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Sample records for active metal phase

  1. Gas-phase activation of methane by ligated transition-metal cations

    PubMed Central

    Schröder, Detlef; Schwarz, Helmut

    2008-01-01

    Motivated by the search for ways of a more efficient usage of the large, unexploited resources of methane, recent progress in the gas-phase activation of methane by ligated transition-metal ions is discussed. Mass spectrometric experiments demonstrate that the ligands can crucially influence both reactivity and selectivity of transition-metal cations in bond-activation processes, and the most reactive species derive from combinations of transition metals with the electronegative elements fluorine, oxygen, and chlorine. Furthermore, the collected knowledge about intramolecular kinetic isotope effects associated with the activation of C–H(D) bonds of methane can be used to distinguish the nature of the bond activation as a mere hydrogen-abstraction, a metal-assisted mechanism or more complex reactions such as formation of insertion intermediates or σ-bond metathesis. PMID:18955709

  2. Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

    DOEpatents

    Doeff, M.M.; Peng, M.Y.; Ma, Y.; Visco, S.J.; DeJonghe, L.C.

    1996-09-24

    An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M{sub x}Z{sub y}Mn{sub (1{minus}y)}O{sub 2}, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell. 11 figs.

  3. Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

    DOEpatents

    Doeff, Marca M.; Peng, Marcus Y.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard C.

    1996-01-01

    An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M.sub.x Z.sub.y Mn.sub.(1-y) O.sub.2, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell.

  4. Measuring the Noble Metal and Iodine Composition of Extracted Noble Metal Phase from Spent Nuclear Fuel Using Instrumental Neutron Activation Analysis

    SciTech Connect

    Palomares, R. I.; Dayman, Kenneth J.; Landsberger, Sheldon; Biegalski, Steven R.; Soderquist, Chuck Z.; Casella, Amanda J.; Brady Raap, Michaele C.; Schwantes, Jon M.

    2015-04-01

    Mass quantities of noble metal and iodine nuclides in the metallic noble metal phase extracted from spent fuel are measured using instrumental neutron activation analysis (NAA). Nuclide presence is predicted using fission yield analysis, and mass quantification is derived from standard gamma spectroscopy and radionuclide decay analysis. The nuclide compositions of noble metal phase derived from two dissolution methods, UO2 fuel dissolved in nitric acid and UO2 fuel dissolved in ammonium-carbonate and hydrogen-peroxide solution, are compared. Lastly, the implications of the rapid analytic speed of instrumental NAA are discussed in relation to potential nuclear forensics applications.

  5. Bond Activation by Metal-Carbene Complexes in the Gas Phase.

    PubMed

    Zhou, Shaodong; Li, Jilai; Schlangen, Maria; Schwarz, Helmut

    2016-03-15

    "Bare" metal-carbene complexes, when generated in the gas phase and exposed to thermal reactions under (near) single-collision conditions, exhibit rather unique reactivities in addition to the well-known metathesis and cyclopropanation processes. For example, at room temperature the unligated [AuCH2](+) complex brings about efficient C-C coupling with methane to produce C2Hx (x = 4, 6), and the couple [TaCH2](+)/CO2 gives rise to the generation of the acetic acid equivalent CH2═C═O. Entirely unprecedented is the thermal extrusion of a carbon atom from halobenzenes (X = F, Cl, Br, I) by [MCH2](+) (M = La, Hf, Ta, W, Re, Os) and its coupling with the methylene ligand to deliver C2H2 and [M(X)(C5H5)](+). Among the many noteworthy C-N bond-forming processes, the formation of CH3NH2 from [RhCH2](+)/NH3, the generation of CH2═NH2(+) from [MCH2](+)/NH3 (M = Pt, Au), and the production of [PtCH═NH2](+) from [PtCH2](+)/NH3 are of particular interest. The latter species are likely to be involved as intermediates in the platinum-mediated large-scale production of HCN from CH4/NH3 (the DEGUSSA process). In this context, a few examples are presented that point to the operation of co-operative effects even at a molecular level. For instance, in the coupling of CH4 with NH3 by the heteronuclear clusters [MPt](+) (M = coinage metal), platinum is crucial for the activation of methane, while the coinage metal M controls the branching ratio between the C-N bond-forming step and unwanted soot formation. For most of the gas-phase reactions described in this Account, detailed mechanistic insight has been derived from extensive computational work in conjunction with time-honored labeling and advanced mass-spectrometry-based experiments, and often a coherent description of the experimental findings has been achieved. As for some transition metals, in particular those from the third row, the metal-carbene complexes can be formed directly from methane, coupling of the so

