge Spectroscopy and single crystal X-ray diffraction of two B12 cofactors - cyano- and methylcobalamin - as well as iron(II) and iron(III) complexes. The obtained results revealed that X-ray induced photoreduction is a ligand dependent process, with a redox reaction taking place within the complex. It could further be shown that selective hydrogen abstraction plays an important role in the process of X-ray induced photoreduction. Based on the experimental results of this work, a model to describe X-ray induced photoreduction of metal organic complexes could be proposed. The process of X-ray induced hydrogen abstraction was further investigated in a combined X-ray and neutron diffraction study on the amino acids L-serine and L-alanine, which were used as model compounds for proteins, and the nucleoside deoxythymidine (thymidine) as a model for DNA. A damage mechanism for L-serine could be found. It involves the abstraction of two hydrogen atoms, one from the hydroxyl group and one from the adjacent methylene group. Such a hydrogen abstraction results in the formation of a carbonyl group. X-ray diffraction measurements on cyano- and methylcobalamin as well as on three metal amino acid complexes, containing nickel(II) and copper(II), respectively, were conducted to investigate the contribution of X-ray induced photoreduction to global radiation damage. Results from these measurements combined with the results from L-serine, L-alanine and thymidine allowed

  11. Valence determination of rare earth elements in lanthanide silicates by L 3-XANES spectroscopy (United States)

    Kravtsova, Antonina N.; Guda, Alexander A.; Goettlicher, Joerg; Soldatov, Alexander V.; Taroev, Vladimir K.; Kashaev, Anvar A.; Suvorova, Lyudmila F.; Tauson, Vladimir L.


    Lanthanide silicates have been hydrothermally synthesized using Cu and Ni containers. Chemical formulae of the synthesized compounds correspond to K3Eu[Si6O15] 2H2O, HK6Eu[Si10O25], K7Sm3[Si12O32], K2Sm[AlSi4O12] 0.375H2O, K4Yb2[Si8O21], K4Ce2[Al2Si8O24]. The oxidation state of lanthanides (Eu, Ce, Tb, Sm, Yb) in these silicates has been determined using XANES spectroscopy at the Eu, Ce, Tb, Sm, Yb, L 3- edges. The experimental XANES spectra were recorded using the synchrotron radiation source ANKA (Karlsruhe Institute of Technology) and the X-ray laboratory spectrometer Rigaku R- XAS. By comparing the absorption edge energies and white line intensities of the silicates with the ones of reference spectra the oxidation state of lanthanides Eu, Ce, Tb, Sm, Yb has been found to be equal to +3 in all investigated silicates except of the Ce-containing silicate from the run in Cu container where the cerium oxidation state ranges from +3 (Ce in silicate apatite and in a KCe silicate with Si12O32 layers) to +4 (starting CeO2 or oxidized Ce2O3).

  12. Participation of bacteria in weathering processes of silicates

    Directory of Open Access Journals (Sweden)

    Peter Javorský


    Full Text Available Biological processes presented by the metabolic activity of different species of bacteria adhered at the mineral surfaces are a part of the geochemical processes. These bacteria accelerate, by the production of organic acids into the minerals structural bonds, the leaching of elements and their subsequent and gradual transformation to the secondary minerals. Microbial destructions of silicates are studied in order to processing low-quality mineral raw-materials and the remediation of soils, sediments and waters contaminated by industrial pollutants. The samples of material, used in our research, were obtained at 9 deposits of non-metallic raw-materials in Slovakia. The sediment sample was taken from the area of Baikal Lake. The presence of microorganisms in the matrix most frequently was determined by a subsequent isolation of microorganisms and identification of bacterial species presented in the silicate matrix. The species of Bacillus and Pseudomonas genus were the common representative of the microorganisms.

  13. In situ growth of monodispersed Fe3O4 nanoparticles on graphene for the removal of heavy metals and aromatic compounds. (United States)

    Wu, Hai-Xia; Wu, Jia-Wei; Niu, Zhi-Gang; Shang, Xiu-Li; Jin, Jun


    We report on the efficient removal of heavy metal ions and aromatic compounds from simulated wastewater with a nanocomposite. The nanocomposite was obtained via thermal decomposition of the precursor Fe(acac)3 onto the surface of graphene, modified by diethylenetriamine pentaacetic anhydride through dopamine. It was found that the maximum adsorption capacity of the nanocomposite toward Cu(2+) and naphthalene was 207.9 and 72.2 mg g(-1) respectively, displaying a high efficiency for the removal of heavy metal ions as well as aromatic compounds at pH 7.0 and 293 K. The Langmuir for naphthalene and the Freundlich for the Cu(2+) adsorption isotherms were applicable for describing the removal processes. Furthermore, the nanocomposite was carefully examined by transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, Raman spectra, and UV-vis spectroscopy. This work provides a very efficient, fast and convenient approach to exploring a promising nanocomposite for water treatment.

  14. Data on occurrence of selected trace metals, organochlorines, and semivolatile organic compounds in edible fish tissues from Lake Worth, Fort Worth, Texas, 1999 (United States)

    Moring, J. Bruce


    A public-health assessment conducted for the Texas Department of Health and the Agency for Toxic Substances and Disease Registry concluded that exposure to contaminants through the aquatic food chain is an indeterminate human-health hazard in Lake Worth, Fort Worth, Texas. In 1999, the U.S. Geological Survey, in cooperation with the U.S. Air Force and in collaboration with the Texas Department of Health, collected samples of edible fish tissues from Lake Worth for analysis of selected trace metals, organochlorines, and semivolatile organic compounds to support a human-health risk assessment. Left-side, skin-off fillet samples were collected from 10 individuals each of channel catfish, common carp, freshwater drum (gaspergou), largemouth bass, and white crappie but only from five smallmouth buffalo. The U.S. Geological Survey National Water Quality Laboratory analyzed the samples for 22 trace metals, 40 organochlorine pesticides and polychlorinated biphenyls, and 75 semivolatile organic compounds.

  15. Performance of metal compound on thermolysis and electrolysis on sugar industries waste water treatment: COD and color removal with sludge analysis (batch-experiment) (United States)

    Sahu, Omprakash


    The sugar cane industry is one of the most water demanding industries. Sugar industries consume and generate excess amount of water. The generated water contains organic compounds, which would cause pollution. The aim of this research work is to study the effectiveness of metal compound for treatment of sugar industry waste water by thermolysis and electrolysis process. The result shows ferrous metal catalyst shows 80 and 85 % chemical oxygen demand and color removal at pH 6, optimum mass loading 4 kg/m3, treatment temperature 85 °C and treatment time 9 h. When ferrous material was used as electrode, maximum 81 % chemical oxygen demand and 84 % color removal at pH 6, current density 156 Am-2, treatment time 120 min and anode consumption 0.7 g for 1.5 L wastewater were obtained.

  16. Cumulate Fragments in Silicic Ignimbrites (United States)

    Bachmann, O.; Ellis, B. S.; Wolff, J.


    Increasingly, studies are concluding that silicic ignimbrites are the result of the amalgamation of multiple discrete magma batches. Yet the existence of discrete batches presents a conundrum for magma generation and storage; if silicic magma batches are not generated nearly in situ in the upper crust, they must traverse, and reside within, a thermally hostile environment with large temperature gradients, resulting in low survivability in their shallow magmatic hearths. The Snake River Plain (Idaho, USA) is a type example of this 'multi-batch' assembly with ignimbrites containing multiple populations of pyroxene crystals, glass shards, and crystal aggregates. The ubiquitous crystal aggregates hint at a mechanism to facilitate the existence of multiple, relatively small batches of rhyolite in the upper crust. These aggregates contain the same plagioclase, pyroxene, and oxide mineral compositions as single phenocrysts of the same minerals in their host rocks, but they have significantly less silicic bulk compositions and lack quartz and sanidine, which occur as single phenocrysts in the deposits. This implies significant crystallization followed by melt extraction from mushy reservoir margins. The extracted melt then continues to evolve (crystallizing sanidine and quartz) while the melt-depleted margins provide an increasingly rigid and refractory network segregating the crystal-poor batches of magma. The hot, refractory, margins insulate the crystal-poor lenses, allowing (1) extended residence in the upper crust, and (2) preservation of chemical heterogeneities among batches. In contrast, systems that produce cumulates richer in low-temperature phases (quartz, K-feldspars, and/or biotite) favour remelting upon recharge, leading to less segregation of eruptible melt pockets and the formation of gradationally zoned ignimbrites. The occurrence of similar crystal aggregates from a variety of magmatic lineages suggests the generality of this process.

  17. Geochemical investigations into the retention of reactive carbon compounds for toxic heavy metals. Final report; Geochemische Untersuchungen zur Retention von reaktiven Kohlenstoffverbindungen fuer toxische Schwermetalle. Abschlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Kupsch, H.; Mansel, A.; Crustewitz, C.


    The composition, reactivity and stability of reactive organic carbon compounds adsorbed on geogenic matrices was investigated. The surface deposits of NOM and its dependence on geochemical parameters was investigated in selected geomatrices. The retention of toxic heavy metals on these surface deposits of NOM was investigated in consideration of the presence of hydroxy species and inorganic ligands. The investigations of the reactivity of the NOM species requires analyses of these compounds and of the heavy metals in the ultratracer region. This was possible by means of radiochemical methods that were further developed in the context of this project. Radioactive labeling of identified reactive carbon compounds, e.g. with radioactive iodine, on the one hand, and the use of radioactive Cu, Pb, Hg isotopes on the other hand enabled speciation analyses in the binary systems (heavy metal + geomatrix, heavy metal + reactive carbon compounds, reactive carbon compounds + geomatrix) and especially in the ternary system (heavy metal + geomatrix + reactive carbon compounds) in defined conditions. The special labelling techniques were a precondition for distribution measurements in the near-natural, low concentration range. (orig.) [German] Ziel des Projektes war es, mit der vorhandenen Analytik und Expertise die Zusammensetzung, die Reaktivitaet und die Stabilitaet der auf den geogenen Matrizes sorbierten reaktiven organischen Kohlenstoffverbindungen und die damit verbundenen Stoffumsaetze aufzuklaeren. An ausgewaehlten Geomatrizes wurde die Ausbildung von Oberflaechendepositen des NOM und deren Abhaengigkeit gegenueber geochemischen Parametern untersucht. Unter der Beruecksichtigung der Gegenwart von Hydroxyspezies und anorganischen Liganden wurde die Retention toxischer Schwermetalle an diesen Oberflaechendepositen des NOM untersucht. Die Untersuchungen zur Reaktivitaet der NOM-Spezies setzt eine Analytik dieser Verbindungen und der Schwermetalle im Ultraspurenbereich

  18. Transition metal-free oxidation of benzylic alcohols to carbonyl compounds by hydrogen peroxide in the presence of acidic silica gel

    Directory of Open Access Journals (Sweden)

    Hossein Ghafuri


    Full Text Available Oxidation of alcohols to carbonyl compounds has become an important issue in the process industry as well as many other applications. In this method, various benzylic alcohols were successfully converted to corresponding aldehydes and ketones under transition metal-free condition using hydrogen peroxide in the presence of some amount of catalytic acidic silica gel. Silica gel is inexpensive and available. One of the most important features of this method is its short reaction time.

  19. Nanoscale zinc silicate from phytoliths (United States)

    Qadri, S. B.; Gorzkowski, E. P.; Rath, B. B.; Feng, C. R.; Amarasinghe, R.; Freitas, J. A.; Culbertson, J. C.; Wollmershauser, J. A.


    We report a faster, less expensive method of producing zinc silicate nanoparticles. Such particles are used in high volume to make phosphors and anti-corrosion coatings. The approach makes use of phytoliths (plant rocks), which are microscopic, amorphous, and largely silicate particles embedded in plants, that lend themselves to being easily broken down into nanoparticles. Nanoparticles of Zn2SiO4 were produced in a two stage process. In the refinement stage, plant residue, mixed with an appropriate amount of ZnO, was heated in an argon atmosphere to a temperature exceeding 1400 °C for four to six hours and then heated in air at 650 °C to remove excess carbon. TEM shows 50-100 nm nanoparticles. Raman scattering indicates that only the -Zn2SiO4 crystalline phase was present. X-ray analysis indicated pure rhombohedral R 3 bar phase results from using rice/wheat husks. Both samples luminesced predominantly at 523 nm when illuminated with X-rays or UV laser light.

  20. Silicate condensation in Mira variables

    CERN Document Server

    Gail, Hans-Peter; Pucci, Annemarie


    We study whether the condensation of silicate dust in Mira envelopes could be caused by cluster formation by the abundant SiO molecules. For a simplified model of the pulsational motions of matter in the the outer layers of a Mira variable which is guided by a numerical model for Mira pulsations, the equations of dust nucleation and growth are solved in the co-moving frame of a fixed mass element. It is assumed that seed particles form by clustering of SiO molecules. The calculation of the nucleation rate is based on the experimental data of Nuth and Donn (1982). The quantity of dust formed is calculated by a moment method and the calculation of radiation pressure on the dusty gas is based on a dirty silicate model. Dust nucleation occurs in the model at the upper culmination of the trajectory of a gas parcel where it stays for a considerable time at low temperatures while subsequent dust growth occurs during the descending part of the motion and continues after the next shock reversed motion. It is found tha...

  1. Crystal structure and physical properties of new transition metal based pnictide compounds: LaTM2AsN (TM = Fe, Co, and Ni) (United States)

    Jeong, Sehoon; Matsuishi, Satoru; Bang, Joonho; Hosono, Hideo


    New 3d transition metal-based mixed-pnictide compounds, LaTM2AsN (TM = Fe, Co, and Ni) are synthesized by solid state reactions under a high pressure of 2.5 GPa. These compounds crystallize with an orthorhombic structure (space group Cmcm) containing four formula units per unit cell. The crystal structure consists of an anisotropic network of TMAs3N tetrahedra sharing As-As edges along the in-plane ac direction and N corners along the b-direction, forming a TM honeycomb lattice with a boat-shape conformation bridged by TM-N-TM linear bonds. The temperature dependences of the electrical resistivity and magnetic susceptibility indicate that these crystals are itinerant antiferromagnets exhibiting parasitic ferromagnetism with transition temperatures of 560, 260, and 410 K for TM = Fe, Co, and Ni, respectively. These compounds are expected to be parent materials for new superconductors.

  2. Interstellar Silicate Dust Grain Properties in Distant Galaxies Probed by Quasar Absorption Systems (United States)

    Aller, Monique C.; Kulkarni, Varsha P.; York, Donald G.; Welty, Daniel E.; Vladilo, Giovanni; Som, Debopam


    Dust grains are a fundamental component of the interstellar medium, and significantly impact many of the physical processes driving galaxy evolution, including star formation, and the heating, cooling and ionization of interstellar material. Using the absorption features produced by dust in the spectra of luminous background quasars, it is possible to study the properties of extragalactic interstellar dust grains. We will present results from an ongoing program utilizing existing Spitzer Space Telescope infrared quasar spectra to probe silicate dust grain properties in z<1.4 quasar absorption systems. In combination with complementary ground-based data on associated gas-phase metal absorption lines, we explore connections between the interstellar dust and gas in the quasar absorption systems. Our project yields clear detections of the 10 micron silicate dust absorption feature in the studied systems, as well as detections of the 18 micron silicate dust absorption feature in sources with adequate spectral coverage. Based on measured variations in the breath, peak wavelength, and substructure of the 10 micron absorption features, there appear to be differences in the silicate dust grain properties from system-to-system. We also show indications of trends between the gas-phase metal properties, such as metallicity and gas velocity spread, with the silicate dust grain absorption properties. Support for this work is provided by NASA through an award issued by JPL/Caltech and through NASA grant NNX14AG74G, and from National Science Foundation grants AST-0908890 and AST-1108830 to the University of South Carolina.

  3. First-Principles Prediction of Electronic, Magnetic, and Optical Properties of Co2MnAs Full-Heusler Half-Metallic Compound (United States)

    Bakhshayeshi, A.; Sarmazdeh, M. Majidiyan; Mendi, R. Taghavi; Boochani, A.


    Electronic, magnetic, and optical properties of Co2MnAs full-Heusler compound have been calculated using a first-principles approach with the full-potential linearized augmented plane-wave (FP-LAPW) method and generalized gradient approximation plus U (GGA + U). The results are compared with various properties of Co2MnZ (Z = Si, Ge, Al, Ga, Sn) full-Heusler compounds. The results of our calculations show that Co2MnAs is a half-metallic ferromagnetic compound with 100% spin polarization at the Fermi level. The total magnetic moment and half-metallic gap of Co2MnAs compound are found to be 6.00μ B and 0.43 eV, respectively. It is also predicted that the spin-wave stiffness constant and Curie temperature of Co2MnAs compound are about 3.99 meV nm2 and 1109 K, respectively. The optical results show that the dominant behavior, at energy below 2 eV, is due to interactions of free electrons in the system. Interband optical transitions have been calculated based on the imaginary part of the dielectric function and analysis of critical points in the second energy derivative of the dielectric function. The results show that there is more than one plasmon energy for Co2MnAs compound, with the highest occurring at 25 eV. Also, the refractive index variations and optical reflectivity for radiation at normal incidence are calculated for Co2MnAs. Because of its high magnetic moment, high Curie temperature, and 100% spin polarization at the Fermi level as well as its optical properties, Co2MnAs is a good candidate for use in spintronic components and magnetooptical devices.

  4. Core Formation on Asteroid 4 Vesta: Iron Rain in a Silicate Magma Ocean (United States)

    Kiefer, Walter S.; Mittlefehldt, David W.


    Geochemical observations of the eucrite and diogenite meteorites, together with observations made by NASA's Dawn spacecraft, suggest that Vesta resembles H chondrites in bulk chemical composition, possibly with about 25% of a CM-chondrite like composition added in. For this model, the core is 15% by mass (or 8 volume %) of the asteroid. The abundances of moderately siderophile elements (Ni, Co, Mo, W, and P) in eucrites require that essentially all of the metallic phase in Vesta segregated to form a core prior to eucrite solidification. Melting in the Fe-Ni-S system begins at a cotectic temperature of 940 deg. C. Only about 40% of the total metal phase, or 3-4 volume % of Vesta, melts prior to the onset of silicate melting. Liquid iron in solid silicate initially forms isolated pockets of melt; connected melt channels, which are necessary if the metal is to segregate from the silicate, are only possible when the metal phase exceeds about 5 volume %. Thus, metal segregation to form a core does not occur prior to the onset of silicate melting.

  5. Removal of lead from cathode ray tube funnel glass by generating the sodium silicate. (United States)

    Hu, Biao; Zhao, Shuangshuang; Zhang, Shuhao


    In the disposal of electronic waste, cathode ray tube (CRT) funnel glass is an environmental problem of old television sets. Removal of the lead from CRT funnel glass can prevent its release into the environment and allow its reuse. In this research, we reference the dry progress productive technology of sodium silicate, the waste CRT glass was dealt with sodium silicate frit melted and sodium silicate frit dissolved. Adding a certain amount of Na ₂CO₃to the waste CRT glass bases on the material composition and content of it, then the specific modulus of sodium silicate frit is obtained by melting progress. The silicon, potassium and sodium compounds of the sodium silicate frit are dissolved under the conditions of high temperature and pressure by using water as solvent, which shows the tendency that different temperature, pressure, liquid-solid ratio and dissolving time have effect on the result of dissolving. At 175°C(0.75MPa), liquid-solid ratio is 1.5:1, the dissolving time is 1h, the dissolution rate of sodium silicate frit is 44.725%. By using sodium sulfide to separate hydrolysis solution and to collect lead compounds in the solution, the recovery rate of lead in dissolving reached 100% and we can get clean sodium silicate and high purity of lead compounds. The method presented in this research can recycle not only the lead but also the sodium, potassium and other inorganic minerals in CRT glass and can obtain the comprehensive utilization of leaded glass.

  6. Metal coordination chemistry: removal and recovery of metal compounds from heavy crude and shale oils with multidentate ligands. Annual report, October 1981-October 1982

    Energy Technology Data Exchange (ETDEWEB)

    Fish, R.H.


    The separation and identification by HPLC-GFAA analysis of organic and organoarsenic compounds occurring in oil shale retort and process waters, shale oils and Green River Formation oil shale are described in this report. The molecular characterization of these compounds has given new insight into developing innovative methods for their removal from oil shale retorting products. Catechol (1,2-dihydrocylbenzene) derivatives of both inorganic and organoarsenic compounds may in fact provide the means by which these compounds can be successfully removed from the above mentioned retort products. In addition to model compounds experiments with catechols and characterized inorganic arsenic and organoarsenic compounds, we have also synthesized a polymer that was modified with catechol and are in the process of determining its reactivity with the characterized arsenic compounds. Progress in preparing these catechol-bonded polymers is discussed. In a complimentary study, we have performed molecular characterizations and profile identifications of vanadyl porphyrin and non-porphyrin complexes in various heavy crude petroleums and their asphaltenes by HPLC-GFAA analysis. Results are discussed. (DMC)

  7. The formation of nuggets of highly siderophile elements in quenched silicate melts at high temperatures: Before or during the silicate quench? (United States)

    Malavergne, V.; Charon, E.; Jones, J.; Cordier, P.; Righter, K.; Deldicque, D.; Hennet, L.


    The Highly Siderophile Elements (HSE) are powerful tracers of planetary differentiation. Despite the importance of their partitioning between silicate and metal for the understanding of planetary core formation, especially for the Earth and Mars, there is still a huge discrepancy between conclusions based on different high temperature (HT) experimental studies. These disagreements may be due to the presence of HSE micro and nanonuggets in HT experiments. The formation of these nuggets is still interpreted in different ways. One hypothesis is that these HSE nuggets formed during the quench of the silicate melt, while another hypothesis supposes that these nuggets formed before the quench and represented artefacts of HT experiments. The goal of this work is to clarify whether the presence of HSE nuggets in silicate melts is linked to a quench effect or not. Understanding the formation of these HSE nuggets represents thus a necessary step towards the resolution of the Earth's core formation scenarios. We performed new HT experiments (1275-2000 °C) at different oxygen fugacities (fO2), between ambient air up to ∼5 log units below the Iron-Wüstite buffer [IW-5], for two different silicate compositions (synthetic martian and terrestrial basalts) mixed with a metallic mixture of Pt-Au-Pd-Ru. Our 1275-1600 °C experiments were contained in either olivine, diopside or graphite crucible; experiments at 2000 °C were performed using a levitation method, so no capsule was necessary. Our samples contained quenched silicate melts, minerals (olivine, pyroxene, spinel depending on the run), a two-phase metallic bead and nano and micro-nuggets of HSE. Our samples underwent fine textural, structural and analytical characterizations. The distribution of the nuggets was not homogeneous throughout the quenched silicate melt. HSE nuggets were present within crystals. Dendritic textures from the quenched silicate melt formed around HSE nuggets, which could be crystallized, showing

  8. Silicate sulfidation and chemical differences between enstatite chondrites and Earth (United States)

    Lehner, S. W.; Petaev, M. I.; Buseck, P. R.


    Isotopic similarity between the Earth-Moon system and enstatite chondrites (ECs) led to the idea that ECs were Earth's building blocks [1-3]. However, compared to Earth's mantle, ECs have low Fe0/Fe ratios, are enriched in volatile elements, and depleted in refractory lithophile elements and Mg [4]. Therefore, deriving Earth composition from ECs requires a loss of volatiles during or prior to accretion and sequestering a large fraction of Si in the deep Earth. Alternatively, the isotopic similarity between the Earth and ECs is explained by their formation from a common precursor that experienced different evolutionary paths resulting in the chemical difference [4]. The vestiges of such a precursor are still present in the unequilibrated ECs as FeO-rich silicates with O isotopic compositions identical to bulk ECs and Earth [5]. Conversion of such a precursor into the characteristic EC mineral assemblage requires high-temperature processing in an H-poor environment with high fS2 and fO2 close to that of the classic solar nebula [6], consistent with redox conditions inferred from Ti4+/Ti3+ ratios in EC pyroxene [7]. Under such conditions reaction of FeO-rich silicates with S-rich gas results in their replacement by the assemblage of FeO-poor silicates; Fe, Mg, Ca sulfides; free silica; and Si-bearing Fe,Ni metal alloy. The progressive sulfidation of ferromagnesian silicates in chondrules results in loss of Mg and addition of Fe, Mn, S, Na, K and, perhaps, other volatiles [6]. At the advanced stages of silicate sulfidation recorded in the metal-sulfide nodules [8], a portion of Si is reduced and dissolved in the Fe,Ni metal. This process is known to fractionate Si isotopes [9,10] and would explain the differences between the ECs and Earth's mantle [11]. The sulfidation of silicates also produces porous S-rich silica, a peculiar phase observed so far only in the ECs. It consists of a sinewy SiO2-rich framework enclosing numerous vesicles filled with beam

  9. Silicates materials of high vacuum technology

    CERN Document Server

    Espe, Werner


    Materials of High Vacuum Technology, Volume 2: Silicates covers silicate insulators of special importance to vacuum technology. The book discusses the manufacture, composition, and physical and chemical properties of technical glasses, quartz glass, quartzware, vycor glass, ceramic materials, mica, and asbestos.

  10. Metal complexes of ONO donor Schiff base ligand as a new class of bioactive compounds: synthesis, characterization and biological evolution. (United States)

    Kumar Naik, K H; Selvaraj, S; Naik, Nagaraja


    Present work reviews that, the synthesis of (E)-N'-((7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzohydrazide [L] ligand and their metal complexes. The colored complexes were prepared of type [M(2+)L]X2, where M(2+)=Mn, Co, Ni, Cu, Sr and Cd, L=(7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzohydrazide, X=Cl(-). Ligand derived from the condensation of 8-formyl-7-hydroxy-4-methylcoumarin and benzohydrazide in the molar ratio 1:1 and in the molar ratio 1:2 for metal complexes have been prepared. The chelation of the ligand to metal ions occurs through the both oxygen groups, as well as the nitrogen atoms of the azomethine group of the ligand. Reactions of the Schiff base ligand with Manganese(II), Cobalt(II), Nickel(II), Copper(II), Strontium(II), and Cadmium(II) afforded the corresponding metal complexes. The structures of the obtained ligand and their respective metal complexes were elucidated by infra-red, elemental analysis, Double beam UV-visible spectra, conductometric measurements, magnetic susceptibility measurements and also thermochemical studies. The metal complex exhibits octahedral coordination geometrical arrangement. Schiff base ligand and their metal complexes were tested against antioxidants, antidiabetic and antimicrobial activities have been studied. The Schiff base metal complexes emerges effective α-glucosidase inhibitory activity than free Schiff base ligand.

  11. Metal complexes of ONO donor Schiff base ligand as a new class of bioactive compounds; Synthesis, characterization and biological evolution (United States)

    Kumar Naik, K. H.; Selvaraj, S.; Naik, Nagaraja


    Present work reviews that, the synthesis of (E)-N";-((7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzohydrazide [L] ligand and their metal complexes. The colored complexes were prepared of type [M2+L]X2, where M2+ = Mn, Co, Ni, Cu, Sr and Cd, L = (7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzohydrazide, X = Cl-. Ligand derived from the condensation of 8-formyl-7-hydroxy-4-methylcoumarin and benzohydrazide in the molar ratio 1:1 and in the molar ratio 1:2 for metal complexes have been prepared. The chelation of the ligand to metal ions occurs through the both oxygen groups, as well as the nitrogen atoms of the azomethine group of the ligand. Reactions of the Schiff base ligand with Manganese(II), Cobalt(II), Nickel(II), Copper(II), Strontium(II), and Cadmium(II) afforded the corresponding metal complexes. The structures of the obtained ligand and their respective metal complexes were elucidated by infra-red, elemental analysis, Double beam UV-visible spectra, conductometric measurements, magnetic susceptibility measurements and also thermochemical studies. The metal complex exhibits octahedral coordination geometrical arrangement. Schiff base ligand and their metal complexes were tested against antioxidants, antidiabetic and antimicrobial activities have been studied. The Schiff base metal complexes emerges effective α-glucosidase inhibitory activity than free Schiff base ligand.

  12. Onset of itinerant ferromagnetism associated with semiconductor-metal transition in TiNb1-CoSn half Heusler solid solution compounds

    Indian Academy of Sciences (India)

    M A Kouacou; A A Koua; J T Zoueu; K Konan; J Pierre


    In this paper, the magnetic and transport properties of the TiNb1−CoSn solid solution compounds with half Heusler cubic MgAgAs-type structure have been studied. This work shows the onset of ferromagnetism associated with a semiconductor to metal transition. The transition occurs directly from ferromagnetic metal to semiconducting state as it is the case in the TiCoNi1−Sn series studied previously. A weak quantity of Ti in NbCoSn is sufficient to allow the appearance of ferromagnetic order and metallic state. The variations of the Curie temperature as a function of saturation and effective paramagnetic moments are related to the itinerant ferromagnetism model. A comparison is made with the TiCoSnSb1− series (also studied previously), where the transition from TiCoSn ferromagnetic metal to non-magnetic semiconductor TiCoSb occurs through an intermediate metallic Pauli-like state.

  13. Design and syntheses of electron-transfer photochromic metal-organic complexes using nonphotochromic ligands: a model compound and the roles of its ligands. (United States)

    Zhang, Cui-Juan; Chen, Zi-Wei; Lin, Rong-Guang; Zhang, Ming-Jian; Li, Pei-Xin; Wang, Ming-Sheng; Guo, Guo-Cong


    The model compound [Zn(HCOO)2(4,4'-bipy)] (1; 4,4'-bipy = 4,4'-bipyridine) is selected in this work to demonstrate the effectiveness of our previously proposed design strategy for electron-transfer photochromic metal-organic complexes. The electron-transfer photochromic behavior of 1 has been discovered for the first time. Experimental and theoretical data illustrate that the photochromism of 1 can be attributed to the electron transfer from formato to 4,4'-bipy and the formation of a radical photoproduct. The electron transfer prefers to occur between formato and 4,4'-bipy, which are combined directly by the Zn(II) atoms. A high-contrast (up to 8.3 times) photoluminescence switch occurs during the photochromic process. The similarity of photochromic behaviors among 1 and its analogues as well as viologen compounds has also been found. Photochromic studies of this model compound indicate that new electron-transfer photochromic metal-organic complexes can be largely designed and synthesized by the rational assembly of nonphotochromic electron-donating and electron-accepting ligands.

  14. Separation of heavy metal from water samples--The study of the synthesis of complex compounds of heavy metal with dithiocarbamates. (United States)

    Kane, Sonila; Lazo, Pranvera; Ylli, Fatos; Stafilov, Trajce; Qarri, Flora; Marku, Elda


    The toxicity and persistence of heavy metal (HM) ions may cause several problems to marine organisms and human beings. For this reason, it is growing the interest in the chemistry of sulphur donor ligands such as dithiocarbamates (DDTC), due to their applications particularly in analytical chemistry sciences. The aim of this work has been the study of heavy metal complexes with DDTC and their application in separation techniques for the preconcentration and/or removing of heavy metals from the water solutions or the water ecosystems prior to their analysis. The HM-DDTC complexes were prepared and characterized by elemental analysis, FTIR and UV-Vis spectroscopic methods. The elemental analysis and the yield of the synthesis (97.5-99.9%) revealed a good purity of the complexes. High values of complex formation yields of HM-DDTC complexes is an important parameter for quantitatively removing/and or preconcentration of heavy metal ions from water solution even at low concentration of heavy metals. Significant differences founded between the characteristic parameters of UV/Vis (λmax and ϵmax) and FTIR absorption spectra of the parent DDTC and HM-DDTC complexes revealed the complex formation. The presence of the peaks at the visible spectral zone is important to M(nd(10-m))-L electron charge transfer of the new complexes. The (C=N) (1450-1500 cm(-1)) and the un-splitting (C-S) band (950-1002 cm(-1)) in HM-DDTC FTIR spectra are important to the identification of their bidentate mode (HM[S2CNC4H10]2). The total CHCl3 extraction of trace level heavy metals from water samples after their complex formation with DDTC is reported in this article.

  15. Universality of the high-temperature viscosity limit of silicate liquids

    DEFF Research Database (Denmark)

    Zheng, Qiuju; Mauro, John C.; Ellison, Adam J.;


    We investigate the high-temperature limit of liquid viscosity by analyzing measured viscosity curves for 946 silicate liquids and 31 other liquids including metallic, molecular, and ionic systems. Our results show no systematic dependence of the high-temperature viscosity limit on chemical compos...

  16. A study of H+ production using metal hydride and other compounds by means of laser ion source

    Energy Technology Data Exchange (ETDEWEB)

    Sekine M.; Kondo K.; Okamura, M.; Hayashizaki, N.


    A laser ion source can provide wide variety of ion beams from solid target materials, however, it has been difficult to create proton beam efficiently. We examined capability of proton production using beeswax, polyethylene, and metal hydrides (MgH2 and ZrH2) as target materials. The results showed that beeswax and polyethylene could not be used to produce protons because these targets are transparent to the laser wavelength of 1064 nm. On the other hand, the metal hydrides could supply protons. Although the obtained particle numbers of protons were less than those of the metal ions, the metal hydrides could be used as a target for proton laser ion source.

  17. A study of H{sup +} production using metal hydride and other compounds by means of laser ion source

    Energy Technology Data Exchange (ETDEWEB)

    Sekine, M. [Department of Nuclear Engineering, Tokyo Institute of Technology, Meguro, Tokyo (Japan); Riken, Wako, Saitama (Japan); Kondo, K.; Okamura, M. [Collider-Accelerator Department, Brookhaven National Laboratory, Upton, New York 11973-5000 (United States); Hayashizaki, N. [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, Meguro, Tokyo (Japan)


    A laser ion source can provide wide variety of ion beams from solid target materials, however, it has been difficult to create proton beam efficiently. We examined capability of proton production using beeswax, polyethylene, and metal hydrides (MgH{sub 2} and ZrH{sub 2}) as target materials. The results showed that beeswax and polyethylene could not be used to produce protons because these targets are transparent to the laser wavelength of 1064 nm. On the other hand, the metal hydrides could supply protons. Although the obtained particle numbers of protons were less than those of the metal ions, the metal hydrides could be used as a target for proton laser ion source.

  18. A study of H+ production using metal hydride and other compounds by means of laser ion sourcea) (United States)

    Sekine, M.; Kondo, K.; Okamura, M.; Hayashizaki, N.


    A laser ion source can provide wide variety of ion beams from solid target materials, however, it has been difficult to create proton beam efficiently. We examined capability of proton production using beeswax, polyethylene, and metal hydrides (MgH2 and ZrH2) as target materials. The results showed that beeswax and polyethylene could not be used to produce protons because these targets are transparent to the laser wavelength of 1064 nm. On the other hand, the metal hydrides could supply protons. Although the obtained particle numbers of protons were less than those of the metal ions, the metal hydrides could be used as a target for proton laser ion source.

  19. A study of H+ production using metal hydride and other compounds by means of laser ion source. (United States)

    Sekine, M; Kondo, K; Okamura, M; Hayashizaki, N


    A laser ion source can provide wide variety of ion beams from solid target materials, however, it has been difficult to create proton beam efficiently. We examined capability of proton production using beeswax, polyethylene, and metal hydrides (MgH(2) and ZrH(2)) as target materials. The results showed that beeswax and polyethylene could not be used to produce protons because these targets are transparent to the laser wavelength of 1064 nm. On the other hand, the metal hydrides could supply protons. Although the obtained particle numbers of protons were less than those of the metal ions, the metal hydrides could be used as a target for proton laser ion source.

  20. Fabrication and characterization of nanostructured Fe3S4, an isostructural compound of half-metallic Fe3O4

    KAUST Repository

    Li, Peng


    High-purity, well-crystallized spinel Fe3S4 nanoplatelets were synthesized by the hydrothermal method, and the saturation magnetic moment of Fe3S4 was measured at 1.83 μB/f.u. The temperature-dependent resistivity of Fe3S4 was metallic-like for T < 180 K: room-temperature resistivity was measured at 7.711 × 103  μΩ cm. The anomalous Hall conductivity of Fe3S4 decreased with increasing longitudinal conductivity, in sharp contrast with the accepted theory of the anomalous Hall effect in a dirty-metal regime. Furthermore, negligible spin-dependent magnetoresistance was observed. Band structure calculations confirmed our experimental observations that Fe3S4 is a metal and not a half metal as expected.

  1. Float processing of high-temperature complex silicate glasses and float baths used for same (United States)

    Cooper, Reid Franklin (Inventor); Cook, Glen Bennett (Inventor)


    A float glass process for production of high melting temperature glasses utilizes a binary metal alloy bath having the combined properties of a low melting point, low reactivity with oxygen, low vapor pressure, and minimal reactivity with the silicate glasses being formed. The metal alloy of the float medium is exothermic with a solvent metal that does not readily form an oxide. The vapor pressure of both components in the alloy is low enough to prevent deleterious vapor deposition, and there is minimal chemical and interdiffusive interaction of either component with silicate glasses under the float processing conditions. Alloys having the desired combination of properties include compositions in which gold, silver or copper is the solvent metal and silicon, germanium or tin is the solute, preferably in eutectic or near-eutectic compositions.

  2. Hard X-ray PhotoElectron Spectroscopy of transition metal oxides: Bulk compounds and device-ready metal-oxide interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Borgatti, F., E-mail: [Istituto per lo Studio dei Materiali Nanostrutturati (ISMN), Consiglio Nazionale delle Ricerche (CNR), via P. Gobetti 101, Bologna I-40129 (Italy); Torelli, P.; Panaccione, G. [Istituto Officina dei Materiali (IOM)-CNR, Laboratorio TASC, Area Science Park, Trieste I-34149 (Italy)


    Highlights: • Hard X-ray PhotoElectron Spectroscopy (HAXPES) applied to buried interfaces of systems involving Transition Metal Oxides. • Enhanced contribution of the s states at high kinetic energies both for valence and core level spectra. • Sensitivity to chemical changes promoted by electric field across metal-oxide interfaces in resistive switching devices. - Abstract: Photoelectron spectroscopy is one of the most powerful tool to unravel the electronic structure of strongly correlated materials also thanks to the extremely large dynamic range in energy, coupled to high energy resolution that this form of spectroscopy covers. The kinetic energy range typically used for photoelectron experiments corresponds often to a strong surface sensitivity, and this turns out to be a disadvantage for the study of transition metal oxides, systems where structural and electronic reconstruction, different oxidation state, and electronic correlation may significantly vary at the surface. We report here selected Hard X-ray PhotoElectron Spectroscopy (HAXPES) results from transition metal oxides, and from buried interfaces, where we highlight some of the important features that such bulk sensitive technique brings in the analysis of electronic properties of the solids.

  3. A first-principle investigation of spin-gapless semiconductivity, half-metallicity, and fully-compensated ferrimagnetism property in Mn2ZnMg inverse Heusler compound (United States)

    Wang, Xiaotian; Cheng, Zhenxiang; Khenata, Rabah; Rozale, Habib; Wang, Jianli; Wang, Liying; Guo, Ruikang; Liu, Guodong


    Recently, spin-gapless semiconductors (SGSs) and half-metallic materials (HMMs) have received considerable interest in the fields of materials sciences and solid-state physics because they can provide a high degree of spin polarization in electron transport. The results on band structure calculations reveal that the metallic fully-compensated ferrimagnet (M-FCF) Mn2ZnMg becomes half-metallic fully-compensated ferrimagnet (HM-FCF), fully-compensated ferrimagnetic semiconductor (FCF-S) and fully-compensated ferrimagnetic spin-gapless semiconductor (FCF-SGS) if the uniform strain applied. However, the metallic fully-compensated ferrimagnetism property of the Mn2ZnMg is robust to the tetragonalization. The structure stability based on the calculations of the cohesion energy and the formation energy of this compound has been tested. Furthermore, a magnetic state transition from antiferromagentic (AFM) state to non-magnetic (NM) state can be observed at the lattice constant of 5.20 Å.

  4. Ferromagnetic exchange anisotropy from antiferromagnetic superexchange in the mixed 3d-5d transition-metal compound Sr3CuIrO6. (United States)

    Yin, Wei-Guo; Liu, X; Tsvelik, A M; Dean, M P M; Upton, M H; Kim, Jungho; Casa, D; Said, A; Gog, T; Qi, T F; Cao, G; Hill, J P


    We report a combined experimental and theoretical study of the unusual ferromagnetism in the one-dimensional copper-iridium oxide Sr(3)CuIrO(6). Utilizing Ir L(3) edge resonant inelastic x-ray scattering, we reveal a large gap magnetic excitation spectrum. We find that it is caused by an unusual exchange anisotropy generating mechanism, namely, strong ferromagnetic anisotropy arising from antiferromagnetic superexchange, driven by the alternating strong and weak spin-orbit coupling on the 5d Ir and 3d Cu magnetic ions, respectively. From symmetry consideration, this novel mechanism is generally present in systems with edge-sharing Cu(2+)O(4) plaquettes and Ir(4+)O(6) octahedra. Our results point to unusual magnetic behavior to be expected in mixed 3d-5d transition-metal compounds via exchange pathways that are absent in pure 3d or 5d compounds.

  5. Analytical chemical system for the determination of heavy metals and organic compounds. Annual progress report, December 1, 1978-November 30, 1979

    Energy Technology Data Exchange (ETDEWEB)

    Siggia, S.; Barnes, R.M.


    Progress has been made in the synthesis and characterization of new resins for sequestering inorganic and organic compounds. The capabilities of the poly(dithiocarbamate) resin have been extended, a new poly(acrylamidoxime) resin prepared and characterized, and a series of resins for organic compounds prepared and tested. Limited actual sample analyses have been performed with these resins. A new inductively coupled plasma source, spectrometer, and computer system have been received and they are undergoing tests and installation. With this system in place, the multielement analysis of metals during the forthcoming period will insure the application of sequestering resins to practical analysis of energy-related materials. An automated sample handling and data system has been designed, some components purchased, and construction is scheduled for 1980.

  6. Aromatic hydrogenation with noble metal basis catalysts: support effect on the sensitivity to sulfur compounds; Hidrogenacao de aromaticos com catalisadores a base de metal nobre: efeito do suporte na sensibilidade a compostos sulfurados

    Energy Technology Data Exchange (ETDEWEB)

    Zotin, J.L.; Duarte, M.A.I.; Silva, C.L.T.; Fonseca, D.L.; Costa, D.; Mattos, E.B.C. [PETROBRAS, S.A., Rio de Janeiro, RJ (Brazil). Centro de Pesquisas


    The production of high quality diesel oil, with lower contents of contaminants and better performance, demands a deep hydrogenation of the aromatics compounds present in this fuel. The process for aromatic saturation are usually based on noble metal catalysts which have high activity but are poisoned by sulfur compounds present in petroleum feedstocks. The tio-tolerance of these catalysts is a function, among others factors, of the nature of the metallic phase and its dispersion and of the nature of the support. In this paper, the effect of the support (silica-alumina or zeolite) on the sulfur tolerance of Pt Pd catalysts is studied. The hydrogenation of iso-propylbenzene in presence of sulfur concentration up to 500 ppm was used as model reaction. The catalyst supported on silica-alumina (SA) was 3 times more active than zeolite based catalyst (ZT), in absence of sulfur. However, this latter one was much more tolerant to sulfur poisoning, with an inhibition constant by sulfur 5 times lower than the one obtained for SA catalyst. These results are explained by the higher Broensted acidity of the zeolitic support, which is known to improve the tio-tolerance of metallic catalysts. (author)

  7. Ground state properties and thermoelectric behavior of Ru2VZ (Z=Si, ge, sn) half-metallic ferromagnetic full-Heusler compounds (United States)

    Yalcin, Battal Gazi


    The ground state properties namely structural, mechanical, electronic and magnetic properties and thermoelectric behavior of Ru2VZ (Z=Si, Ge and Sn) half-metallic ferromagnetic full-Heusler compounds are systematically investigated. These compounds are ferromagnetic and crystallize in the Heusler type L21 structure (prototype: Cu2MnAl, Fm-3m 225). This result is confirmed for Ru2VSi and Ru2VSn by experimental work reported by Yin and Nash using high temperature direct reaction calorimetry. The studied materials are half-metallic ferromagnets with a narrow direct band gap in the minority spin channel that amounts to 31 meV, 66 meV and 14 meV for Ru2VSi, Ru2VGe, and Ru2VSn, respectively. The total spin magnetic moment (Mtot) of the considered compounds satisfies a Slater-Pauling type rule for localized magnetic moment systems (Mtot=(NV-24)μB), where NV=25 is the number of valence electrons in the primitive cell. The Curie temperature within the random phase approximation (RPA) is found to be 23 K, 126 K and 447 K for Ru2VSi, Ru2VGe and Ru2VSn, respectively. Semi-classical Boltzmann transport theories have been used to obtain thermoelectric constants, such as Seebeck coefficient (S), electrical (σ/τ) and thermal conductivity (κ/τ), power factor (PF) and the Pauli magnetic susceptibility (χ). ZTMAX values of 0.016 (350 K), 0.033 (380 K) and 0.063 (315 K) are achieved for Ru2VSi, Ru2VGe and Ru2VSn, respectively. It is expected that the obtained results might be a trigger in future experimentally interest in this type of full-Heusler compounds.