  6. Mechanistic Variants in Gas-Phase Metal-Oxide Mediated Activation of Methane at Ambient Conditions.

    PubMed

    Li, Jilai; Zhou, Shaodong; Zhang, Jun; Schlangen, Maria; Usharani, Dandamudi; Shaik, Sason; Schwarz, Helmut

    2016-09-07

    The C-H bond activation of methane mediated by a prototypical heteronuclear metal-oxide cluster, [Al2Mg2O5](•+), was investigated by using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) in conjunction with high-level quantum mechanical calculations. Experimentally, hydrogen-atom abstraction from methane by the cluster ion [Al2Mg2O5](•+) takes place at ambient conditions. As to the mechanism, according to our computational findings, both the proton-coupled electron transfer (PCET) and the conventional hydrogen-atom transfer (HAT) are feasible and compete with each other. This is in distinct contrast to the [XYO2](+) (X, Y = Mg, Al, Si) cluster oxide ions which activate methane exclusively via the PCET route (Li, J.; Zhou, S.; Zhang, J.; Schlangen, M.; Weiske, T.; Usharani, D.; Shaik, S.; Schwarz, H. J. Am. Chem. Soc. 2016, 138, 7973-7981). The electronic origins of the mechanistically rather complex reactivity scenarios of the [Al2Mg2O5](•+)/CH4 couple were elucidated. For the PCET mechanism, in which the Lewis acid-base pair [Al(+)-O(-)] of the cluster acts as the active site, a clear correlation has been established between the nature of the transition state, the corresponding barrier height, the Lewis acidity-basicity of the [M(+)-O(-)] unit, as well as the bond order of the M(+)-O(-) bond. Also addressed is the role of the spin and charge distributions of a terminal oxygen radical site in the direct HAT route. The knowledge of the factors that control the reactivity of PCET and HAT pathways not only deepens our mechanistic understanding of metal-oxide mediated C-H bond activation but may also provide guidance for the rational design of catalysts.

  7. Formation of sensitive/active phases in metal and polymer-based structural materials

    NASA Astrophysics Data System (ADS)

    Asanuma, Hiroshi

    2002-11-01

    This paper describes new concepts the author has proposed and demonstrated to realize metal and polymer based sensitive and/or active structural material systems suitable for smart structures. Most of the developments have been done by simple and innovative methods without using sophisticated and expensive sensors and actuators. The following topics are mainly examined: (1) embedding optical fiber in aluminum matrix to use as sensors; (2) forming optical interference and loss type strain sensors in epoxy matrix simply by embedding and breaking notched optical fiber in it; (3) forming a multifunctional sensor in aluminum matrix for temperature and strain monitoring by embedding an oxidized nickel fiber; (4) fabricating multifunctional composites by using conventional structural materials - i) an active laminate of CFRP/aluminum of which unidirectional actuation is realized by electrical resistance heating of carbon fiber in the CFRP layer and its curvature change can be monitored using optical fiber multiply fractured in the CFRP layer, and ii) a multifunctional aluminum-matrix composite where oxidized titanium fiber is embedded for sensing temperature and strain, generation of heat for actuation.