  8. Electronic structure, Fermi surface and optical properties of metallic compound Be{sub 8}(B{sub 48})B{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Reshak, A.H. [Institute of Complex Systems, FFPW, CENAKVA, University of South Bohemia in CB, Nove Hrady 37333 (Czech Republic); Center of Excellence Geopolymer and Green Technology, School of Material Engineering, University Malaysia Perlis, 01007 Kangar, Perlis (Malaysia); Azam, Sikander, E-mail: [Institute of Complex Systems, FFPW, CENAKVA, University of South Bohemia in CB, Nove Hrady 37333 (Czech Republic); Alahmed, Z.A. [Department of Physics and Astronomy, King Saud University, Riyadh 11451 (Saudi Arabia); Chyský, Jan [Department of Instrumentation and Control Engineering, Faculty of Mechanical Engineering, CTU in Prague, Technicka 4, 166 07 Prague 6 (Czech Republic)


    The band structure, density of states, electronic charge density, Fermi surface and optical properties for B{sub 8}(Be{sub 48})B{sub 2} compound has been investigated in the support of density functional theory (DFT). The atomic positions of B{sub 8}(Be{sub 48})B{sub 2} compound were optimized by minimization of the forces acting on the atoms using the full potential linear augmented plane wave (FPLAPW) method. We have employed the local density approximation (LDA), generalized gradient approximation (GGA) and Engal-Vosko GGA (EVGGA) to indulgence the exchange correlation potential by solving Kohn–Sham equations. The result shows that the compound is metallic with sturdy hybridization near the Fermi energy level (E{sub F}). The density of states at Fermi energy, N(E{sub F}), is determined by the overlaping between B-p, B-s and Be-s states. This overlaping is strong enough indicating metallic origin with different values of N(E{sub F}). These values are 16.4, 16.27 and 14.89 states/eV, and the corresponding bare linear low-temperature electronic specific heat coefficient (γ) is found to be 2.84, 2.82 and 2.58 mJ/mol K{sup 2} for EVGGA, GGA and LDA respectively. There exists a strong hybridization between B-s and B-p states, also between B-s and Be-p states around the Fermi level. The Fermi surface is composed of three sheets. These sheets consist of set of holes and electrons. The bonding features of the compounds are analyzed using the electronic charge density in the (101 and −101) crystallographic planes and also the analyzing of charge density shows covalent bonding between B and B. The linear optical properties are also deliberated and discussed in particulars. - Highlights: • The compound is metallic. • The density of states at the Fermi energy is calculated. • The bare linear low-temperature electronic specific heat coefficient is obtained. • Fermi surface is composed of three sheets. • The bonding features are analyzed using the electronic

  9. Ion-induced Processing of Cosmic Silicates: A Possible Formation Pathway to GEMS (United States)

    Jäger, C.; Sabri, T.; Wendler, E.; Henning, Th.


    Ion-induced processing of dust grains in the interstellar medium and in protoplanetary and planetary disks plays an important role in the entire dust cycle. We have studied the ion-induced processing of amorphous MgFeSiO4 and Mg2SiO4 grains by 10 and 20 keV protons and 90 keV Ar+ ions. The Ar+ ions were used to compare the significance of the light protons with that of heavier, but chemically inert projectiles. The bombardment was performed in a two-beam irradiation chamber for in situ ion-implantation at temperatures of 15 and 300 K and Rutherford Backscattering Spectroscopy to monitor the alteration of the silicate composition under ion irradiation. A depletion of oxygen from the silicate structure by selective sputtering of oxygen from the surface of the grains was observed in both samples. The silicate particles kept their amorphous structure, but the loss of oxygen caused the reduction of ferrous (Fe2+) ions and the formation of iron inclusions in the MgFeSiO4 grains. A few Si inclusions were produced in the iron-free magnesium silicate sample pointing to a much less efficient reduction of Si4+ and formation of metallic Si inclusions. Consequently, ion-induced processing of magnesium-iron silicates can produce grains that are very similar to the glassy grains with embedded metals and sulfides frequently observed in interplanetary dust particles and meteorites. The metallic iron inclusions are strong absorbers in the NIR range and therefore a ubiquitous requirement to increase the temperature of silicate dust grains in IR-dominated astrophysical environments such as circumstellar shells or protoplanetary disks.

  10. 硅肥施用对重金属污染土壤甘蔗镉吸收的影响研究初探%Preliminary Study on the Effect of Silicate Fertilizers on Cadmium Absorption by Sugarcane in Heavy Metal Polluted Farmland

    Institute of Scientific and Technical Information of China (English)

    郑煜基; 陈能场; 张雪霞; 张晓霞; 冷小艳


    长期采用受铁矿尾矿水污染的河水进行灌溉的农田,其土壤存在一定重金属镉污染,且土壤酸化严重,有效硅活性低。甘蔗是需硅量较大的植物,因此在甘蔗种植过程中施用碱性硅肥既可补充硅营养又可通过硅肥控制镉的吸收。本试验通过硅肥不同施用量及基肥、基肥+追肥的施用方式的比较,结果表明:在甘蔗种植中一次性施用硅肥1500 kg·hm-2,可以使土壤中活性较高的弱酸提取态镉占镉总量的比例从38.45%下降到32.51%,而甘蔗不能利用的残渣态镉的占比从11.19%提高到14.78%;硅肥分为基肥与追肥两次施用的方式,其对土壤镉的形态的影响也存在相似的规律,且变化趋势更加显著,弱酸提取态镉占比从40.93%下降到35.47%,降幅更加显著;同样残渣态镉则随着硅肥施用量的增加而增加,其占比从16.26%增加到22.66%;施用硅肥能有效降低甘蔗汁中镉的含量,从一次性作为基肥施用的结果来看,每公顷施用375~1500 kg硅肥,其蔗汁中镉含量随施肥量增加而下降,从168.54μg·L-1降至57.87μg·L-1,降幅为28.26%~60.30%;蔗渣中镉含量也有相似的变化趋势,从468.36μg·kg-1降至377.77μg·kg-1,降幅为7.86%~19.34%;采用基肥+追肥施用硅肥,无论是蔗汁还是蔗渣,其镉的含量同样随硅肥施用量的增加而下降,蔗汁镉含量的降幅更大,最高可降81.18%,从而达到降低甘蔗汁及蔗渣中镉含量水平的目的。%Farmland irrigated with river water polluted by acid mine drainage from iron ores will become very acidic, toxic with heavy metals like cadmiums and low availability of silicon for plant growth. Sugarcane plants needs a lot of silicon for better growth, thus application of silicate fertilizers not only adjust the low pH, but also supply sugarcane for with silicon for better growth and suppress its uptake of cadmium. Experiments were carried

  11. Carbon Monoxide Silicate Reduction System Project (United States)

    National Aeronautics and Space Administration — The Carbon Monoxide Silicate Reduction System (COSRS) is a novel technology for producing large quantities of oxygen on the Moon. Oxygen yields of 15 kilograms per...

  12. Carbon Monoxide Silicate Reduction System Project (United States)

    National Aeronautics and Space Administration — The Carbon Monoxide Silicate Reduction System (COSRS) is an innovative method that for the first time uses the strong reductant carbon monoxide to both reduce iron...

  13. Characterization of silicate/Si(001) interfaces (United States)

    Copel, M.; Cartier, E.; Narayanan, V.; Reuter, M. C.; Guha, S.; Bojarczuk, N.


    Many of the proposed high permittivity gate dielectrics for silicon-based microelectronics rely on a stack configuration, with an SiO2 buffer layer to provide an interface. We describe a means for creating gate dielectrics with a direct yttrium silicate-silicon interface through the solid-state reaction of yttria and silicon oxynitride, avoiding the preparation of an oxide-free silicon surface. Characterization by medium-energy ion scattering indicates complete consumption of the underlying oxide through silicate formation during high-temperature annealing. Furthermore, the silicate dielectric exhibits small flat-band voltage shifts, indicating low quantities of charge, without passivation steps. Creation of a silicate-silicon interfaces by a simple route may enable the study of an alternate class of dielectrics.

  14. Surface half-metallicity of half-Heusler compound FeCrSe and interface half-metallicity of FeCrSe/GaP (United States)

    Khalaf Al-zyadi, Jabbar M.; Jolan, Mudhahir H.; Yao, Kai-Lun


    Recent studies showed that half-Heusler FeCrSe exhibits half-metallic ferromagnetism (Huang et al. [20]). In this paper, we investigate extensively the electronic, magnetic, and half-metallic properties of the half-Heusler alloy FeCrSe (111) and (001) surfaces and the interface with GaP (111) substrate by using the first-principles calculations within the density functional theory. The atomic density of states demonstrates that the half-me tallicity verified in the bulk FeCrSe is maintained at the CrSe-terminated (001) and Se-terminated (111) surfaces, but lost at both Cr- and Fe-terminated (111) surfaces and the Fe-terminated (001) surface. Alternatively, for the interface of FeCrSe/GaP (111), the bulk half-metallicity is destroyed at Se-P configuration while Se-Ga interface and subinterface show nearly 100% spin polarization. Moreover, the calculated interfacial adhesion energies exhibit that Se-Ga shape is more stable than the Se-P one. The calculated magnetic moments of Se, Ga at the Se-Ga (111) interface and P at the Se-P (111) interface increase with respect to the corresponding bulk values while the atomic magnetic moment of Se atom at the Se-P (111) interface decreases. We also notice that the magnetic moments of subinterface Fe at both Se-Ga and Se-P (111) interfaces decrease compared to the bulk values.

  15. Reductive surface synthesis of gold nanoparticles on silicate glass and their biochemical sensor applicationsa


    M. Li; Kim, D.-P.; Jeong, G.-Y.; Seo, D.-K.; Park, C.-P.


    Gold nanoparticles (Au NPs) were directly synthesized on the surface of polyvinylsilazane (PVSZ, -[(vinyl)SiH-NH2]-) without use of extra reductive additives. The reductive Si-H functional groups on the surface of cured PVSZ acted as surface bound reducing agents to form gold metal when contacted with an aqueous Au precursor (HAuCl4) solution, leading to formation of Au NPs adhered to silicate glass surface. The Au NPs-silicate platforms were preliminarily tested to detect Rhodamine B (1 μM) ...

  16. Electrophoretic deposition of calcium silicate-reduced graphene oxide composites on titanium substrate

    DEFF Research Database (Denmark)

    Mehrali, Mehdi; Akhiani, Amir Reza; Talebian, Sepehr


    silicate-reduced graphene oxide (CS-rGO) composites were synthesized, using an in situ hydrothermal method. CS nanowires were uniformly decorated on the rGO, with an appropriate interfacial bonding. The CS-rGO composites behaved like hybrid composites when deposited on a titanium substrate by cathodic......Calcium silicate (CS)/graphene coatings have been used to improve the biological and mechanical fixation of metallic prosthesis. Among the extraordinary features of graphene is its very high mechanical strength, which makes it an attractive nanoreinforcement material for composites. Calcium...

  17. Reinterpretation of reduction potential measurements done by linear sweep voltammetry in silicate melts (United States)

    Colson, R. O.; Haskin, L. A.; Keedy, C. R.


    The equilibrium concentrations of Ni between silicate melt and Pt were determined experimentally as a function of oxygen fugacity. The results demonstrate that metallic species derived in linear sweep voltammetry experiments in silicate melts are diffusing into Pt electrodes and not into the melt, as was concluded by previoius studies. This requires reinterpretation of previous linear sweep voltammetry results and recalculation and correction of reported reduction potentials. This paper reports these corrected reduction potentials. Also reported are the activity coefficients for Ni in synthetic basalt and diopsidic melts and for Co in diopsidic melt.

  18. Experimental bond critical point and local energy density properties determined for Mn-O, Fe-O, and Co-O bonded interactions for tephroite, Mn2SiO4, fayalite, Fe2SiO4, and Co2SiO4 olivine and selected organic metal complexes: comparison with properties calculated for non-transition and transition metal M-O bonded interactions for silicates and oxides. (United States)

    Gibbs, G V; Downs, R T; Cox, D F; Rosso, K M; Ross, N L; Kirfel, A; Lippmann, T; Morgenroth, W; Crawford, T D


    Bond critical point (bcp) and local energy density properties for the electron density (ED) distributions, calculated with first-principle quantum mechanical methods for divalent transition metal Mn-, Co-, and Fe-containing silicates and oxides are compared with experimental model ED properties for tephroite, Mn 2SiO 4, fayalite, Fe 2SiO 4, and Co 2SiO 4 olivine, each determined with high-energy synchrotron single-crystal X-ray diffraction data. Trends between the experimental bond lengths, R(M-O), (M = Mn, Fe, Co), and the calculated bcp properties are comparable with those observed for non-transition M-O bonded interactions. The bcp properties, local total energy density, H( r c), and bond length trends determined for the Mn-O, Co-O, and Fe-O interactions are also comparable. A comparison is also made with model experimental bcp properties determined for several Mn-O, Fe-O, and Co-O bonded interactions for selected organometallic complexes and several oxides. Despite the complexities of the structures of the organometallic complexes, the agreement between the calculated and model experimental bcp properties is fair to good in several cases. The G( r c)/rho( r c) versus R(M-O) trends established for non-transition metal M-O bonded interactions hold for the transition metal M-O bonded interactions with G( r c)/rho( r c) increasing in value as H( r c) becomes progressively more negative in value, indicating an increasing shared character of the interaction as G( r c)/rho( r c) increases in value. As observed for the non-transition metal M-O bonded interactions, the Laplacian, nabla (2)rho( r c), increases in value as rho( r c) increases and as H( r c) decreases and becomes progressive more negative in value. The Mn-O, Fe-O, and Co-O bonded interactions are indicated to be of intermediate character with a substantial component of closed-shell character compared with Fe-S and Ni-S bonded interactions, which show greater shared character based on the | V( r c)|/ G( r c

  19. Polycyclic aromatic compounds (PAHs and oxygenated PAHs) and trace metals in fish species from Ghana (West Africa): bioaccumulation and health risk assessment. (United States)

    Bandowe, Benjamin A Musa; Bigalke, Moritz; Boamah, Linda; Nyarko, Elvis; Saalia, Firibu Kwesi; Wilcke, Wolfgang


    We report the concentrations of 28 PAHs, 15 oxygenated PAHs (OPAHs) and 11 trace metals/metalloids (As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Se, and Zn) in muscle and gut+gill tissues of demersal fishes (Drapane africana, Cynoglossus senegalensis and Pomadasys peroteti) from three locations along the coast of the Gulf of Guinea (Ghana). The concentrations of ∑28PAHs in muscle tissues averaged 192ngg(-1) dw (range: 71-481ngg(-1) dw) and were not statistically different between locations. The concentrations of ∑28 PAHs were higher in guts+gills than in muscles. The PAH composition pattern was dominated by low molecular weight compounds (naphthalene, alkyl-naphthalenes and phenanthrene). All fish tissues had benzo[a]pyrene concentrations lower than the EU limit for food safety. Excess cancer risk from consumption of some fish was higher than the guideline value of 1×10(-6). The concentrations of ∑15 OPAHs in fish muscles averaged 422ngg(-1) dw (range: 28-1715ngg(-1)dw). The ∑15 OPAHs/∑16 US-EPA PAHs concentration ratio was >1 in 68% of the fish muscles and 100% of guts+gills. The log-transformed concentrations of PAHs and OPAHs in muscles, guts+gills were significantly (ptrace metal concentrations in the fish tissues were in the medium range when compared to fish from other parts of the world. The concentrations of some trace metals (Cd, Cu, Fe, Mn, Zn) were higher in guts+gills than in muscle tissues. The target hazard quotients for metals weretrace metals content) is minimal. Copyright © 2014 Elsevier Ltd. All rights reserved.


    NARCIS (Netherlands)

    Kerssemakers, J.W J; de Hosson, J.T.M.


    Various layered transition metal dichalcogenides were scanned with an optical-lever atomic force microscope (AFM). The microscopic images indicate the occurrence of strong lateral stick-slip effects. In this letter, two models are presented to describe the observations due to stick-slip, i.e.,


    NARCIS (Netherlands)

    Kerssemakers, J.W J; de Hosson, J.T.M.


    Various layered transition metal dichalcogenides were scanned with an optical-lever atomic force microscope (AFM). The microscopic images indicate the occurrence of strong lateral stick-slip effects. In this letter, two models are presented to describe the observations due to stick-slip, i.e., eithe

  2. Atomic force microscopy imaging of transition metal layered compounds : A two-dimensional stick–slip system

    NARCIS (Netherlands)

    Kerssemakers, J.; Hosson, J.Th.M. De


    Various layered transition metal dichalcogenides were scanned with an optical-lever atomic force microscope (AFM). The microscopic images indicate the occurrence of strong lateral stick–slip effects. In this letter, two models are presented to describe the observations due to stick–slip, i.e., eithe

  3. Determination of carbon in uranium and its compounds; Determinacion de carbono en uranio metal y sus compuestos

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Garcia, M. M.


    This paper collects the analytical methods used our laboratories for the determination of carbon in uranium metal, uranate salts and the oxides, fluorides and carbides of uranium. The carbon is usually burned off in a induction or resistance oven under oxygen flow. The CO{sub 2} is collected in barite solution. Where it is backtitrated with potassium biphthalate. (Author)

  4. Synthesis of azomethine macrocycles by condensation of dicarbonyl compounds with diamines without using metal ions as template agents

    Energy Technology Data Exchange (ETDEWEB)

    Borisova, Natalia E; Reshetova, Marina D; Ustynyuk, Yuri A [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation)


    Different strategies for the synthesis of symmetrical and unsymmetrical macrocyclic Schiff bases in the absence of metal ions are considered. General methods for performing macrocyclisation under thermodynamic or kinetic control are analysed. The key factors influencing the structure of macrocyclic azomethines are discussed.

  5. Solid state 1D and 2D NMR spectroscopic investigations of conformational changes of metal phytate compounds (United States)

    Phytate (myo-inositol-1,2,3,4,5,6-hexakisphosphate) (IP6) is the major organic phosphorus component in ceral grains, legumes and seeds high in oil. The high chelating ability of phytate decreases the nutritional availabilty of dietary metal ions (e.g., Ca2+, Fe3+ and Zn2+). Phytate could also decrea...

  6. The effect of sulfide dissolved in silicate melts on enhancing the solubility of the Highly Siderophile Elements (United States)

    O'Neill, H. S.


    There are large inconsistencies among experimental studies of Highly Siderophile Element (HSE) partitioning relations between silicates and metal or sulfide phases, which has usually been attributed to "micronuggets", a general term for sub-optical (approximately HSE sulfide-melt/silicate-melt partition coefficients, where results range over several orders of magnitude. Moreover, nearly all the reported results of directly determined sulfide-melt/silicate-melt partition coefficients are considerably lower than values calculated by combining metal/silicate-melt with metal/sulfide-melt partition coefficients. This discrepancy has been attributed to large effects of S dissolved as sulfide in the silicate melts on HSE solubilities. As such large effects are not expected from the thermodynamic modeling of sulfide solubilities in silicate melts, it has been proposed that HSEs dissolve in sulfide-containing silicate melts by forming HSE-S complexes. This idea has been tested by experiments that compare the solubilities of Ir, Re and Ru in a high-TiO2 silicate melt both with and without dissolved sulfide at 1400 to 1600ºC at atmospheric pressure. The high TiO2 suppresses micronuggets. Experiments were analysed by LA-ICP-MS, with detection limits approaching 2 ppb. For Ir, the results show that at fO2 low enough to enable measurable sulfide in the melt, the presence of the sulfide just raises the level of dissolved Ir above detection limits. These results suggest a fairly large influence of the sulfide, but are not quantitative. By contrast, the experiments on Ru and Re clearly show only a modest effect of dissolved sulfide.

  7. Thermodynamics and Kinetics of Silicate Vaporization (United States)

    Jacobson, Nathan S.; Costa, Gustavo C. C.


    Silicates are a common class of materials that are often exposed to high temperatures. The behavior of these materials needs to be understood for applications as high temperature coatings in material science as well as the constituents of lava for geological considerations. The vaporization behavior of these materials is an important aspect of their high temperature behavior and it also provides fundamental thermodynamic data. The application of Knudsen effusion mass spectrometry (KEMS) to silicates is discussed. There are several special considerations for silicates. The first is selection of an appropriate cell material, which is either nearly inert or has well-understood interactions with the silicate. The second consideration is proper measurement of the low vapor pressures. This can be circumvented by using a reducing agent to boost the vapor pressure without changing the solid composition or by working at very high temperatures. The third consideration deals with kinetic barriers to vaporization. The measurement of these barriers, as encompassed in a vaporization coefficient, is discussed. Current measured data of rare earth silicates for high temperature coating applications are discussed. In addition, data on magnesium-iron-silicates (olivine) are presented and discussed.

  8. Phytoremediation of soils co-contaminated by organic compounds and heavy metals: bioassays with Lupinus luteus L. and associated endophytic bacteria. (United States)

    Gutiérrez-Ginés, M J; Hernández, A J; Pérez-Leblic, M I; Pastor, J; Vangronsveld, J


    In the central part of the Iberian Peninsula there are old sealed landfills containing soils co-contaminated by several heavy metals (Cu, Zn, Pb, Cd, Ni, As, Cr, Fe, Al, Mn) and organic pollutants of different families (hydrocarbons, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, pesticides and other organochlorinated compounds, phenols and volatile compounds), which this work will address. We have focused on phytoremedial plants that are able to deal with this type of complex pollution, not only species that tolerate the joint effect of heavy metals in the soil, but also those that can take advantage of associated bacteria to efficiently break down organic compounds. This study was carried out with Lupinus luteus and its endophytes in two greenhouse experiments: A) growing in a substrate artificially contaminated with benzo(a)pyrene (BaP), and B) using real co-contaminated landfill soils. Endophytes of roots and shoots were isolated in both bioassays. Plant growth-promotion tests and organic pollutant tolerance and degradation tests were conducted on all strains isolated in bioassay A), and on those proving to be pure cultures from bioassay B). The selected landfill is described as are isolation and test procedures. Results indicate that plants did not show toxicity symptoms when exposed to BaP but did when grown in landfill soil. Some endophytes demonstrated plant growth-promotion capacity and tolerance to BaP and other organic compounds (diesel and PCB commercial mixtures). A few strains may even have the capacity to metabolize those organic pollutants. The overall decline in plant growth-promotion capacity in those strains isolated from the landfill soil experiment, compared with those from the bioassay with BaP, may indicate that lupin endophytes are not adapted to metal concentration in roots and shoots and fail to grow. As a result, most isolated root endophytes must have colonized root tissues from the soil. While preliminary degradation tests

  9. Group 11 Metal Compounds with Tripodal Bis(imidazole Thioether Ligands. Applications as Catalysts in the Oxidation of Alkenes and as Antimicrobial Agents

    Directory of Open Access Journals (Sweden)

    Armando Varela-Ramírez


    Full Text Available New group 11 metal complexes have been prepared using the previously described tripodal bis(imidazole thioether ligand (N-methyl-4,5-diphenyl-2-imidazolyl2C(OMeC(CH32S(tert-Bu ({BITOMe,StBu}, 2. The pincer ligand offers a N2S donor atom set that can be used to coordinate the group 11 metals in different oxidation states [AuI, AuIII, AgI, CuI and CuII]. Thus the new compounds [Au{BITOMe,StBu}Cl][AuCl4]2 (3, [Au{BITOMe,StBu}Cl] (4, [Ag{BITOMe,StBu}X] (X = OSO2CF3- 5, PF6- 6 and [Cu{BITOMe,StBu}Cl2] (7 have been synthesized from reaction of 2 with the appropriate metal precursors, and characterized in solution. While attempting characterization in the solid state of 3, single crystals of the neutral dinuclear mixed AuIII-AuI species [Au2{BITOMe,S}Cl3] (8 were obtained and its crystal structure was determined by X-ray diffraction studies. The structure shows a AuIII center coordinated to the pincer ligand through one N and the S atom. The soft AuI center coordinates to the ligand through the same S atom that has lost the tert-butyl group, thus becoming a thiolate ligand. The short distance between the AuI-AuIII atoms (3.383 Å may indicate a weak metal-metal interaction. Complexes 2-7 and the previously described CuI compound [Cu{BITOMe,StBu}]PF6 (9 have been evaluated in the oxidation of biphenyl ethylene with tert-butyl hydrogen peroxide (TBHP as the oxidant. Results have shown that the AuI and AgI complexes 4 and 6 (at 10 mol % loading are the more active catalysts in this oxidative cleavage. The antimicrobial activity of compounds 2-5, 7 and 9 against Gram-positive and Gram-negative bacteria and yeast has also been evaluated. The new gold and silver compounds display moderate to high antibacterial activity, while the copper derivatives are mostly inactive. The gold and silver complexes were also potent against fungi. Their cytotoxic properties have been analyzed in vitro utilizing HeLa human cervical carcinoma cells. The compounds displayed a

  10. Group 11 Metal Compounds with Tripodal Bis(imidazole) Thioether Ligands. Applications as Catalysts in the Oxidation of Alkenes and as Antimicrobial Agents. (United States)

    Liu, Fangwei; Anis, Reema; Hwang, Eunmi; Ovalle, Rafael; Varela-Ramírez, Armando; Aguilera, Renato J; Contel, María


    New group 11 metal complexes have been prepared using the previously described tripodal bis(imidazole) thioether ligand (N-methyl-4,5-diphenyl-2-imidazolyl)2C(OMe)C(CH3)2S(tert-Bu) ({BITOMe,StBu}, 2). The pincer ligand offers a N2S donor atom set that can be used to coordinate the group 11 metals in different oxidation states [AuI, AuIII, AgI, CuI and CuII]. Thus the new compounds [Au{BITOMe,StBu}Cl][AuCl4]2 (3), [Au{BITOMe,StBu}Cl] (4), [Ag{BITOMe,StBu}X] (X = OSO2CF3- 5, PF6- 6) and [Cu{BITOMe,StBu}Cl2] (7) have been synthesized from reaction of 2 with the appropriate metal precursors, and characterized in solution. While attempting characterization in the solid state of 3, single crystals of the neutral dinuclear mixed AuIII-AuI species [Au2{BITOMe,S}Cl3] (8) were obtained and its crystal structure was determined by X-ray diffraction studies. The structure shows a AuIII center coordinated to the pincer ligand through one N and the S atom. The soft AuI center coordinates to the ligand through the same S atom that has lost the tert-butyl group, thus becoming a thiolate ligand. The short distance between the AuI-AuIII atoms (3.383 Å) may indicate a weak metal-metal interaction. Complexes 2-7 and the previously described CuI compound [Cu{BITOMe,StBu}]PF6 (9) have been evaluated in the oxidation of biphenyl ethylene with tert-butyl hydrogen peroxide (TBHP) as the oxidant. Results have shown that the AuI and AgI complexes 4 and 6 (at 10 mol % loading) are the more active catalysts in this oxidative cleavage. The antimicrobial activity of compounds 2-5, 7 and 9 against Gram-positive and Gram-negative bacteria and yeast has also been evaluated. The new gold and silver compounds display moderate to high antibacterial activity, while the copper derivatives are mostly inactive. The gold and silver complexes were also potent against fungi. Their cytotoxic properties have been analyzed in vitro utilizing HeLa human cervical carcinoma cells. The compounds displayed a very

  11. Obtaining half-metallic ferrimagnetism and antiferromagnetism by doping Mn and Fe for DO{sub 3}-type Heusler compound Cr{sub 3}Si

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jia, E-mail: [School of Science, Hebei University of Technology, Tianjin 300130 (China); Liu, Heyan [School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130 (China); Zhang, Zhidong [School of Science, Hebei University of Technology, Tianjin 300130 (China); Zhang, Shaoling; Xu, Xuewen [School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130 (China)


    Highlights: • Six doped Heusler compounds are predicted to be half-metallic magnetism. • New feature of occupation rule for doping 3d transition metal atoms is found. • The uniformity rule of occupation for doped Heusler compound is verified. - Abstract: The electronic structure, magnetic properties and occupation feature of DO{sub 3}-type Heusler compounds (Cr{sub 1−x}Mn{sub x}){sub 3}Si and (Cr{sub 1−x}Fe{sub x}){sub 3}Si (x = n/12, n = 0, 2, 4, 6, 8, 10, 12) have been investigated by first principles calculations. The compounds Cr{sub 3}Si, (Cr{sub 1–4/12}Mn{sub 4/12}){sub 3}Si, Mn{sub 3}Si, (Cr{sub 1–2/12}Fe{sub 2/12}){sub 3}Si, and (Cr{sub 1–6/12}Fe{sub 6/12}){sub 3}Si are predicted to be half-metallic ferrimagnets. The compound (Cr{sub 1–4/12}Fe{sub 4/12}){sub 3}Si is predicted to be half-metallic antiferromagnet, which is applicable to spintronic devices due to its zero magnetization. The Fe atoms of (Cr{sub 1−x}Fe{sub x}){sub 3}Si prefer to occupy the (A,C) sites while the Mn atoms of (Cr{sub 1−x}Mn{sub x}){sub 3}Si tend to occupy the B site, indicating that the occupation of doping atoms is affected strongly by the inter-atom hybridization and the 3d electrons number of doping atoms is not a determining factor. In addition, the results confirm the uniformity rule that the A site is equivalent to C site and the doping atoms prefer to enter the two sublattice uniformly. The more symmetric surroundings of atom coordination in B site in contrast to (A,C) site leads to a typical 3d electronic splitting peaks. The total moment for all the doped compounds (Cr{sub 1−x}Mn{sub x}){sub 3}Si and (Cr{sub 1−x}Fe{sub x}){sub 3}Si agrees well with the Slater–Pauling rule. The coexisting Cr(B) and Cr(A,C) atoms show antiferromagnetic coupling character for both (Cr{sub 1−x}Mn{sub x}){sub 3}Si and (Cr{sub 1−x}Fe{sub x}){sub 3}Si. The coexisting doping Mn(B) and Mn(A,C) atoms show antiferromagnetic coupling character for (Cr{sub 1−x}Mn{sub x

  12. First-principles point defect models in Zr7Ni10 and Zr2Ni7 binary intermetallic compounds and their implications in nickel-metal hydride batteries (United States)

    Wong, Diana F.

    Zr-Ni-based alloys as nickel-metal hydride battery anode materials offer low-cost, flexible and tunable battery performance. Zr7Ni 10 is an important secondary phase found in multi-phased AB2 Laves-phase-based metal hydride alloys, and the synergetic effect between the Zr-Ni and the Laves phases allows access to the high hydrogen storage of the Zr-Ni phases despite the lower absorption/desorption kinetics. Zr7Ni10 displays a small solubility window for Zr-rich compositions, while Zr2Ni7, with no solubility window, shows poor capacity with good kinetics. Stability of point defects within the crystal structure allows Zr7Ni10 to maintain the same structure at off-stoichiometric compositions, thus it is theorized that defects may play a role in the difference between the electrochemical behaviors in Zr7Ni10 and Zr2Ni7. Defect models in Zr7Ni10 and Zr2Ni7 compounds computed using a combination of density functional theory and statistical mechanics offer a starting point for understanding the possible roles that point defects have on the performance of Zr-Ni based active negative electrode materials in Ni/MH batteries. Theoretical vacancy and anti-site defect formation energies are calculated and reported for Zr-rich, Ni-rich, and stoichiometric compounds of Zr7Ni 10 and Zr2Ni7, and the implications of the defect models on nickel-metal hydride negative electrode active material design and performance are discussed.

  13. Removal of organic compounds and trace metals from oil sands process-affected water using zero valent iron enhanced by petroleum coke. (United States)

    Pourrezaei, Parastoo; Alpatova, Alla; Khosravi, Kambiz; Drzewicz, Przemysław; Chen, Yuan; Chelme-Ayala, Pamela; Gamal El-Din, Mohamed


    The oil production generates large volumes of oil sands process-affected water (OSPW), referring to the water that has been in contact with oil sands or released from tailings deposits. There are concerns about the environmental impacts of the release of OSPW because of its toxicity. Zero valent iron alone (ZVI) and in combination with petroleum coke (CZVI) were investigated as environmentally friendly treatment processes for the removal of naphthenic acids (NAs), acid-extractable fraction (AEF), fluorophore organic compounds, and trace metals from OSPW. While the application of 25 g/L ZVI to OSPW resulted in 58.4% removal of NAs in the presence of oxygen, the addition of 25 g petroleum coke (PC) as an electron conductor enhanced the NAs removal up to 90.9%. The increase in ZVI concentration enhanced the removals of NAs, AEF, and fluorophore compounds from OSPW. It was suggested that the electrons generated from the oxidation of ZVI were transferred to oxygen, resulting in the production of hydroxyl radicals and oxidation of NAs. When OSPW was de-oxygenated, the NAs removal decreased to 17.5% and 65.4% during treatment with ZVI and CZVI, respectively. The removal of metals in ZVI samples was similar to that obtained during CZVI treatment. Although an increase in ZVI concentration did not enhance the removal of metals, their concentrations effectively decreased at all ZVI loadings. The Microtox(®) bioassay with Vibrio fischeri showed a decrease in the toxicity of ZVI- and CZVI-treated OSPW. The results obtained in this study showed that the application of ZVI in combination with PC is a promising technology for OSPW treatment. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Combined effects of ultrasonic vibration and manganese on Fe-containing inter-metallic compounds and mechanical properties of Al-17Si alloy with 3wt.%Fe

    Directory of Open Access Journals (Sweden)

    Lin Chong


    Full Text Available The research studied the combined effects of ultrasonic vibration (USV and manganese on the Fe-containing inter-metallic compounds and mechanical properties of Al-17Si-3Fe-2Cu-1Ni (wt.% alloys. The results showed that, without USV, the alloys with 0.4wt.% Mn or 0.8wt.% Mn both contain a large amount of coarse plate-like δ-Al4(Fe,MnSi2 phase and long needle-like β-Al5(Fe,MnSi phase. When the Mn content changes from 0.4wt.% to 0.8wt.% in the alloys, the amount and the length of needle-like β-Al5(Fe,MnSi phase decrease and the plate-like δ-Al4(Fe,MnSi2 phase becomes much coarser. After USV treatment, the Fe-containing compounds in the alloys are refined and exist mainly as δ-Al4(Fe,MnSi2 particles with an average grain size of about 20 μm, and only a small amount of β-Al5(Fe,MnSi phase remains. With USV treatment, the ultimate tensile strengths (UTS of the alloys containing 0.4wt.%Mn and 0.8wt.%Mn at room temperature are 253 MPa and 262 MPa, respectively, and the ultimate tensile strengths at 350 °C are 129 MPa and 135 MPa, respectively. It is considered that the modified morphology and uniform distribution of the Fe-containing inter-metallic compounds, which are caused by the USV process, are the main reasons for the increase in the tensile strength of these two alloys.

  15. Electrophoretic deposition of magnesium silicates on titanium implants: Ion migration and silicide interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Afshar-Mohajer, M. [Center for Advanced Manufacturing and Material Processing, Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur 50603 (Malaysia); Yaghoubi, A., E-mail: [Center for High Impact Research, University of Malaya, Kuala Lumpur 50603 (Malaysia); Ramesh, S., E-mail: [Center for Advanced Manufacturing and Material Processing, Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur 50603 (Malaysia); Bushroa, A.R.; Chin, K.M.C.; Tin, C.C. [Center for Advanced Manufacturing and Material Processing, Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur 50603 (Malaysia); Chiu, W.S. [Low Dimensional Materials Research Center, Department of Physics, University of Malaya, Kuala Lumpur 50603 (Malaysia)


    Magnesium silicates (Mg{sub x}SiO{sub y}) and in particular forsterite (Mg{sub 2}SiO{sub 4}) owing to their low thermal expansion mismatch with metals are promising materials for bioactive coating of implants. Here, we report the electrophoretic deposition (EPD) of forsterite onto titanium substrates using different precursors. Unlike bulk samples which achieve full stoichiometry only beyond 1400 °C, non-stoichiometric magnesium silicate rapidly decomposes into magnesium oxide nanowires during sintering. Elemental mapping and X-ray diffraction suggest that oxygen diffusion followed by ion exchange near the substrate leads to formation of an interfacial Ti{sub 5}Si{sub 3} layer. Pre-annealed forsterite powder on the other hand shows a comparatively lower diffusion rate. Overall, magnesium silicate coatings do not exhibit thermally induced microcracks upon sintering as opposed to calcium phosphate bioceramics which are currently in use.

  16. Modified Mesoporous Silicate MCM-41 for Zinc Ion Adsorption: Synthesis, Characterization and Its Adsorption Behavior

    Institute of Scientific and Technical Information of China (English)



    Modified MCM-41 has been prepared by bi-functionalization of thiol and amino functional groups onto mesoporous silicate MCM-41. Elemental analysis (EA), thermogravimetry analysis (TGA) and FTIR techniques were used to quantify the attachment of the thiol and amino functional groups to the mesoporous silicate pore wall.Powder X-ray diffraction (PXRD) and nitrogen adsorption techniques were used to establish the pore diameter,packing of the pores and specific surface area of the modified mesoporous silicate MCM-41. Adsorption behavior for 18 metal ions on this sorbent has been studied and discussed. This sorbent has high affinity for zinc ions against amino- or thiol-functionalized MCM-41 sorbents.

  17. Empirical evaluation of metal deposition for the analysis of organic compounds with static secondary ion mass spectrometry (S-SIMS) (United States)

    De Mondt, R.; Adriaensen, L.; Vangaever, F.; Lenaerts, J.; Van Vaeck, L.; Gijbels, R.


    Metal-assisted (MetA) SIMS using the deposition of a thin Au or Ag layer on non-conducting samples prior to analysis has been advocated as a means to improve the secondary ion (S.I.) yields of organic analytes. This study focuses on the influence of time and temperature on the yield enhancement in MetA-SIMS using thick layers of poly(vinylbutyral- co-vinylalcohol- co-vinylacetate) (PVB) containing dihydroxybenzophenone (DHBPh) or a cationic carbocyanine dye (CBC) and spin-coated layers of the cationic dye on Si. Pristine samples as well as Au- and Ag-coated ones were kept between -8 °C and 80 °C and analysed with S-SIMS at intervals of a few days over a period of 1 month. The yield enhancement was found to depend strongly on the kind of evaporated metal, the storage temperature and time between coating and analysis.

  18. Molecular characterization of aromatic compound and heavy metal detoxification systems in thermophilic microorganisms: impact on biomonitoring and bioremediation.


    Del Giudice, Immacolata


    Both arsenic and aromatic compounds are naturally present in the environment but human activities, such as the chemical and pharmaceutical industries, use of fossil fuels and pesticides, have contributed to their anomalous accumulation in the biosphere, determining severe damages to all living organisms. Many microorganisms possess tuned mechanisms for sensing the level of pollutants in their growth environment and controlling intracellular concentrations according to their biochemical needs....

  19. Structure determination of a novel metal-organic compound synthesized from aluminum and 2,5-pyridinedicarboxylic acid

    DEFF Research Database (Denmark)

    Ståhl, Kenny; Brink, Bastian; Andersen, Jonas


    The structure of [Al2(pydc)2(μ2-OH)2(H2O)2]n(pydc=2,5-pyridinedicarboxylate) was successfully determined from powder X-ray diffraction data. The compound crystallizes in the triclinic system (space group P -1) with a=6.7813(1) A° , b=7.4944(1) A°, c=8.5013(1) A° , α=95.256(1)°, β=102.478(1)°, γ=1...

  20. Interaction of dispersed polyvynil acetate with silicate in finishing materials

    Directory of Open Access Journals (Sweden)

    Runova, R. F.


    Full Text Available This article focuses on the processes of interaction between calcium silicate hydrates and dispersed polyvinyl acetate in tight films with the aim of developing compounds meant for restoration and finishing works. The basis of this development relies on the concept concerning the determining role of the crystal-chemical factor of the silicate phase in the formation of organic-mineral compounds of increased durability. The characteristics of dispersed calcium silicate hydrates are portrayed. The preparation conditions, accounting for the synthesis of the product of submicrocrystalline structure, conforming with the stoichiometry CaO∙SiO2 =0.8-2.0 have been determined. The interaction has been studied for compounds achieved by mixing ingredients in a rapid whirling mixer, and subjected to hardening at T=20+2 T. With the aid of XRD, DTA and Infra-Red Spectrometry methods the formation process of the sophisticated polymer silicate phase in the material was observed for a period of 90 days. The properties of the film were investigated and its high resistance against the influence of external factors was established. On this basis a conclusion concerning the quite high effectiveness of substituting portland cement with dispersed calcium silicate hydrate in polymer cement compounds has been made. White colour and other various special properties determine the suitability for repair and finishing works on facades of buildings.

    Este artículo está orientado a estudiar los procesos de interacción entre los silicatos cálcicos hidratados y el acetato de polivinilo disperso en capas impermeables, con el objeto de desarrollar compuestos destinados para la restauración. El fundamento de estos estudios es determinar el papel que los factores cristaloquímicos de las fases silicato tienen en la formación de compuestos órganominerales de elevada durabilidad. Se han descrito las características de los silicatos cálcicos hidratados

  1. Influence of silicate anions structure on desilication in silicate-bearing sodium aluminate solution

    Institute of Scientific and Technical Information of China (English)

    刘桂华; 张闻; 齐天贵; 彭志宏; 周秋生; 李小斌


    The structural changes of silicate anions in the desilication process with the addition of calcium hydrate alumino-carbonate were studied by measuring Raman spectra, infrared spectra and corresponding second derivative spectra. The results show that the desilication ratio in the solution prepared by the addition of sodium silicate (solution-SS) is much greater than that in the solution by the addition of green liquor (solution-GL), and low alumina concentration in the sodium aluminate solutions facilitates the desilication process. It is also shown that alumino-silicate anions in the solution-GL, and Q3 polymeric silicate anions in solution-SS are predominant, respectively. In addition, increasing the concentration of silica favors respectively the formation of the alumino-silicate or the Q3 silicate anions in the solution-GL or the solution-SS. Therefore, it can be inferred that the low desilication ratio in the silicate-bearing aluminate solution is mainly attributed to the existence of alumino-silicate anions.

  2. Nafion-Induced Metal-Metal Interactions in a Platinum(Ⅱ) Terpyridyl Acetylide Complex:a Luminescent Sensor for Detection of Volatile Organic Compounds

    Institute of Scientific and Technical Information of China (English)

    TONG,Qing-Xiao(佟庆笑); LI,Xiao-Hong(李晓红); WU,Li-Zhu(吴骊珠); YANG,Qing-Zheng(杨清正); ZHANG,Li-Ping(张丽萍); TUNG,Chen-Ho(佟振合)


    The platinum(Ⅱ) terpyridyl acetylide complex [Pt(terpy)(C≡CR)]C1O4 (terpy=2,2′: 6′2″-terpyridine, R=CH2CH2CH3) (1) was incorporated into Nafion membranes. At high loading the dry membranes exhibit intense photoluminescence with λmax at 707 nm from the 3MMLCT state, which was not observed in fluid solution. Upon exposure to the vapor of polar volatile organic compounds (VOC), this photoluminescence was significantly red-shifed. This process was fully reversible when the VOC-incorporated membrane was dried in air. The dramatic and reversible changes in the emission spectra made the Nafion-supported complex as an interesting sensor candidate for polar VOC.

  3. Investigation of SiO{sub 2}:Na{sub 2}O ratio as a corrosion inhibitor for metal alloys

    Energy Technology Data Exchange (ETDEWEB)

    Mohamad, N.; Othman, N. K. [School of Applied Physics, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan (Malaysia); Jalar, A. [Institute of Micro Engineering and Nanoelectronics (IMEN), Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan (Malaysia)


    The silicate is one of the potential compounds used as a corrosion inhibitor for metal alloys. The mixture between silica and sodium hydroxide (NaOH) succeeded to produce the silicate product. The formulation of a silicate product normally variable depended by the different ratio of SiO{sub 2}:Na{sub 2}O. This research utilized the agriculture waste product of paddy using its rice husk. In this study, the amorphous silica content in rice husk ash was used after rice husk burnt in a muffle furnace at a certain temperature. The X-ray diffraction (XRD) analysis was done to determine the existence of amorphous phase of silica in the rice husk ash. There are several studies that recognized rice husk as an alternative source that obtained high silica content. The X-ray fluorescence (XRF) analysis was carried out to clarify the percentage amount of Si and O elements, which referred the silica compound in rice husk ash. The preparation of sodium silicate formulation were differ based on the SiO{sub 2}:Na{sub 2}O ratio (SiO{sub 2}:Na{sub 2}O ratio = 1.00, 2.00 and 3.00). These silicate based corrosion inhibitors were tested on several testing samples, which were copper (99.9%), aluminum alloy (AA 6061) and carbon steel (SAE 1045). The purpose of this study is to determine the appropriate SiO{sub 2}:Na{sub 2}O ratio and understand how this SiO{sub 2}:Na{sub 2}O ratio can affect the corrosion rate of each metal alloys immersed in acidic medium. In order to investigate this study, weight loss test was conducted in 0.5 M hydrochloric acid (HCl) for 24 hours at room temperature.