  8. Electronically controlled optical beam-steering by an active phased array of metallic nanoantennas.

    PubMed

    DeRose, C T; Kekatpure, R D; Trotter, D C; Starbuck, A; Wendt, J R; Yaacobi, A; Watts, M R; Chettiar, U; Engheta, N; Davids, P S

    2013-02-25

    An optical phased array of nanoantenna fabricated in a CMOS compatible silicon photonics process is presented. The optical phased array is fed by low loss silicon waveguides with integrated ohmic thermo-optic phase shifters capable of 2π phase shift with ∼ 15 mW of applied electrical power. By controlling the electrical power to the individual integrated phase shifters fixed wavelength steering of the beam emitted normal to the surface of the wafer of 8° is demonstrated for 1 × 8 phased arrays with periods of both 6 and 9 μm.

  9. Phase stability in metallic multilayers

    NASA Astrophysics Data System (ADS)

    Genc, Arda

    this problem has been solved by the correction of the spherical aberration of the microscope using a set of non-round lenses and consequently the information limit in an aberration corrected microscope (<0.1nm) has been pushed beyond an uncorrected microscope (˜0.13nm). In 2007, such a corrector system in the probe-forming lens of a Scanning TEM microscope was successfully installed at The Ohio State University. The preliminary results from this microscope were presented in the content of this work where we have studied the microscope and performed first hand experiments. Finally we have addressed the phase stability in Cu/Nb and Ti/Nb nanoscale metallic multilayers by extensive use of these advance characterization techniques and tools. At reduced layer thickness (<2nm) the change in fcc to bcc phase in Cu and hcp to bcc phase in Ti were experimentally confirmed using X-ray diffraction electron diffraction and electron imaging techniques along the plan-view and cross-section directions. These structural transformations were often referred to as being thermodynamic in nature and a classical thermodynamical model explains and predicts the formation of such pseudomorphic phases through the competition of volumetric and interfacial free energy variables. We have investigated both the structural and chemical changes in the Cu/Nb and Ti/Nb nanoscale metallic mutilayers as a function of length scale in order to understand and predict the phase stability. The important constituents: volumetric free energy and interfacial energy changes were experimentally derived considering the chemistry and structure of the multilayers and competition between these thermodynamic terms well explains the observed structural changes in nanoscale metallic multilayers.

  10. Improvement of oxygen-containing functional groups on olive stones activated carbon by ozone and nitric acid for heavy metals removal from aqueous phase.

    PubMed

    Bohli, Thouraya; Ouederni, Abdelmottaleb

    2016-08-01

    Recently, modification of surface structure of activated carbons in order to improve their adsorption performance toward especial pollutants has gained great interest. Oxygen-containing functional groups have been devoted as the main responsible for heavy metal binding on the activated carbon surface; their introduction or enhancement needs specific modification and impregnation methods. In the present work, olive stones activated carbon (COSAC) undergoes surface modifications in gaseous phase using ozone (O3) and in liquid phase using nitric acid (HNO3). The activated carbon samples were characterized using N2 adsorption-desorption isotherm, SEM, pHpzc, FTIR, and Boehm titration. The activated carbon parent (COSAC) has a high surface area of 1194 m(2)/g and shows a predominantly microporous structure. Oxidation treatments with nitric acid and ozone show a decrease in both specific surface area and micropore volumes, whereas these acidic treatments have led to a fixation of high amount of surface oxygen functional groups, thus making the carbon surface more hydrophilic. Activated carbon samples were used as an adsorbent matrix for the removal of Co(II), Ni(II), and Cu(II) heavy metal ions from aqueous solutions. Adsorption isotherms were obtained at 30 °C, and the data are well fitted to the Redlich-Peterson and Langmuir equation. Results show that oxidized COSACs, especially COSAC(HNO3), are capable to remove more Co(II), Cu(II), and Ni(II) from aqueous solution. Nitric acid-oxidized olive stones activated carbon was tested in its ability to remove metal ions from binary systems and results show an important maximum adsorbed amount as compared to single systems.

  11. Partitioning of Alkali Metal Salts and Boric Acid from Aqueous Phase into the Polyamide Active Layers of Reverse Osmosis Membranes.