  4. First-principles and Monte Carlo studies on the magnetic stability of half-metallic zinc-blende CaC and similar compounds

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Shengjie [Department of Physics, Tianjin Normal University, Tianjin 300387 (China); Ding, Hang-Chen [Key Laboratory of Polar Materials and Devices, East China Normal University, Shanghai 200062 (China); Zhou, Baozeng [Department of Applied Physics, Faculty of Science, Tianjin University, Tianjin 300072 (China); Duan, Chun-Gang [Key Laboratory of Polar Materials and Devices, East China Normal University, Shanghai 200062 (China); National Laboratory for Infrared Physics, Chinese Academy of Sciences, Shanghai 200083 (China); Wu, Ping [Department of Applied Physics, Faculty of Science, Tianjin University, Tianjin 300072 (China); Zhao, Hui, E-mail: [Department of Physics, Tianjin Normal University, Tianjin 300387 (China)


    Using the first-principles calculation based on density functional theory and Monte Carlo simulation within the Heisenberg Hamiltonian, we have investigated the magnetic stability at finite pressure and temperature of CaC and some other selected hypothetical II{sup A}–IV{sup A} compounds with the zinc-blende crystal structure. The results from simulated external pressure and temperature test indicate that the magnetic stability is dependent on the variation in atomic number of anion or cation element. Additionally, the origin of sp magnetism is mentioned briefly in this work and the dependence of Curie temperature on the volume is also discussed. First-principles computational charge-injection test show that the magnetization of these sp compounds originates in the spin polarization of the p shell of anions. For CaC, the exchange parameter J{sub 1} of the Heisenberg Hamiltonian depends strongly on the lattice constant, while the J{sub 2} and J{sub 3} are weakly dependent on the lattice constant. Moreover, discussion of volume-conserving deformations for CaC further demonstrates the stability of ferromagnetism and half metallicity for the compounds. - Highlights: • CaC and some other compounds with the zinc-blende crystal structure. • The first-principles calculation and Monte Carlo simulation within the Heisenberg Hamiltonian. • The magnetic stability is dependent on the variation in atomic number of anion or cation element. • The magnetic properties depend on the deformation of the lattice. • The normalized magnetic moment and specific heat capacity as a function of temperature.

  5. Resistance to Antibiotics, Biocides, Preservatives and Metals in Bacteria Isolated from Seafoods: Co-Selection of Strains Resistant or Tolerant to Different Classes of Compounds (United States)

    Romero, José L.; Grande Burgos, María J.; Pérez-Pulido, Rubén; Gálvez, Antonio; Lucas, Rosario


    Multi-drug resistant bacteria (particularly those producing extended-spectrum β-lactamases) have become a major health concern. The continued exposure to antibiotics, biocides, chemical preservatives, and metals in different settings such as the food chain or in the environment may result in development of multiple resistance or co-resistance. The aim of the present study was to determine multiple resistances (biocides, antibiotics, chemical preservatives, phenolic compounds, and metals) in bacterial isolates from seafoods. A 75.86% of the 87 isolates studied were resistant to at least one antibiotic or one biocide, and 6.90% were multiply resistant to at least three biocides and at least three antibiotics. Significant (P isolates selected according to antimicrobial resistance profile and food type were identified by 16S rDNA sequencing and tested for copper and zinc tolerance. Then, the genetic determinants for biocide and metal tolerance and antibiotic resistance were investigated. The selected isolates were identified as Pseudomonas (63.33%), Acinetobacter (13.33%), Aeromonas (13.33%), Shewanella, Proteus and Listeria (one isolate each). Antibiotic resistance determinants detected included sul1 (43.33% of tested isolates), sul2 (6.66%), blaTEM (16.66%), blaCTX−M (16.66%), blaPSE (10.00%), blaIMP (3.33%), blaNDM−1 (3.33%), floR (16.66%), aadA1 (20.0%), and aac(6′)-Ib (16.66%). The only biocide resistance determinant detected among the selected isolates was qacEΔ1 (10.00%). A 23.30 of the selected isolates were able to grow on media containing 32 mM copper sulfate, and 46.60% on 8 mM zinc chloride. The metal resistance genes pcoA/copA, pcoR, and chrB were detected in 36.66, 6.66, and 13.33% of selected isolates, respectively. Twelve isolates tested positive for both metal and antibiotic resistance genes, including one isolate positive for the carbapenemase gene blaNDM−1 and for pcoA/copA. These results suggest that exposure to metals could co-select for

  6. Concentrations of metals and potential metal-binding compounds and speciation of Cd, Zn and Cu in phloem and xylem saps from castor bean plants (Ricinus communis) treated with four levels of cadmium. (United States)

    Hazama, Kenji; Nagata, Shinji; Fujimori, Tamaki; Yanagisawa, Shuichi; Yoneyama, Tadakatsu


    We examined the concentrations of metals (Cd, Zn, Cu, Fe and Mn) and potential metal-binding compounds [nicotianamine (NA), thiol compounds and citrate] in xylem and phloem saps from 4-week-old castor bean plants (Ricinus communis) treated with 0 (control), 0.1, 1.0, and 10 μM Cd for 3 weeks. Treatment with 0.1 and 1 μM Cd produced no visible damage, while 10 μM Cd retarded growth. Cadmium concentrations in both saps were higher than those in the culture solution at 0.1 μM, similar at 1.0 μM and lower at 10 μM. Cd at 10 μM reduced Cu and Fe concentrations in both saps. NA concentrations measured by capillary electrophoresis-mass spectrometry (MS) in xylem sap (20 μM) were higher than the Cu concentrations, and those in phloem sap (150 μM) were higher than those of Zn, Fe and Cu combined. Reduced glutathione concentrations differed in xylem and phloem saps (1-2 and 30-150 μM, respectively), but oxidized glutathione concentrations were similar. Phloem sap phytochelatin 2 concentration increased from 0.8 μM in controls to 8 μM in 10 μM Cd. Free citrate was 2-4 μM in xylem sap and 70-100 μM in phloem sap. Total bound forms of Cd in phloem and xylem saps from 1 μM Cd-treated plants were 54 and 8%, respectively. Treatment of phloem sap with proteinaseK reduced high-molecular compounds while increasing fractions of low-molecular Cd-thiol complexes. Zinc-NA, Fe-NA and Cu-NA were identified in the phloem sap fraction of control plants by electrospray ionization time-of-flight MS, and the xylem sap contained Cu-NA.

  7. Pressure-induced metal-insulator transition in spinel compound CuV{sub 2}S{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Okada, H. [High Field Laboratory for Superconducting Materials, Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan)], E-mail:; Koyama, K. [High Field Laboratory for Superconducting Materials, Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Hedo, M. [Faculty of Science, University of the Ryukyus, Okinawa 903-0213 (Japan); Uwatoko, Y. [Institute for Solid State Physics, University of Tokyo, Kashiwa, Chiba 277-8581 (Japan); Watanabe, K. [High Field Laboratory for Superconducting Materials, Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan)


    In order to investigate the pressure effect on electrical properties of CuV{sub 2}S{sub 4}, we performed the electrical resistivity measurements under high pressures up to 8 GPa for a high-quality polycrystalline sample. The charge density wave (CDW) transition temperatures increase with increasing pressure. The residual resistivity rapidly increases with increasing pressure over 4 GPa, and the temperature dependence of the electrical resistivity at 8 GPa exhibits a semiconducting behavior below about 150 K, indicating that a pressure-induced metal-insulator transition occurs in CuV{sub 2}S{sub 4} at 8 GPa.

  8. Polyoxometalate-based organic-inorganic hybrid compounds containing transition metal mixed-organic-ligand complexes of N-containing and pyridinecarboxylate ligands. (United States)

    Zhao, De-Chuan; Hu, Yang-Yang; Ding, Hong; Guo, Hai-Yang; Cui, Xiao-Bing; Zhang, Xiao; Huo, Qi-Sheng; Xu, Ji-Qing


    Five new organic–inorganic hybrid compounds based on the Keggin-type polyoxoanion [SiW12O40]4−, namely [Cu3(2,2′-bpy)3(inic)(μ2-OH)(H2O)][SiW12O40]·2H2O (1), [Cu6(phen)6(μ3-Cl)2(μ2-Cl)2Cl2(inic)2][SiW12O40]·6H2O (2), [Cu2(hnic)(2,2′-bpy)2Cl]2[H2SiW12O40] (3), [Cu2(nic)(phen)2Cl2]2[SiW12O40] (4) and [Cu2(pic)(2,2′-bpy)2Cl]2[SiW12O40] (5) (inic = isonicotinic acid, hnic = 2-hydroxy-nicotinic acid, nic = nicotinic acid, pic = picolinic acid, 2,2′-bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) have been synthesized and characterized by IR, UV-Vis, XPS, XRD, cyclic voltammetric measurements, photoluminescence analysis and single crystal X-ray diffraction analysis. Crystal analysis reveals that compound 1 exhibits a 2-D double layered framework structure constructed from [SiW12O40]4− and copper-aqua-2,2′-bipy-hydroxyl-isonicotinate complexes. Compound 2 is a 0-D discrete structure formed by [SiW12O40]4− and copper-chloro-isonicotinate-phenanthroline complexes. Compound 3 shows a 1-D single chain structure based on the linkage of copper-2,2-bpy-chloro-2-hydroxy-nicotinate complexes and [SiW12O40]4−. Compounds 4 and 5 both contain polyoxometalate supported transition metal complexes, one is a polyoxometalate supported copper-chloro-nicotinate-phenanthroline complex in 4, and the other is a polyoxometalate supported copper-2,2-bpy-chloro-nicotinate complex in 5. It should be noted that nicotinic, isonicotinic and picolinic acids are structural isomers and 2-hydroxy-nicotinic acid is an in situ hydroxylated product of nicotinic acid. In addition, photocatalytic degradation of Rhodamine B (RhB) by compounds 1–5 has been investigated in aqueous solutions.

  9. FINAL TECHNICAL REPORT Synthetic, Structural and Mechanistic Investigations of Olefin Polymerization Catalyzed by Early Transition Metal Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Bercaw, John E. [California Institute of Technology


    The goal of this project is to develop new catalysts and provide understanding of ligand effects on catalyst composition in order to guide development of superior catalyst systems for polymerization of olefins. Our group is designing and synthesizing new “LX2”,“pincer” type ligands and complexing early transition metals to afford precatalysts. In a collaboration with Hans Brintzinger from the University of Konstanz, we are also examining the structures of the components of catalyst systems obtained from reaction of zirconocene dichlorides with aluminum alkyls and aluminum hydrides. Such systems are currently used commercially to produce polyolefins, but the nature of the active and dormant species as well as the mechanisms of their interconversions are not understood. New information on catalyst design and performance may lead to new types of polymers and/or new chemical transformations between hydrocarbons and transition metal centers, ultimately contributing to the development of catalytic reactions for the production of fuels, commodity and polymeric materials.

  10. Synthesis of lithium silicates generators of tritium by a modified method of combustion; Sintesis de silicatos de litio generadores de tritio por un metodo modificado de combustion

    Energy Technology Data Exchange (ETDEWEB)

    Cruz G, D


    The ceramics of lithium have been proposed as generating materials of tritium through the following reaction: {sup 6} Li + {sup 1} n {yields} {sup 4} He + {sup 3} H . In previous works carried out by Pfeiffer and collaborators, the lithium silicates generators of tritium were prepared using the following methods: reactions of solid state, precipitation and sol-gel synthesis. Although those methods have advantages, it is required of heating at high temperatures (900 C during four hours) to be able to obtain the crystalline compounds. Those products found in these works were diverse crystallization forms of the lithium silicates and of SiO{sub 2}, such as, Li{sub 2}SiO{sub 3}, Li{sub 2}Si{sub 2}0{sub 5}, Li{sub 4}SiO{sub 4}, and quartz (SiO{sub 2}). The combustion method uses exothermic reactions to take place ceramic compounds. The precursor solutions are mixtures of the nitrate of metal oxidizer and the fuels (urea, glycine, carbohydrazide). However the reported method in the literature, it is not useful to prepare lithium silicates, for what was modified using non oxidizers compounds. The lithium hydroxide (LiOH) and the silicic acid (H{sub 2}SiO{sub 3}) they were the compounds non oxidizers used, and the urea (CH{sub 4}N{sub 2}O) it was the one fuel. They were carried out two series of experiments; inside the series 1 of experiments are varied the molar ratio of lithium hydroxide and urea (LiOH : H{sub 2}SiO{sub 3} = 1, 2 and 3, LiOH : CH{sub 4}N{sub 2}O = 1, 2, 3, 4 and 5) and the prepared mixtures were taken to one muffle previously preheated to a temperature of 450 C during 5 minutes. In the series 2 of experiments was studied the effect of the temperature and of the washed with distilled water in the prepared samples with the following molar ratios: LiOH : H{sub 2}SiO{sub 3} : CH{sub 4}N{sub 2}O = 1:1:3, 2:1:3, 3:1:3 and 3:1:6, those which were heated to temperatures from 450 C up to 750 C and were washed. The obtained samples were characterized by X

  11. Hybrid Photonic Cavity with Metal-Organic Framework Coatings for the Ultra-Sensitive Detection of Volatile Organic Compounds with High Immunity to Humidity (United States)

    Tao, Jifang; Wang, Xuerui; Sun, Tao; Cai, Hong; Wang, Yuxiang; Lin, Tong; Fu, Dongliang; Ting, Lennon Lee Yao; Gu, Yuandong; Zhao, Dan


    Detection of volatile organic compounds (VOCs) at parts-per-billion (ppb) level is one of the most challenging tasks for miniature gas sensors because of the high requirement on sensitivity and the possible interference from moisture. Herein, for the first time, we present a novel platform based on a hybrid photonic cavity with metal-organic framework (MOF) coatings for VOCs detection. We have fabricated a compact gas sensor with detection limitation ranging from 29 to 99 ppb for various VOCs including styrene, toluene, benzene, propylene and methanol. Compared to the photonic cavity without coating, the MOF-coated solution exhibits a sensitivity enhancement factor up to 1000. The present results have demonstrated great potential of MOF-coated photonic resonators in miniaturized gas sensing applications.

  12. Interplay of metals and bromine with dioxin-related compounds concentrated in e-waste open burning soil from Agbogbloshie in Accra, Ghana. (United States)

    Fujimori, Takashi; Itai, Takaaki; Goto, Akitoshi; Asante, Kwadwo A; Otsuka, Masanari; Takahashi, Shin; Tanabe, Shinsuke


    Open burning of electronic waste (e-waste) releases various metals and organohalogen compounds in the environment. Here we investigated the interplay of metals (Cu, Pb, Zn, Fe, Co, and Sr) and bromine (Br) in the formation of dioxin-related compounds (DRCs), including polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs), as well as non-regulated DRCs such as polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) and their monobrominated PCDD/Fs in soils sampled from open burning e-waste sites at Agbogbloshie in Accra, Ghana. The predominant DRCs were PBDFs, PCDFs, PCDDs, and DL-PCBs. Statistical analyzes, X-ray absorption spectroscopy, and the PCDF/PCDD ratio suggested possible formation paths of PCDD/Fs and DL-PCBs by catalytic behaviors of copper chlorides (CuCl, CuCl2, and Cu2(OH)3Cl) and thermal breakdown of polyvinyl chloride. Predominant formation of brominated furans may be derived from electron transfer from intermediates of PBDE to copper, Cu(II) → Cu(I). Lead chloride also contributed to generate DRCs and may become highly bioaccessible through the open burning of e-waste. The main zinc species (ZnCl2 and ZnS) suggested a possible relationship to generate DRCs and specific zinc source such as tire burning. Cu, Pb, Zn, and Br contained in various e-wastes, wires/cables, plastics, and tires strongly influenced generation of many DRCs.

  13. Prediction of half-metallic ferromagnetism (HMF) in hypothetical Heusler compound Co{sub 2}VSb using modified Becke Johnson (mBJ) potential

    Energy Technology Data Exchange (ETDEWEB)

    Rai, D.P., E-mail: [Beijing Computational Science Research Center, Heqing Rd. 3, Beijing 100084 (China); Maibam, J. [Department of Physics, Manipur University, Canchipur 795003 (India); Sharma, B.I. [Department of Physics, Assam University, Silchar 788 011 (India); Shankar, A.; Sandeep,; Thapa, R.K. [Department of Physics, Mizoram University, Aizawl 796004 (India); Ke, San Huang [Beijing Computational Science Research Center, Heqing Rd. 3, Beijing 100084 (China); Key Laboratory of Advanced Microstructure Materials, MOE, Dept. of Physics, Tongji University, 1239 Siping Rd. Shanghai 200092 (China)


    Highlights: • Half-metallic ferromagnetism were studied using GGA, LSDA+U and mBJ. • The calculated magnetic moment of 4.00 μ{sub B} (LSDA+U and mBJ). • mBJ is more effective to band gap calculation as compare to others. -- Abstract: In search of half-metallic ferromagnetism, we have studied the electronic and magnetic properties of Co{sub 2}VSb by using the different tools like GGA, LSDA+U and mBJ potential based on density functional theory (DFT). The compound Co{sub 2}VSb is analogous to Co{sub 2}VAl, Co{sub 2}VSn and Co{sub 2}VGa , these compounds were studied theoretically and experimentally by Buschow and Engen. We expect the similar kind of properties from Co{sub 2}VSb as that of Co{sub 2}VAl, Co{sub 2}VSn and Co{sub 2}VGa. The mBJ potential is considered to be more effective as compared to LDA and GGA which gives higher value of band gap. The theoretical lattice constant obtained from volume optimization is 6.072 Å. The calculated value of energy gaps was found to be 0.20 eV, 1.00 eV and 1.30 eV for GGA, LSDA+U and mBJ respectively. Our results of band gap calculation predicts that mBJ overestimate the results of GGA, LSDA and LSDA+U.

  14. Meeting report on 8th International Symposium on Platinum and Other Metal Coordination Compounds in Cancer Chemotherapy. (United States)

    Kelland, L R


    The platinum-based drugs, cisplatin and carboplatin, represent major agents in the chemotherapeutic treatment of a variety of types of cancer. Novel, "third-generation" agents aimed at broadening the clinical activity of this class of drug are currently undergoing clinical evaluation. These include oxaliplatin, ZD0473 and BBR3464. Clinical trials and preclinical studies are also being conducted with liposomal (SPI-077 and L-NDDP) and polymeric platinum complexes (linked to HPMA or albumin). Combination studies of cisplatin/carboplatin with other anticancer drugs such as gemcitabine and UCN-01 (7-hydroxystaurosporine) and agents designed to reduce platinum drug toxicities (e.g., BNP-7787, DIMESNA) are ongoing. Preclinically, there is interest in trans platinum complexes, terpyridine platinum(II) complexes and other metal-containing agents (ruthenium and gold).

  15. Carbon based magnetism an overview of the magnetism of metal free carbon-based compounds and materials

    CERN Document Server

    Makarova, Tatiana


    Magnetism is one of the most intriguing phenomena observed in nature. Magnetism is relevant to physics and geology, biology and chemistry. Traditional magnets, an ubiquitous part of many everyday gadgets, are made of heavy iron- or nickel based materials. Recently there have been reports on the observation of magnetism in carbon, a very light and biocompatible element. Metal-free carbon structures exhibiting magnetic ordering represent a new class of materials and open a novel field of research that could lead to many new technologies. · The most complete, detailed, and accurate Guide in the magnetism of carbon · Dynamically written by the leading experts · Deals with recent scientific highlights · Gathers together chemists and physicists, theoreticians and experimentalists · Unified treatment rather than a series of individually authored papers · Description of genuine organic molecular ferromagnets · Unique description of new carbon materials with Curie temperatures well above ambient.

  16. Surface Properties of Unintentionally Doped GaN Film and Its Contact Behaviour with Ni/Cr/Au Compound Metals

    Institute of Scientific and Technical Information of China (English)

    苑进社; 陈光德; 齐鸣; 李爱珍; 谢伦军


    The surface properties of GaN films grown by plasma-assisted molecular beam epitaxy were investigated by using x-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy, while the depth profile was analysed by the Ar ion sputtering method. The contaminants carbon and silicon are chiefly adsorbed onto the surface while oxygen and aluminium diffuse into the bulk to distribute in a certain depth. The mixture oxides is roughly 0.1 μm in thickness. Based on the analytical results of XPS of the GaN films, the Ni/Cr/Au interdigital metalsemiconductor-metal (MSM) structure has been fabricated. It has been found that the contact behaviour of the Ni/Cr/Au/undoped GaN exhibits a linear Ⅰ-Ⅴ characteristic under dark and 362-nm light excitation without annealing treatment. The lower resistance of the MSM structure has also been observed.

  17. Heavy metals and organic compounds contamination in soil from an e-waste region in South China. (United States)

    Liu, Ming; Huang, Bo; Bi, Xinhui; Ren, Zhaofang; Sheng, Guoying; Fu, Jiamo


    Heavy metals and persistent organic pollutants polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were analyzed in 34 surface soil samples collected from farmland and 7 soil or dust samples collected from the workshops in South China, where e-waste was dismantled using primitive techniques. The results show that Cd, Cu and Hg were the most abundant metals, in particular Cd pollution was serious in farmland soils, and the median concentrations in farmland soils were beyond the environmental quality standard for soils (China Grade II). A correlation between Cd, Cu, Zn, Pb and PCBs or PBDEs was significant indicating similar sources. Among the PCB congeners, high relative similarity was observed between the e-waste dump site soil (EW1) and Aroclor 1254, implying that the technical product Aroclor 1254 was one of the major sources of PCB contamination. High concentrations of PCBs in workshop dusts (D2 and D3) (1958 and 1675 μg kg(-1)) demonstrated that the workshops dismantling electrical wires and cables, electrical motors, compressors and aluminum apparatus containing PCBs in lubricants represent strong PCB emission sources to this area. Principal component analysis (PCA) and PBDE homologue patterns verify that farmland soils surrounding the e-waste recycling sites were enriched with lower brominated congeners, and the major source of PBDEs in dust samples might potentially be associated with the extensive use of deca-mix technical products as a flame retardant. The difference between e-waste soils, dusts and farmland soils can be observed in the PCA score plot of PCBs and PBDEs, and E-waste soils and dusts exhibited more diversity than farmland soils. Furthermore, a prediction of the particular kinds of pollution from different recycling activities through the analysis of each contamination and the connections between them was investigated.

  18. Benchmark Results and Theoretical Treatments for Valence-to-Core X-ray Emission Spectroscopy in Transition Metal Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Mortensen, Devon R.; Seidler, Gerald T.; Kas, Joshua J.; Govind, Niranjan; Schwartz, Craig; Pemmaraju, Das; Prendergast, David


    We report measurement of the valence-to-core (VTC) region of the K-shell x-ray emission spectra from several Zn and Fe inorganic compounds, and their critical comparison with several existing theoretical treatments. We find generally good agreement between the respective theories and experiment, and in particular find an important admixture of dipole and quadrupole character for Zn materials that is much weaker in Fe-based systems. These results on materials whose simple crystal structures should not, a prior, pose deep challenges to theory, will prove useful in guiding the further development of DFT and time-dependent DFT methods for VTC-XES predictions and their comparison to experiment.

  19. Nanostructure of Calcium Silicate Hydrates in Cements

    KAUST Repository

    Skinner, L. B.


    Calcium silicate hydrate (CSH) is the major volume phase in the matrix of Portland cement concrete. Total x-ray scattering measurements with synchrotron x rays on synthetic CSH(I) shows nanocrystalline ordering with a particle diameter of 3.5(5) nm, similar to a size-broadened 1.1 nm tobermorite crystal structure. The CSH component in hydrated tricalcium silicate is found to be similar to CSH(I). Only a slight bend and additional disorder within the CaO sheets is required to explain its nanocrystalline structure. © 2010 The American Physical Society.

  20. Probing Interstellar Silicate Dust Grain Properties in Quasar Absorption Systems at Redshifts z<1.4 (United States)

    Aller, M.; Kulkarni, V. P.; York, D. G.; Welty, D. E.; Vladilo, G.; Som, D.

    indications of trends between silicate dust absorption strength and both carbonaceous dust properties and gas-phase metal properties, such as the gas velocity spread, determined from UV/optical spectra.

  1. [Design and synthesis of imine compound for metal cation logical gates recognition and setup of double-control fluorescent molecule switch]. (United States)

    Huang, Tao; Zhu, Yu-lian; Dai, Xue-qin; Zhang, Qi; Huang, Yan


    The Schiff base's reduced product N,N-bis(4-methoxybenzyl) ethane-1,2-diamine, which was used as a receptor L, was designed and synthesized for the first time in the present article. It was found that Cu2+ and Fe3+ could quench L in fluorescence observably and Zn2+ and Cd2+ could enhance L remarkably. So the two pair metal cation could set up "OR" logical gate relation with the receptor molecule L, then a logical recognition system be formed. The data of resolved ZnL's single crystal indicated that ZnL belonged to monoclinic (CCDC No. 747994). Integrated spectrum instrument was used to characterize the structure of its alike series of complex compound. According to ZnL's excellent fluorescence character and the ability to exchange with contiguous metal cation, ZnZ+/ZnL/Co2+, Zn2+/ZnL/Nit+ fluorescent molecule switch was designed. It is hoped that the work above could be positive for the development of molecule computer, bio-intellectualized inspection technology (therapy) and instrument.

  2. Completely compensated ferrimagnetism and sublattice spin crossing in the half-metallic Heusler compound Mn1.5FeV0.5Al (United States)

    Stinshoff, Rolf; Nayak, Ajaya K.; Fecher, Gerhard H.; Balke, Benjamin; Ouardi, Siham; Skourski, Yurii; Nakamura, Tetsuya; Felser, Claudia


    The Slater-Pauling rule states that L 21 Heusler compounds with 24 valence electrons never exhibit a total spin magnetic moment. In the case of strongly localized magnetic moments at one of the atoms (here Mn) they will exhibit a fully compensated half-metallic ferrimagnetic state instead, in particular, when symmetry does not allow for antiferromagnetic order. With the aid of magnetic and anomalous Hall effect measurements, it is experimentally demonstrated that Mn1.5V0.5FeAl follows such a scenario. The ferrimagnetic state is tuned by the composition. A small residual magnetization, which arises due to a slight mismatch of the magnetic moments in the different sublattices, results in a pronounced change of the temperature dependence of the ferrimagnet. A compensation point is confirmed by observation of magnetic reversal and sign change of the anomalous Hall effect. Theoretical models are presented that correlate the electronic structure and the compensation mechanisms of the different half-metallic ferrimagnetic states in the Mn-V-Fe-Al Heusler system.

  3. Order-disorder phase transition and multiferroic behaviour in a metal organic framework compound (CH3)2NH2Co(HCOO)3 (United States)

    Yadav, Ruchika; Swain, Diptikanta; Bhat, H. L.; Elizabeth, Suja


    We have investigated the multiferroic and glassy behaviour of metal-organic framework (MOF) material (CH3)2NH2Co(CHOO)3. The compound has perovskite-like architecture in which the metal-formate forms a framework. The organic cation ( CH3 ) 2 NH2 + occupies the cavities in the formate framework in the framework via N-H...O hydrogen bonds. At room temperature, the organic cation is disordered and occupies three crystallographically equivalent positions. Upon cooling, the organic cation is ordered which leads to a structural phase transition at 155 K. The structural phase transition is associated with a para-ferroelectric phase transition and is revealed by dielectric and pyroelectric measurements. Further, a PE hysteresis loop below 155 K confirms the ferroelectric behaviour of the material. Analysis of dielectric data reveal large frequency dispersion in the values of dielectric constant and tanδ which signifies the presence of glassy dielectric behaviour. The material displays a antiferromagnetic ordering below 15 K which is attributed to the super-exchange interaction between Co2+ ions mediated via formate linkers. Interestingly, another magnetic transition is also found around 11 K. The peak of the transition shifts to lower temperature with increasing frequency, suggesting glassy magnetism in the sample.

  4. A Metal-Organic Compound as Cathode Material with Superhigh Capacity Achieved by Reversible Cationic and Anionic Redox Chemistry for High-Energy Sodium-Ion Batteries. (United States)

    Fang, Chun; Huang, Ying; Yuan, Lixia; Liu, Yaojun; Chen, Weilun; Huang, Yangyang; Chen, Kongyao; Han, Jiantao; Liu, Qingju; Huang, Yunhui


    Although sodium-ion batteries (SIBs) are considered as alternatives to lithium-ion batteries (LIBs), the electrochemical performances, in particular the energy density, are much lower than LIBs. A metal-organic compound, cuprous 7,7,8,8-tetracyanoquinodimethane (CuTCNQ), is presented as a new kind of cathode material for SIBs. It consists of both cationic (Cu(II) ↔Cu(I) ) and anionic (TCNQ(0) ↔TCNQ(-) ↔ TCNQ(2-) ) reversible redox reactions, delivering a discharge capacity as high as 255 mAh g(-1) at a current density of 20 mA g(-1) . The synergistic effect of both redox-active metal cations and organic anions brings an electrochemical transfer of multiple electrons. The transformation of cupric ions to cuprous ions occurs at near 3.80 V vs. Na(+) /Na, while the full reduction of TCNQ(0) to TCNQ(-) happens at 3.00-3.30 V. The remarkably high voltage is attributed to the strong inductive effect of the four cyano groups. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Synthesis, structure and magnetic properties of mono-, dinuclear and polymeric compounds of transition metals with 4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole (United States)

    Martín-Ramos, Pablo; Silva, Manuela Ramos; de A. e Silva, Joana; Martins, Nuno D.; Yuste-Vivas, Consuelo; Pereira da Silva, Pedro S.; Sobral, Abílio J. F. N.; Pereira, Laura C. J.


    Five new complexes were obtained from solution of transition metal salts (M=Co(II), Cu(II)) with 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole (abpt) in different molar ratios. X-ray structural elucidation revealed low-dimensional compounds with the metal ions assembled in monomers, dimers or chains. Two similar polymorphs were obtained for the monomer synthesized from Cu(II) chloride. Temperature-dependent magnetic susceptibility measurements were conducted for the non-monomeric compounds, and efficient super-exchange interaction was found for the mostly planar dinuclear Co(II) complex.

  6. Metal-organic framework UiO-67-coated fiber for the solid-phase microextraction of nitrobenzene compounds from water. (United States)

    Zang, Xiaohuan; Zhang, Xi; Chang, Qingyun; Li, Sen; Wang, Chun; Wang, Zhi


    A sol-gel coating technique was applied for the preparation of a solid-phase microextraction fiber by coating the metal-organic framework UiO-67 onto a stainless-steel wire. The prepared fiber was explored for the headspace solid-phase microextraction of five nitrobenzene compounds from water samples before gas chromatography with mass spectrometric detection. The effects of the extraction temperature, extraction time, sample solution volume, salt addition, and desorption conditions on the extraction efficiency were optimized. Under the optimal conditions, the linearity was observed in the range of 0.015-12.0 μg/L for the compounds in water samples, with the correlation coefficients (r) of 0.9945-0.9987. The limits of detection of the method were 5.0-10.0 ng/L, and the recoveries of the analytes from spiked water samples for the method were in the range of 74.0-102.0%. The precision for the measurements, expressed as the relative standard deviation, was less than 11.9%.

  7. Structures and heats of formation of simple alkali metal compounds: hydrides, chlorides, fluorides, hydroxides, and oxides for Li, Na, and K. (United States)

    Vasiliu, Monica; Li, Shenggang; Peterson, Kirk A; Feller, David; Gole, James L; Dixon, David A


    Geometry parameters, frequencies, heats of formation, and bond dissociation energies are predicted for simple alkali metal compounds (hydrides, chlorides, fluorides, hydroxides and oxides) of Li, Na, and K from coupled cluster theory [CCSD(T)] calculations including core-valence correlation with the aug-cc-pwCVnZ basis set (n = D, T, Q, and 5). To accurately calculate the heats of formation, the following additional correction were included: scalar relativistic effects, atomic spin-orbit effects, and vibrational zero-point energies. For calibration purposes, the properties of some of the lithium compounds were predicted with iterative triple and quadruple excitations via CCSDT and CCSDTQ. The calculated geometry parameters, frequencies, heats of formation, and bond dissociation energies were compared with all available experimental measurements and are in excellent agreement with high-quality experimental data. High-level calculations are required to correctly predict that K(2)O is linear and that the ground state of KO is (2)Sigma(+), not (2)Pi, as in LiO and NaO. This reliable and consistent set of calculated thermodynamic data is appropriate for use in combustion and atmospheric simulations.

  8. On the formation of molecules and solid-state compounds from the AGB to the PN phases

    CERN Document Server

    Garcia-Hernandez, D A


    During the asymptoyic giant branch (AGB) phase, different elements are dredge-up to the stellar surface depending on progenitor mass and metallicity. When the mass loss increases at the end of the AGB, a circumstellar dust shell is formed, where different (C-rich or O-rich) molecules and solid-state compounds are formed. These are further processed in the transition phase between AGB stars and planetary nebulae (PNe) to create more complex organic molecules and inorganic solid-state compounds (e.g., polycyclic aromatic hydrocarbons, fullerenes, and graphene precursors in C-rich environments and oxides and crystalline silicates in O-rich ones). We present an observational review of the different molecules and solid-state materials that are formed from the AGB to the PN phases. We focus on the formation routes of complex fullerene (and fullerene-based) molecules as well as on the level of dust processing depending on metallicity.

  9. On the formation of molecules and solid-state compounds from the AGB to the PN phases (United States)

    García-Hernández, D. A.; Manchado, A.


    During the asymptoyic giant branch (AGB) phase, different elements are dredge- up to the stellar surface depending on progenitor mass and metallicity. When the mass loss increases at the end of the AGB, a circumstellar dust shell is formed, where different (C-rich or O-rich) molecules and solid-state compounds are formed. These are further processed in the transition phase between AGB stars and planetary nebulae (PNe) to create more complex organic molecules and inorganic solid-state compounds (e.g., polycyclic aromatic hydrocarbons, fullerenes, and graphene precursors in C-rich environments and oxides and crystalline silicates in O-rich ones). We present an observational review of the different molecules and solid-state materials that are formed from the AGB to the PN phases. We focus on the formation routes of complex fullerene (and fullerene-based) molecules as well as on the level of dust processing depending on metallicity.

  10. The Role of Gas-Silicate Chemisorption Reactions in Modifying Planetary Crusts and Surfaces (United States)

    King, P. L.; Henley, R. W.; Wykes, J. L.; Renggli, C.; Troitzsch, U.; Clark, D.; O'Neill, H. S.


    Evidence for gas-solid reactions is found throughout the solar system: for example, sulfidation reactions in some meteorites and secondary phases coating lunar pyroclastic glasses. On Earth, the products of gas-solid reactions are documented in volcanic systems, metalliferous mineral deposits, impact craters, and on dust or meteorites after passage through the atmosphere - such reactions are also likely on the surfaces of Mars and Venus. To understand the chemical dynamics of such gas-solid reactions, we are undertaking systematic experiments and thermochemical modelling. Experiments were conducted in a vertical gas-mixing furnace at 600 - 800 °C and 1 bar, using SO2and a range of Ca-bearing materials: labradorite, feldspar glass and anorthosite (rock). In each case, anhydrite formed rapidly. In shorter experiments with labradorite, isolated anhydrite is observed surrounded by 'moats' of Ca-depleted silicate. In longer experiments, anhydrite is found as clusters of crystals that, in some cases, extend from the substrate forming precarious 'towers' (Figure). Anhydrite fills cracks in porous samples. We propose that the nucleation and rapid growth of anhydrite on the surface of these Ca-rich phases occurs by chemisorption of SO2(g) molecules with slightly negatively charged oxygen onto available near-surface calcium with slight positive charge. Anhydrite growth is sustained by SO2(g) chemisorption and Ca migration through the reacting silicate lattice, accelerated by increased bond lengths at high temperature. Significantly, the chemisorption reaction indicates that SO2 disproportionates to form both oxidized sulfur (as anhydrite) and a reduced sulfur species (e.g., an S* radical ion). On Earth, in the presence of H2O, the predominant reduced sulfur species is H2S, through an overall reaction: 3CaAl2Si2O8 + 4 SO2(g)+ H2O(g) → 3CaSO4 + 3Al2SiO5 + 3SiO2 + H2S(g)The reduced sulfur may react with gas phase Fe, Ni, Zn and Cu cluster compounds to form metal sulfides

  11. Cr-Free Metallic-Ceramic Coatings (United States)


    Cr -FREE METALLIC-CERAMIC COATINGS ASETS Defense 2014 Fort Myer, VA, November 18-20, 2014 Bruce McMordie Coatings for Industry 319...SNECMA Alseal® 5K Aluminum-Silicate Al-Silicate Coating System Now Available That Can Eliminate Hazards of Carcinogenic Cr +6 in Al...OMB control number. 1. REPORT DATE NOV 2014 2. REPORT TYPE 3. DATES COVERED 00-00-2014 to 00-00-2014 4. TITLE AND SUBTITLE Cr -Free Metallic

  12. Influence of compound deoxidation of steel with Al, Zr, rare earth metals, and Ti on properties of heavy castings

    Directory of Open Access Journals (Sweden)

    J. Senberger


    Full Text Available Heavy steel castings deoxidized with aluminium are sometimes brittle intercrystalline failed during their service along primary grain boundaries what is initiated by aluminium nitrides and so called conchoidal fractures are formed. The tendency to forming the conchoidal fractures depends in particular on cooling rate (the casting modulus, aluminium and nitrogen contents in steel. During deoxidation, when manufacturing heavy castings, the elements with high affinity to nitrogen, zirconium or titanium, are added to steel that would decrease nitrogen activity by the bond on stable nitrides. The formation of stable nitrides should reduce the tendency of steel to the formation of conchoidal fractures. Deoxidation was thermodynamically analyzed at presence of the mentioned elements. For particular conditions a probable course of deoxidation was estimated at test castings. The deoxidation course was checked by microanalysis of deoxidation products (inclusions. For service and experimental castings the anticipated composition of inclusions was compared. It has been proved that in heavy castings with high aluminium contents in steel under studied conditions neither the addition of zirconium nor of titanium nor of rare earth metals will prevent the formation of conchoidal fractures.

  13. Comparative evaluation of several small mammal species as monitors of heavy metals, radionuclides, and selected organic compounds in the environment

    Energy Technology Data Exchange (ETDEWEB)

    Talmage, S.S. (Tennessee Univ., Knoxville, TN (USA) Oak Ridge National Lab., TN (USA)); Walton, B.T. (Oak Ridge National Lab., TN (USA))


    The primary purpose of this study was to evaluate which small mammal species are the best monitors of specific environmental contaminants. The evaluation is based on the published literature and on an analysis of small mammals trapped at several sites on the Oak Ridge National Laboratory (ORNL) Reservation in Oak Ridge, Tennessee. Studies on the uptake of heavy metals, radionuclides, and organic chemicals are reviewed in Chapter II to evaluate several small mammal species for their capacity to serve as sentinels for the presence, accumulation, and effects of various contaminants. Where several species were present at a site, a comparative evaluation was made and species are ranked for their capacity to serve as monitors of specific contaminants. Food chain accumulation and food habits of the species are used to establish a relationship with suitability as a biomonitor. Tissue-specific concentration factors were noted in order to establish target tissues. Life histories, habitat, and food habits are reviewed in order to make generalizations concerning the ability of similar taxa to serve as biomonitor. Finally, the usefulness of several small mammal species as monitors of three contaminants -- benzo(a)pyrene, mercury, and strontium-90 -- present on or near the ORNL facilities was investigated. 133 refs., 5 figs., 20 tabs.

  14. Chemical stabilization of metals in mine wastes by transformed red mud and other iron compounds: laboratory tests. (United States)

    Ardau, C; Lattanzi, P; Peretti, R; Zucca, A


    A series of static and kinetic laboratory-scale tests were designed in order to evaluate the efficacy of transformed red mud (TRM) from bauxite refining residues, commercial zero-valent iron, and synthetic iron (III) hydroxides as sorbents/reagents to minimize the generation of acid drainage and the release of toxic elements from multi-contaminant-laden mine wastes. In particular, in some column experiments the percolation of meteoric water through a waste pile, alternated with periods of dryness, was simulated. Wastes were placed in columns together with sorbents/reagents in three different set-ups: as blended amendment (mixing method), as a bed at the bottom of the column (filtration method), or as a combination of the two previous methods. The filtration methods, which simulate the creation of a permeable reactive barrier downstream of a waste pile, are the most effective, while the use of sorbents/reagents as amendments leads to unsatisfactory results, because of the selective removal of only some contaminants. The efficacy of the filtration method is not significantly affected by the periods of dryness, except for a temporary rise of metal contents in the leachates due to dissolution of soluble salts formed upon evaporation in the dry periods. These results offer original information on advantages/limits in the use of TRM for the treatment of multi-contaminant-laden mine wastes, and represent the starting point for experimentation at larger scale.

  15. High performance all-solid-state symmetric supercapacitor based on porous carbon made from a metal-organic framework compound (United States)

    Yu, Feng; Wang, Teng; Wen, Zubiao; Wang, Hongxia


    In this work, we demonstrate the synthesis of porous carbon material with high specific surface area by using metal-organic framework (MOF) as precursor. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) have confirmed that the material was amorphous and consisted of nanoparticles (5-6 nm) and hierarchical distribution of pores. The characterization of the material by N2 adsorption/desorption isotherm measurement have shown that the material had a high specific surface area reaching to 2618.7 m2 g-1 and abundant porosity with pore size less than 10 nm. The investigation of the electrochemical properties of the material has shown the porous carbon electrode possessed excellent rate performance with high specific capacitances of 150.8 F g-1 at a current density of 5 A g-1, and 133.6 F g-1 at a current density of 50 A g-1, respectively. An all-solid-state symmetric supercapacitor assembled using the as-prepared porous carbon as electrodes and Na2SO4/PVA gel as an electrolyte delivered a high power density of 13 516.4 W kg-1 with an energy density of 8.26 Wh kg-1. A high energy density of 17.37 Wh kg-1 was obtained at discharge current density of 1 A g-1. In addition, the device exhibited superior cycling performance with 94.8% retention rate after 10 000 cycles at a current density of 10 A g-1.

  16. Sol-Gel Synthesis and Luminescent Characteristic of Doped Eu3+ Silicate-Silica Phosphor

    Institute of Scientific and Technical Information of China (English)

    Yang Liangzhun; Yu Xibin; Yang Shiping; Zhou Pingle; Tang Jinfeng; Peng Xiudong


    Eu-doped silicate complex gel nano-particles was obtained by sol-gel process and characterized with TEM, XRD, PL, etc. The well dispersed particles have particle size about 60~70 nm with specific surface area 98.3 m2·g-1. The complex gel phosphor gives a broad and strong luminescent emission originating from Eu2+ ions centered at 425 nm. The emission band shifts to shorter wavelengths with the increase of the ion radius of the alkali earth metals, but the band becomes red-shifted gradually with the increase of the ion radius of the alkali metals(except Li+). These divalent Eu2+ ions originate in inequivalent substitution of the alkaline earth ions. The presence of alkaline ions is favorable for the increasing emission intensity of the Eu2+ and lowering crystalline temperature of the silicate complex gel.

  17. 21 CFR 172.410 - Calcium silicate. (United States)


    ... CONSUMPTION (CONTINUED) FOOD ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Anticaking... agent in food in an amount not in excess of that reasonably required to produce its intended effect. (b... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Calcium silicate. 172.410 Section 172.410 Food...

  18. Stability of calcium silicate in basic solution

    Institute of Scientific and Technical Information of China (English)

    刘桂华; 李小斌; 彭志宏; 周秋生


    Mixture of CaO and SiO2 was sintered at 1 200 or 1 400 ℃ according to the mole ratio of CaO/SiO2 of 1 or 2, and then calcium silicate was leached in pure caustic or soda solution. The results indicated that calcium silicate exists much more stably in caustic solution than that in soda solution, and CaO*SiO2 is more stable than β-2CaO*SiO2 whether in caustic solution or in soda solution. The increase of sintering temperature favored the stability of calcium silicate in the leaching process. When β-2CaO*SiO2 was leached in soda solution, the increase of leaching temperature and time resulted in decomposing of more calcium silicate. And when β-2CaO*SiO2 was leached in caustic solution at high temperature, much 2CaO*SiO2*H2O but little CaO*SiO2*H2O appeared in slag.


    Directory of Open Access Journals (Sweden)



    Full Text Available This article presents results of a study on coating of a polymeric substrate ca-talyst on metallic surface. Stability of coating on metallic surfaces is a proper specification. Sol-gel technology was used to synthesize adhesion promoters of polysilane compounds that act as a mediator. The intermediate layer was coated by synthesized sulfonated polystyrene-divinylbenzene as a catalyst for production of MTBE in catalytic distillation process. Swelling of catalyst and its separation from the metal surface was improved by i increasing the quantity of divinylbenzene in the resin’s production process and ii applying adhesion pro¬moters based on the sol-gel process. The rate of ethyl silicate hydrolysis was intensified by increasing the concentration of utilized acid while the conden¬sation polymerization was enhanced in the presence of OH–. Sol was formed at pH 2, while the pH should be 8 for the formation of gel. By setting the ratio of the initial concentrations of water to ethyl silicate to 8, the gel formation time was minimized.