    PubMed

    Wang, Jingbo; Kingsbury, Ryan S; Perry, Lamar A; Coronell, Orlando

    2017-02-21

    The partition coefficient of solutes into the polyamide active layer of reverse osmosis (RO) membranes is one of the three membrane properties (together with solute diffusion coefficient and active layer thickness) that determine solute permeation. However, no well-established method exists to measure solute partition coefficients into polyamide active layers. Further, the few studies that measured partition coefficients for inorganic salts report values significantly higher than one (∼3-8), which is contrary to expectations from Donnan theory and the observed high rejection of salts. As such, we developed a benchtop method to determine solute partition coefficients into the polyamide active layers of RO membranes. The method uses a quartz crystal microbalance (QCM) to measure the change in the mass of the active layer caused by the uptake of the partitioned solutes. The method was evaluated using several inorganic salts (alkali metal salts of chloride) and a weak acid of common concern in water desalination (boric acid). All partition coefficients were found to be lower than 1, in general agreement with expectations from Donnan theory. Results reported in this study advance the fundamental understanding of contaminant transport through RO membranes, and can be used in future studies to decouple the contributions of contaminant partitioning and diffusion to contaminant permeation.

  12. Active aperture phased arrays

    NASA Astrophysics Data System (ADS)

    Shenoy, R. P.

    1989-04-01

    Developments towards the realization of active aperture phased arrays are reviewed. The technology and cost aspects of the power amplifier and phase shifter subsystems are discussed. Consideration is given to research concerning T/R modules, MESFETs, side lobe control, beam steering, optical control techniques, and printed circuit antennas. Methods for configuring the array are examined, focusing on the tile and brick configurations. It is found that there is no technological impediment for introducing active aperture phased arrays.

  13. Metals distributions in activated sludge systems

    SciTech Connect

    Patterson, J.W.; Kodukula, P.S.

    1984-05-01

    Despite extensive laboratory and field studies over the past 25 years, little advance has been made in prediction of metals distribution and removal in activated sludge treatment systems. This paper reports the results of carefully controlled pilot studies, from which empirical metals distribution models were developed. The models accurately predict the distribution of process stream metals at each point in the activated sludge process between the soluble and solids phases. The distribution models together with data on primary and secondary clarifier suspended solids removal efficiencies, are easily applied to predict the removals of influent metals in activated sludge systems. 36 references, 2 figures.

  14. Hydrated metal ions in the gas phase.

    PubMed

    Beyer, Martin K

    2007-01-01

    Studying metal ion solvation, especially hydration, in the gas phase has developed into a field that is dominated by a tight interaction between experiment and theory. Since the studied species carry charge, mass spectrometry is an indispensable tool in all experiments. Whereas gas-phase coordination chemistry and reactions of bare metal ions are reasonably well understood, systems containing a larger number of solvent molecules are still difficult to understand. This review focuses on the rich chemistry of hydrated metal ions in the gas phase, covering coordination chemistry, charge separation in multiply charged systems, as well as intracluster and ion-molecule reactions. Key ideas of metal ion solvation in the gas phase are illustrated with rare-gas solvated metal ions.

  15. Gas phase metal cluster model systems for heterogeneous catalysis.

    PubMed

    Lang, Sandra M; Bernhardt, Thorsten M

    2012-07-14

    Since the advent of intense cluster sources, physical and chemical properties of isolated metal clusters are an active field of research. In particular, gas phase metal clusters represent ideal model systems to gain molecular level insight into the energetics and kinetics of metal-mediated catalytic reactions. Here we summarize experimental reactivity studies as well as investigations of thermal catalytic reaction cycles on small gas phase metal clusters, mostly in relation to the surprising catalytic activity of nanoscale gold particles. A particular emphasis is put on the importance of conceptual insights gained through the study of gas phase model systems. Based on these concepts future perspectives are formulated in terms of variation and optimization of catalytic materials e.g. by utilization of bimetals and metal oxides. Furthermore, the future potential of bio-inspired catalytic material systems are highlighted and technical developments are discussed.