  20. Cluster expansion reactions of group 6 and 8 metallaboranes using transition metal carbonyl compounds of groups 7-9. (United States)

    Geetharani, K; Bose, Shubhankar Kumar; Sahoo, Satyanarayan; Varghese, Babu; Mobin, Shaikh M; Ghosh, Sundargopal


    The reinvestigation of an early synthesis of heterometallic cubane-type clusters has led to the isolation of a number of new clusters which have been characterized by spectroscopic and crystallographic techniques. The thermolysis of [(Cp*Mo)(2)B(4)H(4)E(2)] (1: E = S; 2: E = Se; Cp* = η(5)-C(5)Me(5)) in presence of [Fe(2)(CO)(9)] yielded cubane-type clusters [(Cp*Mo)(2)(μ(3)-E)(2)B(2)H(μ-H){Fe(CO)(2)}(2)Fe(CO)(3)], 4 and 5 (4: E = S; 5: E = Se) together with fused clusters [(Cp*Mo)(2)B(4)H(4)E(2)Fe(CO)(2)Fe(CO)(3)] (8: E = S; 9: E = Se). In a similar fashion, reaction of [(Cp*RuCO)(2)B(2)H(6)], 3, with [Fe(2)(CO)(9)] yielded [(Cp*Ru)(2)(μ(3)-CO)(2)B(2)H(μ-H){Fe(CO)(2)}(2)Fe(CO)(3)], 6, and an incomplete cubane cluster [(μ(3)-BH)(3)(Cp*Ru)(2){Fe(CO)(3)}(2)], 7. Clusters 4-6 can be described as heterometallic cubane clusters containing a Fe(CO)(3) moiety exo-bonded to the cubane, while 7 has an incomplete cubane [Ru(2)Fe(2)B(3)] core. The geometry of both compounds 8 and 9 consist of a bicapped octahedron [Mo(2)Fe(2)B(3)E] and a trigonal bipyramidal [Mo(2)B(2)E] core, fused through a common three vertex [Mo(2)B] triangular face. In addition, thermolysis of 3 with [Mn(2)(CO)(10)] permits the isolation of arachno-[(Cp*RuCO)(2)B(3)H(7)], 10. Cluster 10 constitutes a diruthenaborane analogue of 8-sep pentaborane(11) and has a structural isomeric relationship to 1,2-[{Cp*Ru}(2)(CO)(2)B(3)H(7)].

  1. Organic photoredox catalysis for the oxidation of silicates: applications in radical synthesis and dual catalysis. (United States)

    Lévêque, Christophe; Chenneberg, Ludwig; Corcé, Vincent; Ollivier, Cyril; Fensterbank, Louis


    Metal free photooxidation of alkyl bis(catecholato)silicates with the organic dye 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyano-benzene (4CzIPN) allows the smooth formation of alkyl radicals. The latter can be efficiently engaged either with radical acceptors to provide homolytic addition products or in photoredox/nickel dual catalysis reactions to obtain cross-coupling products.

  2. 40 CFR 721.9513 - Modified magnesium silicate polymer (generic). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Modified magnesium silicate polymer... Specific Chemical Substances § 721.9513 Modified magnesium silicate polymer (generic). (a) Chemical... as modified magnesium silicate polymer (PMN P-98-604) is subject to reporting under this section for...

  3. Differentiation of Asteroid 4 Vesta: Core Formation by Iron Rain in a Silicate Magma Ocean (United States)

    Kiefer, Walter S.; Mittlefehldt, David W.


    Geochemical observations of the eucrite and diogenite meteorites, together with observations made by NASA's Dawn spacecraft while orbiting asteroid 4 Vesta, suggest that Vesta resembles H chondrites in bulk chemical composition, possible with about 25 percent of a CM-chondrite like composition added in. For this model, the core is 15 percent by mass (or 8 percent by volume) of the asteroid, with a composition of 73.7 percent by weight Fe, 16.0 percent by weight S, and 10.3 percent by weight Ni. The abundances of moderately siderophile elements (Ni, Co, Mo, W, and P) in eucrites require that essentially all of the metallic phase in Vesta segregated to form a core prior to eucrite solidification. The combination of the melting phase relationships for the silicate and metal phases, together with the moderately siderophile element concentrations together require that complete melting of the metal phase occurred (temperature is greater than1350 degrees Centigrade), along with substantial (greater than 40 percent) melting of the silicate material. Thus, core formation on Vesta occurs as iron rain sinking through a silicate magma ocean.

  4. Microwave-Assisted Conversion of Levulinic Acid to γ-Valerolactone Using Low-Loaded Supported Iron Oxide Nanoparticles on Porous Silicates

    Directory of Open Access Journals (Sweden)

    Alfonso Yepez


    Full Text Available The microwave-assisted conversion of levulinic acid (LA has been studied using low-loaded supported Fe-based catalysts on porous silicates. A very simple, productive, and highly reproducible continuous flow method has been used for the homogeneous deposition of metal oxide nanoparticles on the silicate supports. Formic acid was used as a hydrogen donating agent for the hydrogenation of LA to effectively replace high pressure H2 mostly reported for LA conversion. Moderate LA conversion was achieved in the case of non-noble metal-based iron oxide catalysts, with a significant potential for further improvements to compete with noble metal-based catalysts.

  5. Production of reactive oxygen species from abraded silicates. Implications for the reactivity of the Martian soil (United States)

    Bak, Ebbe N.; Zafirov, Kaloyan; Merrison, Jonathan P.; Jensen, Svend J. Knak; Nørnberg, Per; Gunnlaugsson, Haraldur P.; Finster, Kai


    The results of the Labeled Release and the Gas Exchange experiments conducted on Mars by the Viking Landers show that compounds in the Martian soil can cause oxidation of organics and a release of oxygen in the presence of water. Several sources have been proposed for the oxidizing compounds, but none has been validated in situ and the cause of the observed oxidation has not been resolved. In this study, laboratory simulations of saltation were conducted to examine if and under which conditions wind abrasion of silicates, a process that is common on the Martian surface, can give rise to oxidants in the form of hydrogen peroxide (H2O2) and hydroxyl radicals (ṡOH). We found that silicate samples abraded in simulated Martian atmospheres gave rise to a significant production of H2O2 and ṡOH upon contact with water. Our experiments demonstrated that abraded silicates could lead to a production of H2O2 facilitated by atmospheric O2 and inhibited by carbon dioxide. Furthermore, during simulated saltation the silicate particles became triboelectrically charged and at pressures similar to the Martian surface pressure we observed glow discharges. Electrical discharges can cause dissociation of CO2 and through subsequent reactions lead to a production of H2O2. These results indicate that the reactions linked to electrical discharges are the dominant source of H2O2 during saltation of silicates in a simulated Martian atmosphere, given the low pressure and the relatively high concentration of CO2. Our experiments provide evidence that wind driven abrasion could enhance the reactivity of the Martian soil and thereby could have contributed to the oxidation of organic compounds and the O2 release observed in the Labeled Release and the Gas Exchange experiments. Furthermore, the release of H2O2 and ṡOH from abraded silicates could have a negative effect on the persistence of organic compounds in the Martian soil and the habitability of the Martian surface.

  6. Oxidations of Organic and Inorganic Substrates by Superoxo-, hydroperoxo-, and oxo-compounds of the transition metals.

    Energy Technology Data Exchange (ETDEWEB)

    Vasbinder, Michael John [Iowa State Univ., Ames, IA (United States)


    fitting the observed rate constants to the Hammett correlation. It was found that the values of the Hammett reaction constant PN were -1.0(1) for 4-nitro-2-methylpyridine-N-oxide and -2.6(4) for 4-methylpyridine-N-oxide as substrates. The negative value confirms pyridine is acting as a nucleophile. Nucleophiles other than pyridine derivatives were also tested. In the end, it was found that the most effective nucleophiles were the pyridine-N-oxides themselves, meaning that a second equivalent of substrate serves as the most efficient promoter of this oxygen-atom transfer reaction. This relative nucleophilicity of pyridines and pyridine-N-oxides is similar to what is observed in other OAT reactions generating high-valent metal-oxo species.

  7. Tysnes Island - An unusual clast composed of solidified, immiscible, Fe-FeS and silicate melts. [in meteorite (United States)

    Wilkening, L. L.


    An inclusion found in the Tysnes Island gas-rich H4 chondrite is described. The clast consists of two distinct portions, separated by a smooth boundary; the portions are a tear-drop shaped Fe-FeS eutecticlike intergrowth (0.5 cm greatest dimension) and a silicate consisting primarily of olivine in glass. Nickel enrichment is found in the metal at the metal-sulfide boundaries and in nodules within the metal. It is thought that the portions separated from one another as immiscible liquids and that the modal composition of each portion agrees with the compositions predicted for a total melt of an H-group chondrite. The inclusion is discussed in terms of the process of metal-silicate fractionation suggested by Fodor and Keil (1976).

  8. Bonding of metal oxides in sodium silicate glass

    Energy Technology Data Exchange (ETDEWEB)

    Lam, D.J.; Veal, B.W.; Chen, H.; Knapp, G.S.


    X-ray photoelectron spectroscopy (XPS) and extended x-ray absorption fine structure (EXAFS) studies have been undertaken on sodium disilicate glasses containing varying amounts of Fe/sub 2/O/sub 3/ and UO/sub 2/. The XPS results enable one to distinguish the different bonding characteristics of iron and uranium in these glasses. A three dimensional model for the iron coordination in the sodium disilicate glass is inferred from the combined XPS and EXAFS results.

  9. Assessment of the risk of pollution by sulfur compounds and heavy metals in soils located in the proximity of a disused for 20 years sulfur mine (SE Poland). (United States)

    Sołek-Podwika, Katarzyna; Ciarkowska, Krystyna; Kaleta, Dorota


    The study assessed the long-term effects of anthropogenic pressure of the sulfur industry on turf-covered soils located in the vicinity of the sulfur mine Grzybów. The study assumes that 20 years which elapsed since the end of the exploitation of sulfur is a period sufficiently long for the content of sulfur compounds in soils not to exceed the permissible level and that soil of the region can be classified as not contaminated. A part of the study involved identification of changes in the contents Stot. and SSO4(2-) in soils collected in the 1970s and early twenty-first century. It was also traced the relationship between the content of sulfur compounds and selected soil properties and estimated risk of soil environment pollution by heavy metals. Mean contents of trace elements studied amounted to 10.2-10.8 mg kg(-1) for Pb, 14.3-39.4 mg kg(-1) for Zn, 0.2-0.4 mg kg(-1) for Cd, 3.8-32.2 mg kg(-1) for Cr, 2.7-15.1 mg kg(-1) for Cu and 2.9-18.7 mg kg(-1) for Ni. Based on the results of SSO4(2-) content in soils collected at a distance of 1 km from the mine, it was found out that despite the passage of years, the amount of this type of sulfur still is increased and exceeds 0.14 g kg(-1). As the distance from the mine grew lower (from 0.017 to 0.03 g kg(-1)) average content of the sulfur form was observed. In the studied soil material we found generally positive, strong correlation between the Stot. and SSO4(2-) content and analyzed trace elements. The degree of contamination of examined soils with heavy metals was estimated on the basis of the integrated pollution index, which pointed to a moderate and low level of antropogenization of this area. In addition, the relationship between the determined characteristics of soils (Corg. contents, the fraction soils do not occur in mobile forms in the soil solution.

  10. Refrigeration effect of La(FeCoSi)13B0.25 compounds and gadolinium metal in reciprocating magnetic refrigerator

    Institute of Scientific and Technical Information of China (English)

    程娟; 刘国栋; 黄焦宏; 刘翠兰; 金培育; 闫宏伟


    The LaFe11.9-xCoxSi1.1B0.25 with x=0.9 and x=0.82 compounds were synthesized from commercial purity raw materials. The magnetic property of LaFe11.9-xCoxSi1.1B0.25 and Gd particles were tested on the reciprocating refrigerator at the same condition in or-der to compare the cooling capacity of the two materials. The results showed that the cooling velocity of Gd was obviously higher than that of LaFe11.9-xCoxSi1.1B0.25. The maximum temperature span was 12.7 ºC for LaFe11.0Co0.9Si1.1B0.25, 14.9 ºC for Gd metal whose mass is the same as that of LaFe11.0Co0.9Si1.1B0.25, 8.1 ºC for Gd metal whose volume is the same as that of LaFe11.0Co0.9Si1.1B0.25. Se-ries connection of LaFe11.0Co0.9Si1.1B0.25 and LaFe11.08Co0.82Si1.1B0.25 had the maximum cooling temperature span of 15.3 ºC.

  11. The vertical distribution of selected trace metals and organic compounds in bottom materials of the proposed lower Columbia River export channel, Oregon, 1984 (United States)

    Fuhrer, Gregory J.; Horowitz, Arthur J.


    A proposal to deepen the lower Columbia River navigation channel in Oregon prompted a study of the vertical distribution of selected trace metals and organic compounds in bottom sediments. These data are needed to evaluate the effects of dredging and disposal operations. Elutriation testing of bottom material indicated chemical concentrations as large as 900 ug/L for barium, 6,500 ug/L for manganese, and 14 ug/L for nickel. The amount of oxygen present during elutriation testing of reduced bottom material was shown to have a negligble effect on manganese elutriate-test concentrations, but it did affect barium and iron concentrations. Sediment-associated organochlorine compounds detected in bottom-sediment core samples were as large as 0.1 ug/kg (micrograms/kilogram) for aldrin, 2.0 ug/kg for chlordane, 27 ug/kg for DDD, 5.0 ug/kg for DDE, 0.2 ug/kg for DDT, 0.2 ug/kg for dieldrin, 37 ug/kg for PCB 's 1.0 ug/kg for PCN 's and 1.0 ug/kg for heptachlor epoxide. Concentrations of cadmium, lead, and zinc in selected cores were found to exceed those of local basalts. Concentrations of cadmium, lead, and zinc were as large as 3.6 ug/g, 26 ug/g, and 210 ug/g respectively. Bottom-sediment concentrations of cadmium , chromium, copper, iron, and zinc associated with the less-than-100-micrometer size fraction are larger than those associated with the greater-than-100-micrometer fraction. (USGS)

  12. On new ternary equiatomic scandium transition metal aluminum compounds ScTAl with T = Cr, Ru, Ag, Re, Pt, and Au

    Energy Technology Data Exchange (ETDEWEB)

    Radzieowski, Mathis; Janka, Oliver [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Benndorf, Christopher [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; Haverkamp, Sandra [Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; Eckert, Hellmut [Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; University of Sao Paulo, Sao Carlos, SP (Brazil). Inst. of Physics


    The new equiatomic scandium transition metal aluminides ScTAl for T = Cr, Ru, Ag, Re, Pt, and Au were obtained by arc-melting of the elements followed by subsequent annealing for crystal growth. The samples were studied by powder and single crystal X-ray diffraction. The structures of three compounds were refined from single crystal X-ray diffractometer data: ScCrAl, MgZn{sub 2} type, P6{sub 3}/mmc, a = 525.77(3), c = 858.68(5) pm, R{sub 1} = 0.0188, wR{sub 2} = 0.0485, 204 F{sup 2} values, 13 variables, ScPtAl, TiNiSi type, Pnma, a = 642.83(4), b = 428.96(2), c = 754.54(5) pm, R{sub 1} = 0.0326, wR{sub 2} = 0.0458, 448 F{sup 2} values, 20 variables and ScAuAl, HfRhSn type, P anti 62c, a = 722.88(4), c = 724.15(4) pm, R{sub 1} = 0.0316, wR{sub 2} = 0.0653, 512 F{sup 2} values, 18 variables. Phase pure samples of all compounds were furthermore investigated by magnetic susceptibility measurements, and Pauli-paramagnetism but no superconductivity was observed down to 2.1 K for all of them. The local structural features and disordering phenomena have been characterized by {sup 27}Al and {sup 45}Sc magic angle spinning (MAS) and static NMR spectroscopic investigations.

  13. Characterizing Amorphous Silicates in Extraterrestrial Materials (United States)

    Fu, X.; Wang, A.; Krawczynski, M. J.


    Amorphous silicates are common in extraterrestrial materials. They are seen in the matrix of carbonaceous chondrites as well as in planetary materials. Tagish Lake is one of the most primitive carbonaceous meteorites in which TEM and XRD analyses found evidence for poorly crystalline phyllosilicate-like species; Raman spectra revealed amorphous silicates with variable degree of polymerization and low crystallinity. On Mars, CheMin discovered amorphous phases in all analyzed samples, and poorly crystalline smectite in mudstone samples. These discoveries pose questions on the crystallinity of phyllosilicates found by remote sensing on Mars, which is directly relevant to aqueous alteration during geologic history of Mars. Our goal is to use spectroscopy to better characterize amorphous silicates. We use three approaches: (1) using silicate glasses synthesized with controlled chemistry to study the effects of silicate polymerization and (2) using phyllosilicates synthesized with controlled hydrothermal treatment to study the effect of crystallinity on vibrational spectroscopy, finally (3) to use the developed correlations in above two steps to study amorphous phases in meteorites, and those found in future missions to Mars. In the 1st step, silicate glasses were synthesized from pure oxides in a range of NBO/T ratios (from 0 to 4). Depending on the targeted NBO/T and composition of mixed oxides, temperatures for each experiment fell in a range from 1260 to 1520 °C, run for ~ 4 hrs. The melt was quenched in liquid N2 or water. Homogeneity of glass was checked under optical microscopy. Raman spectra were taken over 100 spots on small chips free of bubbles and crystals. We have observed that accompanying an increase of NBO/T, there is a strengthening and a position shift of the Raman peak near 1000 cm-1 (Si-Onon-bridging stretching mode), and the weakening of broad Raman peaks near 500 cm-1 (ring breathing mode) and 700cm-1 (Si-Obridging-Si mode). We are building the

  14. A comparison between HfO2/Al2O3 nano-laminates and ternary HfxAlyO compound as the dielectric material in InGaAs based metal-oxide-semiconductor (MOS) capacitors (United States)

    Krylov, Igor; Pokroy, Boaz; Eizenberg, Moshe; Ritter, Dan


    We compare the electrical properties of HfO2/Al2O3 nano-laminates with those of the ternary HfxAlyO compound in metal oxide semiconductor (MOS) capacitors. The dielectrics were deposited by atomic layer deposition on InGaAs. Water, ozone, and oxygen plasma were tested as oxygen precursors, and best results were obtained using water. The total dielectric thickness was kept constant in our experiments. It was found that the effective dielectric constant increased and the leakage current decreased with the number of periods. Best results were obtained for the ternary compound. The effect of the sublayer thicknesses on the electrical properties of the interface was carefully investigated, as well as the role of post-metallization annealing. Possible explanations for the observed trends are provided. We conclude that the ternary HfxAlyO compound is more favorable than the nano-laminates approach for InGaAs based MOS transistor applications.

  15. Mid-infrared Extinction and Fresh Silicate Dust towards the Galactic Center (United States)

    Voshchinnikov, Nikolai V.; Henning, Thomas; Il’in, Vladimir B.


    We interpret the interstellar extinction observed toward the Galactic center (GC) in the wavelength range λ = 1–20 μm. Its main feature is the flat extinction at 3–8 μm whose explanation is still a problem for cosmic dust models. We search for the structure and chemical composition of dust grains that could explain the observed extinction. In contrast to earlier works, we use laboratory measured optical constants and consider particles of different structures. We show that a mixture of compact grains of aromatic carbon and of some silicate is better suited for reproducing the flat extinction in comparison with essentially porous grains or aliphatic carbon particles. Metallic iron should be located inside the particle, i.e., it cannot form layers on silicate grains as the extinction curves then become very peculiar. We find a model including aromatic carbonaceous particles and three-layered particles with an olivine-type silicate core, a thin, very porous layer and a thin envelope of magnetite that provides a good (but still not perfect) fit to the observational data. We suggest that such silicate dust should be fresh, i.e., recently formed in the atmospheres of late-type stars in the central region of the Galaxy. We assume that this region has a radius of about 1 kpc and produces about half of the observed extinction. The remaining part of extinction is caused by a “foreground” material being practically transparent at λ =4{--}8 μ {{m}}.

  16. On the dielectric response of complex layered oxides: Mica-type silicates and layered double hydroxides (United States)

    Mehrotra, Vivek; Giannelis, Emmanuel P.


    The dielectric properties of mica-type silicates and layered double hydroxides have been studied in the pristine and various intercalated forms in the frequency range 101-107 Hz. A relaxation peak has been observed for the pristine silicate, whereas the pristine layered double hydroxide exhibits an anomalous low-frequency dispersion. The dielectric response is rationalized in terms of structural ordering and fluctuation of charge carriers as well as models invoking fractal time processes and fractal structure. The response is also related to the structure and mobility of the intercalated water molecules. In both pristine hosts, the predominant conduction mechanism is proton hopping between sites generated by a network of intercalated water molecules. Silicate intercalated with the insulating form of polyaniline exhibits an almost frequency-independent response. In the case of conducting polyaniline intercalated silicate, where polarons are the majority charge carriers, an anomalous low-frequency dispersion is observed and the response is typical of a metal-insulator composite. Finally, impedance measurements have been used to calculate the spatial disorder and/or surface irregularity of the host layers, expressed by the fractal dimension ds. The changes observed in ds upon intercalation of high-charge ions are correlated to the stacking disorder of the host layers.

  17. Separation of Metal Chelates and Organometallic Compounds by Supercritical Fluid Chromatography%超临界流体色谱在金属络合物和金属有机化合物中的分析应用

    Institute of Scientific and Technical Information of China (English)

    王少芬; 魏建谟


    超临界流体色谱(SFC)在色谱分离过程中能在较低的温度下分析对热不稳定的化合物,包括金属络合物和金属有机化合物。本文总结了近来文献报道的各种过渡金属、重金属、镧系和锕系以及铅、汞和锡的金属有机化合物的SFC分离,还讨论了SFC检测系统和金属有机化合物的溶解度的测定。%Supercritical fluid chromatography (SFC) combines the hig h diffusion coefficients of gas chromatography (GC) and the solubility propertie s of liquid chromatography (LC). SFC generally requires lower temperatures for chromatographic separations and thus is more suitable for analyzing thermally l abile compounds including a number of metal chelates and organometallic compound s. SFC also allows interfacing between supercritical fluid extraction (SFE) and chromatographic analysis of metal-containing compounds. A large number of metal chelates and organometallic compounds can be separated b y SFC. This article summarizes SFC separation of various chelates of transitio n metals, heavy metals, lanthanides and actinides as well as organometallic comp ounds of lead, mercury and tin reported in the recent literature. This articl e also discusses SFC detection systems and the determination of solubility of or ganometallic compounds by SFC.

  18. Oxygen isotope and petrological study of silicate inclusions in IIE iron meteorites and their relationship with H chondrites (United States)

    McDermott, Kathryn H.; Greenwood, Richard C.; Scott, Edward R. D.; Franchi, Ian A.; Anand, Mahesh


    The origin of silicate-bearing irons, especially those in groups IAB, IIICD, and IIE, is poorly understood as silicate should have separated rapidly from molten metal. Here we report the results of high precision oxygen isotope analysis of silicate inclusions in eleven group IIE meteorites and a petrological study of silicate inclusions in ten IIE irons including those in Garhi Yasin and Tarahumara, which have not been described in detail before. Oxygen isotopes have also been analysed in 20 H chondrites to investigate their possible relationship with the IIE irons. Based on petrographic observations and mineral analysis, the silicate-bearing IIE meteorites have been divided into four types according to the nature of their silicate inclusions: (1) primitive chondritic, (2) evolved chondritic, (3) differentiated with >10 vol.% orthopyroxene, and (4) differentiated with source for Colomera is deemed unlikely. Three IIE irons with primitive chondritic inclusions, Garhi Yasin, Netschaëvo, and Techado, have relatively low mean Δ17O values of 0.56-0.57‰ as well as relatively reduced silicates with Fa15-17 olivine, which have been called HH chondrites. Given the significant overlap in their oxygen isotope compositions, a genetic relationship between IIE irons and H chondrites is supported by our new data. However, derivation of both groups from one parent body seems unlikely. Instead, both groups probably sampled similar precursor materials and accreted at a similar nebular location. Our data suggest that the IIE meteorites formed on an internally heated H/HH chondrite-like body that experienced the initial stages of differentiation in response to radiogenic heating. However, prior to full differentiation the IIE parent body experienced a major hit-and-run style collision that resulted in silicate-metal mixing. The initial stages of this event involved a phase of rapid cooling that prevented unmixing of metal and silicates. Reassembly of the IIE parent body produced a

  19. 金属核心 /高聚物膜复合悬浮相电流变流体材料%Metal Core/Polymer Coating Compounded Suspension for Electrorheologic Fluid

    Institute of Scientific and Technical Information of China (English)

    丁文; 范志康; 徐传骧; 卢凤纪


    Aiming at researching and developing new compounded suspensions to sever as electrorheological fluid (ERF), a metal core/polymer coating compounded suspension for ERF has been designed according to the principle of media polarization. Based on this evolution,a series of metal core/high polymer coating compounded particles such as Zn/poly-styrene-butyl-acrylate compounded particles, Ni/poly-styrene-butyl-acrylate compounded particles, Ni/polystyrene compounded particles, Zn/polystyrene compounded particles have been prepared adopting the emulsion polymerization together with the micro-encapsulation techniques as well as the acid-alkali matching theory which was initially suggested by Fowkes(schematically depicted in Fig.1). The micro-morphologies of these compounded particles were measured using scan electron microscophy(the SEM photography of Fig.2 exhibits the coated condition of these particles) and the ERF performance of these compounded particles have alse been carried out. The performance test results indicate that the mechanical properties (refer to Fig.5~ 10 ) and the stability of ERF were improved, i.e. shear strength was no less than 2 kPa and segregation resistance was intensified significantly compared with that of metal core, which shows that these materials are promising for acting as ERF though further modification should be necessary. Besides, from the performance test results it is apparently found that different compounded suspensions made up of different metal cores or polymer coatings possess various mechanical properties,and explanations for this phenomenon will discussed in detail elsewhere.%针对电流变流体悬浮相材料的开发与研究,根据介质极化原理,设计开发了金属核心 /高聚物膜复合悬浮相电流变流体材料,在乳液聚合与微胶囊包覆技术的基础上,制备出了金属核心 /高聚物膜复合颗粒 .并对这种金属核心 /高聚物膜复合颗粒的电流变流体

  20. Blue/pink/purple electroluminescence from metal-oxide-semiconductor devices fabricated by spin-coating of [tantalum:(gadolinium/praseodymium)] and (praseodymium:cerium) organic compounds on silicon (United States)

    Ohzone, Takashi; Matsuda, Toshihiro; Fukuoka, Ryouhei; Hattori, Fumihiro; Iwata, Hideyuki


    Blue/pink/purple electroluminescence (EL) from metal-oxide-semiconductor (MOS) devices with an indium tin oxide (ITO)/[Gd/(Ta + Gd/Pr)/(Pr + Ce)-Si-O] insulator layer/n+-Si substrate surface is reported. The insulator layers were fabricated from organic liquid sources of Gd or (Ta + Gd/Pr)/(Pr + Ce) mixtures, which were spin-coated on the n+-Si substrate and annealed at 950 °C for 30 min in air. The EL emission could be observed by the naked eye in the dark in the Fowler-Nordheim (FN) tunnel current regions. Peak wavelengths in the measured EL spectra were independent of the positive current. The EL intensity ratio of ultraviolet (UV) to the visible range varied with the composition ratio of the (Ta + Gd) liquids, and an optimum Ta to Gd ratio existed for the strongest blue emission, which could be attributed to the Ta-related oxide/silicate. The pink EL of the device fabricated with the (\\text{Ta}:\\text{Pr} = 6:4) mixture ratio can be explained by EL emission peaks related to the Pr3+ ions. The purple EL observed from the (\\text{Pr}:\\text{Ce} = 6:4) device corresponds to the strong and broad emission profile near the 357 nm peak, which cannot be assigned to Ce3+ ions. The results suggest that the EL can be attributed to the double-layer oxides with different compositions in the MOS devices. The upper layer consists of various Ta-, Gd-, Pr-, and Ce-related oxides and their silicates, while the lower SiO x -rich layer contributes to the FN current due to the high electric field, and thus the various EL colors.

  1. Cooling rate calculations for silicate glasses. (United States)

    Birnie, D. P., III; Dyar, M. D.


    Series solution calculations of cooling rates are applied to a variety of samples with different thermal properties, including an analog of an Apollo 15 green glass and a hypothetical silicate melt. Cooling rates for the well-studied green glass and a generalized silicate melt are tabulated for different sample sizes, equilibration temperatures and quench media. Results suggest that cooling rates are heavily dependent on sample size and quench medium and are less dependent on values of physical properties. Thus cooling histories for glasses from planetary surfaces can be estimated on the basis of size distributions alone. In addition, the variation of cooling rate with sample size and quench medium can be used to control quench rate.

  2. Tracking bubble evolution inside a silicic dike (United States)

    Álvarez-Valero, Antonio M.; Okumura, Satoshi; Arzilli, Fabio; Borrajo, Javier; Recio, Clemente; Ban, Masao; Gonzalo, Juan C.; Benítez, José M.; Douglas, Madison; Sasaki, Osamu; Franco, Piedad; Gómez-Barreiro, Juan; Carnicero, Asunción


    Pressure estimates from rapidly erupted crustal xenoliths constrain the depth of intrusion of the silicic lavas hosting them. This represents an opportunity for tracking magmatic bubble's evolution and quantifying the variation in bubble volume during rapid magma ascent through a volcanic dike just prior to eruption. The petrology, stable-isotope geochemistry and X-ray micro-tomography of dacites containing crustal xenoliths, erupted from a Neogene volcano in SE Spain, showed an increase in porosity from ~ 1.7 to 6.4% from ~ 19 to 13 km depth, at nearly constant groundmass and crystal volumes. This result provides additional constraints for experimental and numerical simulations of subvolcanic magma-crust degassing processes in silicic systems, and may allow the characterization of volcanic eruptive styles based on volatile content.

  3. Recycle of silicate waste into mesoporous materials. (United States)

    Kim, Jung Ho; Kim, Minwoo; Yu, Jong-Sung


    Template synthesis of porous carbon materials usually requires selective removal of template silica from the carbon/silica composites. It not only involves waste of valuable chemicals, but also poses significant environmental concerns including high waste treatment cost. Recycling of silicates released from such nanocasting methods is successfully performed for the first time to regenerate valuable mesoporous MCM and SBA type silica materials, which will not only help in saving valuable chemicals, but also in decreasing chemical waste, contributing in improvement of our environmental standards. This approach can thus improve cost effectiveness for the mass production of nanostructured carbon and others utilizing silica directed nanocasting method by recycling otherwise silicate waste into highly desirable valuable mesoporous silica.

  4. Role of a silicate phase in the reduction of iron and chromium and their oxidation with carbide formation during the manufacture of carbon ferrochrome (United States)

    Roshchin, V. E.; Roshchin, A. V.; Akhmetov, K. T.; Salikhov, S. P.


    The reactions of reduction of chromium and iron from chromospinelide and the reactions of carbide formation from the reduced metals are separated in space in experiments performed on ore grains with an artificially applied silicate shell. It is found that the silicate layer that isolates spinelide fro direct contact with carbon takes part in the reactions of both reduction and carbide formation. Free carbon extracts oxygen anions from the layer at the contact surface with the formation of CO, and the forming anion vacancies transfer "excess" electrons to the iron and chromium cations in the spinelide lattice and reduce them. Free and carbide-fixed carbon extracts iron and chromium cations from the silicate layer, and carbides form on the surface. The cation vacancies and electron holes (high-charge cations) that form in the silicate phase under these conditions are involved in the oxidation of the metal reduced in spinelide and cause its dissolution in the silicate phase and the precipitation of lower carbides on the surface of the silicate phase. The structure that is characterized of carbon ferrochrome forms on the surface of the silicate phase. Carbide formation is slower than reduction because of higher energy consumed for the formation of high-charge cations and the transfer of cations from the spinelide volume to the outer surface of the silicate phase. In the absence of a silicate layer, a carbide shell blocks the contact of carbon with oxides, which leads to the stop of reduction and, then, carbide formation. In the presence of a silicate (slag) shell around a spinelide grain, the following two concentration galvanic cells operate in parallel: an oxygen (reduction) cell and a metal (oxidation) cell. The parallel operation of the two galvanic cells with a common electrolyte (silicate phase) results in a decrease in the electric potentials between spinelide inside the silicate phase and carbon and carbides on its surface, and each of the processes is

  5. Bias-Switchable Permselectivity and Redox Catalytic Activity of a Ferrocene-Functionalized, Thin-Film Metal-Organic Framework Compound. (United States)

    Hod, Idan; Bury, Wojciech; Gardner, Daniel M; Deria, Pravas; Roznyatovskiy, Vladimir; Wasielewski, Michael R; Farha, Omar K; Hupp, Joseph T


    The installation of ferrocene molecules within the wide-channel metal-organic framework (MOF) compound, NU-1000, and subsequent configuration of the modified MOF as thin-film coatings on electrodes renders the MOF electroactive in the vicinity of the ferrocenium/ferrocene (Fc(+)/Fc) redox potential due to redox hopping between anchored Fc(+/0) species. The observation of effective site-to-site redox hopping points to the potential usefulness of the installed species as a redox shuttle in photoelectrochemical or electrocatalytic systems. At low supporting electrolyte concentration, we observe bias-tunable ionic permselectivity; films are blocking toward solution cations when the MOF is in the ferrocenium form but permeable when in the ferrocene form. Additionally, with ferrocene-functionalized films, we observe that the MOF's pyrene-based linkers, which are otherwise reversibly electroactive, are now redox-silent. Linker electroactivity is fully recovered, however, when the electrolyte concentration is increased 10-fold, that is, to a concentration similar to or exceeding that of an anchored shuttle molecule. The findings have clear implications for the design and use of MOF-based sensors, electrocatalysts, and photoelectrochemical devices.

  6. Geobacter metallireducens gen. nov. sp. nov., a microorganism capable of coupling the complete oxidation of organic compounds to the reduction of iron and other metals (United States)

    Lovley, D.R.; Giovannoni, S.J.; White, D.C.; Champine, J.E.; Phillips, E.J.P.; Gorby, Y.A.; Goodwin, S.


    The gram-negative metal-reducing microorganism, previously known as strain GS-15, was further characterized. This strict anaerobe oxidizes several short-chain fatty acids, alcohols, and monoaromatic compounds with Fe(III) as the sole electron acceptor. Furthermore, acetate is also oxidized with the reduction of Mn(IV), U(VI), and nitrate. In whole cell suspensions, the c-type cytochrome(s) of this organism was oxidized by physiological electron acceptors and also by gold, silver, mercury, and chromate. Menaquinone was recovered in concentrations comparable to those previously found in gram-negative sulfate reducers. Profiles of the phospholipid ester-linked fatty acids indicated that both the anaerobic desaturase and the branched pathways for fatty acid biosynthesis were operative. The organism contained three lipopolysaccharide hydroxy fatty acids which have not been previously reported in microorganisms, but have been observed in anaerobic freshwater sediments. The 16S rRNA sequence indicated that this organism belongs in the delta proteobacteria. Its closest known relative is Desulfuromonas acetoxidans. The name Geobacter metallireducens is proposed.

  7. The role of the substrate on the dispersion in accumulation in III-V compound semiconductor based metal-oxide-semiconductor gate stacks

    Energy Technology Data Exchange (ETDEWEB)

    Krylov, Igor, E-mail: [The Russell Berrie Nanotechnology Institute, Technion – Israel Institute of Technology, Haifa 32000 (Israel); Ritter, Dan [The Russell Berrie Nanotechnology Institute, Technion – Israel Institute of Technology, Haifa 32000 (Israel); Department of Electrical Engineering, Technion – Israel Institute of Technology, Haifa 32000 (Israel); Eizenberg, Moshe [The Russell Berrie Nanotechnology Institute, Technion – Israel Institute of Technology, Haifa 32000 (Israel); Department of Materials Science and Engineering, Technion – Israel Institute of Technology, Haifa 32000 (Israel)


    Dispersion in accumulation is a widely observed phenomenon in metal-oxide-semiconductor gate stacks based on III-V compound semiconductors. The physical origin of this phenomenon is attributed to border traps located in the dielectric material adjacent to the semiconductor. Here, we study the role of the semiconductor substrate on the electrical quality of the first layers at atomic layer deposited (ALD) dielectrics. For this purpose, either Al{sub 2}O{sub 3} or HfO{sub 2} dielectrics with variable thicknesses were deposited simultaneously on two technology important semiconductors—InGaAs and InP. Significantly larger dispersion was observed in InP based gate stacks compared to those based on InGaAs. The observed difference is attributed to a higher border trap density in dielectrics deposited on InP compared to those deposited on InGaAs. We therefore conclude that the substrate plays an important role in the determination of the electrical quality of the first dielectric monolayers deposited by ALD. An additional observation is that larger dispersion was obtained in HfO{sub 2} based capacitors compared to Al{sub 2}O{sub 3} based capacitors, deposited on the same semiconductor. This phenomenon is attributed to the lower conduction band offset rather than to a higher border trap density.

  8. Interfacial reactions and compound formation of Sn-Ag-Cu solders by mechanical alloying on electroless Ni-P/Cu under bump metallization (United States)

    Kao, Szu-Tsung; Duh, Jenq-Gong


    Electroless Ni-P under bump metallization (UBM) has been widely used in electronic interconnections due to the good diffusion barrier between Cu and solder. In this study, the mechanical alloying (MA) process was applied to produce the SnAgCu lead-free solder pastes. Solder joints after annealing at 240°C for 15 min were employed to investigate the evolution of interfacial reaction between electroless Ni-P/Cu UBM and SnAgCu solder with various Cu concentrations ranging from 0.2 to 1.0 wt.%. After detailed quantitative analysis with an electron probe microanalyzer, the effect of Cu content on the formation of intermetallic compounds (IMCs) at SnAgCu solder/electroless Ni-P interface was evaluated. When the Cu concentration in the solder was 0.2 wt.%, only one (Ni, Cu)3Sn4 layer was observed at the solder/electroless Ni-P interface. As the Cu content increased to 0.5 wt.%, (Cu, Ni)6Sn5 formed along with (Ni, Cu)3Sn4. However, only one (Cu, Ni)6Sn5 layer was revealed, if the Cu content was up to 1 wt.%. With the aid of microstructure evolution, quantitative analysis, and elemental distribution by x-ray color mapping, the presence of the Ni-Sn-P phase and P-rich layer was evidenced.

  9. Aspherical-atom modeling of coordination compounds by single-crystal X-ray diffraction allows the correct metal atom to be identified. (United States)

    Dittrich, Birger; Wandtke, Claudia M; Meents, Alke; Pröpper, Kevin; Mondal, Kartik Chandra; Samuel, Prinson P; Amin Sk, Nurul; Singh, Amit Pratap; Roesky, Herbert W; Sidhu, Navdeep


    Single-crystal X-ray diffraction (XRD) is often considered the gold standard in analytical chemistry, as it allows element identification as well as determination of atom connectivity and the solid-state structure of completely unknown samples. Element assignment is based on the number of electrons of an atom, so that a distinction of neighboring heavier elements in the periodic table by XRD is often difficult. A computationally efficient procedure for aspherical-atom least-squares refinement of conventional diffraction data of organometallic compounds is proposed. The iterative procedure is conceptually similar to Hirshfeld-atom refinement (Acta Crystallogr. Sect. A- 2008, 64, 383-393; IUCrJ. 2014, 1,61-79), but it relies on tabulated invariom scattering factors (Acta Crystallogr. Sect. B- 2013, 69, 91-104) and the Hansen/Coppens multipole model; disordered structures can be handled as well. Five linear-coordinate 3d metal complexes, for which the wrong element is found if standard independent-atom model scattering factors are relied upon, are studied, and it is shown that only aspherical-atom scattering factors allow a reliable assignment. The influence of anomalous dispersion in identifying the correct element is investigated and discussed.

  10. Six White Dwarfs with Circumstellar Silicates

    CERN Document Server

    Jura, M; Zuckerman, B


    Spitzer Space Telescope spectra reveal 10 micron silicate emission from circumstellar dust orbiting six externally-polluted white dwarfs. Micron-size glasses with an olivine stoichiometry can account for the distinctively broad wings that extend to 12 microns; these particles likely are produced by tidal-disruption of asteroids. The absence of infrared PAH features is consistent with a scenario where extrasolar rocky planets are assembled from carbon-poor solids.

  11. Adsorption of dimeric surfactants in lamellar silicates

    Energy Technology Data Exchange (ETDEWEB)

    Balcerzak, Mateusz; Pietralik, Zuzanna [Department of Macromolecular Physics, Faculty of Physics, A. Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland); Domka, Ludwik [Department of Metalorganic Chemistry, Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Poznań (Poland); Skrzypczak, Andrzej [Institute of Chemical Technology, Poznań University of Technology, Berdychowo 4, 60-965 Poznań (Poland); Kozak, Maciej, E-mail: [Department of Macromolecular Physics, Faculty of Physics, A. Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland)


    Highlights: • The intercalation of dimeric surfactants changed the morphology of MMT samples. • XRD indicated structures formed by surfactant molecules in interlayer space. • The four-step thermal decomposition of dimeric surfactant, confirms intercalation. - Abstract: The adsorption of different types of cationic surfactants in lamellar silicates changes their surface character from hydrophilic to hydrophobic. This study was undertaken to obtain lamellar silicates modified by a series of novel dimeric (gemini) surfactants of different length alkyl chains and to characterise these organophilised materials. Synthetic sodium montmorillonite SOMASIF® ME 100 (M) and enriched bentonite of natural origin (Nanoclay – hydrophilic bentonite®) were organophilised with dimeric (gemini) surfactants (1,1′-(1,4-butanediyl)bis(alkoxymethyl)imidazolium dichlorides). As a result of surfactant molecule adsorption in interlamellar space, the d-spacing (d{sub 001}) increased from 0.97 nm (for the anhydrous structure) to 2.04 nm. A Fourier transform infrared spectroscopy (FTIR) analysis of the modified systems reveals bands assigned to the stretching vibrations of the CH{sub 2} and CH{sub 3} groups and the scissoring vibrations of the NH group from the structure of the dimeric surfactants. Thermogravimetric (TG) and derivative thermogravimetric (DTG) studies imply a four-stage process of surfactant decomposition. Scanning electron microscopy (SEM) images provide information on the influence of dimeric surfactant intercalation into the silicate structures. Particles of the modified systems show a tendency toward the formation of irregularly shaped agglomerates.

  12. Production of reactive oxygen species from abraded silicates. Implications for the reactivity of the Martian soil

    DEFF Research Database (Denmark)

    Bak, Ebbe N.; Zafirov, Kaloyan; Merrison, Jonathan P.


    lead to a production of H(2)O(2)facilitated by atmospheric O-2 and inhibited by carbon dioxide. Furthermore, during simulated saltation the silicate particles became triboelectrically charged and at pressures similar to the Martian surface pressure we observed glow discharges. Electrical discharges can......The results of the Labeled Release and the Gas Exchange experiments conducted on Mars by the Viking Landers show that compounds in the Martian soil can cause oxidation of organics and a release of oxygen in the presence of water. Several sources have been proposed for the oxidizing compounds...

  13. Production of reactive oxygen species from abraded silicates. Implications for the reactivity of the Martian soil

    DEFF Research Database (Denmark)

    Bak, Ebbe Norskov; Zafirov, Kaloyan; Merrison, Jonathan P.


    of H2O2 facilitated by atmospheric O2 and inhibited by carbon dioxide. Furthermore, during simulated saltation the silicate particles became triboelectrically charged and at pressures similar to the Martian surface pressure we observed glow discharges. Electrical discharges can cause dissociation of CO......The results of the Labeled Release and the Gas Exchange experiments conducted on Mars by the Viking Landers show that compounds in the Martian soil can cause oxidation of organics and a release of oxygen in the presence of water. Several sources have been proposed for the oxidizing compounds...

  14. Effect of Zn addition on non-resonant third-order optical nonlinearity of the Cu-doped germano-silicate optical glass fiber. (United States)

    Ju, Seongmin; Watekar, Pramod R; Jeong, Seongmook; Kim, Youngwoong; Han, Won-Taek


    Cu/Zn-codoped germano-silicate optical glass fiber was manufactured by using the modified chemical vapor deposition (MCVD) process and solution doping process. To investigate the reduction effect of Zn addition on Cu metal formation in the core of the Cu/Zn-codoped germano-silicate optical glass fiber, the optical absorption property and the non-resonant third-order optical nonlinearity were measured. Absorption peaks at 435 nm and 469 nm in the Cu/Zn-codoped germano-silicate optical glass fiber were contributed to Cu metal particles and ZnO semiconductor particles, respectively. The effective non-resonant optical nonlinearity, gamma, of the Cu/Zn-codoped germano-silicate optical glass fiber was measured to be 1.5097 W(-1) x km(-1) by using the continuous-wave self-phase modulation method. The gamma of the Cu/Zn-codoped germano-silicate optical glass fiber was about four times larger than that of the reference germano-silicate optical glass fiber without any dopants. The increase of the effective non-resonant optical nonlinearity, gamma, of the Cu/Zn-codoped germano-silicate optical glass fiber, can be attributed to the enhanced nonlinear polarization due to incorporated ZnO semiconductor particles and Cu metal ions in the glass network. The Cu/Zn-codoped germano-silicate optical glass fiber showed high nonlinearity and low transmission loss at the optical communication wavelength, which makes it suitable for high-speed-high-capacity optical communication systems.