  16. Athena: Assessment Phase Activities

    NASA Astrophysics Data System (ADS)

    Lumb, David; Ayre, Mark

    2015-09-01

    The Athena mission concept has been proposed by the community in response to science themes of the Hot and Energetic Universe. Unlike other, competitive, mission selection exercises this "Large" class observatory mission has essentially been pre-selected. Nevertheless it has to be demonstrated that Athena meets the programmatic constraints of 1Bn euro cost cap, and a readiness level appropriate for formal mission adoption by the end 2019. This should be confirmed through a Phase A study conducted with two parallel industry activities. We describe the technical and programmatic content of these and latest progress in space and ground segment definition.

  17. Phase reactions at semiconductor metallization interfaces

    NASA Astrophysics Data System (ADS)

    Bhansali, A. S.; Ko, D. H.; Sinclair, R.

    1990-11-01

    During, or following, the fabrication of a microelectronic device, it is possible for the material phases at critical interfaces to react with one another, and so alter the elec-trical performance. This is particularly important for metallization contacts to semi-conductors and for multilevel interconnects. The present article shows that application of phase diagram principles can successfully predict the mutual stability or chemical reactivity in such circumstances. Since most relevant phase diagrams are not available, it is shown how they may be calculated from known thermochemical data, or deduced from observations on thin-film reactions. The article is illustrated by the behavior of titanium silicide with a diffusion barrier layer (TiN) and the surrounding dielectric SiO2. In addition the Al-Si-O-N and W-N-Ga-As systems are described, and metastable amor-phous phase formation at the Ti-Si interface is discussed.

  18. Bose Metal Phase from Inhomogeneous Flow

    NASA Astrophysics Data System (ADS)

    Zimanyi, Gergely; Jensen, Niels

    2008-03-01

    Numerous experiments report a Bose Metal phase between the Superconducting (S) and the Insulating (I) phases at an SI transition. [1,2] However, theoretically the origin of the corresponding dissipation remains unclear. We propose a picture in which inhomogeneous superconducting flow occurs in channels/filaments, defined by islands of localized Bose Glass. The superconducting bosons interact with the localized bosons of the Bose Glass via the Coulomb interaction. This Coulomb drag generates an effective dissipation for the superflow. We developed a new numerical technique to simulate superconductivity by inertial dynamics and a current generator. We found a Bose Metal phase in a finite range of the disorder, bracketed by the superconducting and insulating phases. The noise spectrum was also determined and compared to recent experiments. [1] H.M. Jaeger, D.B. Haviland, B.G. Orr and A.M. Goldman, Phys. Rev. B 40, 182 (1989). [2] A. Yazdani and A. Kapitulnik, Phys. Rev. Lett. 74, 3037 (1995); M. Steiner, N. Breznay and A. Kapitulnik, arxiv: 0710.1822.

  19. Actively convected liquid metal divertor

    NASA Astrophysics Data System (ADS)

    Shimada, Michiya; Hirooka, Yoshi

    2014-12-01

    The use of actively convected liquid metals with j × B force is proposed to facilitate heat handling by the divertor, a challenging issue associated with magnetic fusion experiments such as ITER. This issue will be aggravated even more for DEMO and power reactors because the divertor heat load will be significantly higher and yet the use of copper would not be allowed as the heat sink material. Instead, reduced activation ferritic/martensitic steel alloys with heat conductivities substantially lower than that of copper, will be used as the structural materials. The present proposal is to fill the lower part of the vacuum vessel with liquid metals with relatively low melting points and low chemical activities including Ga and Sn. The divertor modules, equipped with electrodes and cooling tubes, are immersed in the liquid metal. The electrode, placed in the middle of the liquid metal, can be biased positively or negatively with respect to the module. The j × B force due to the current between the electrode and the module provides a rotating motion for the liquid metal around the electrodes. The rise in liquid temperature at the separatrix hit point can be maintained at acceptable levels from the operation point of view. As the rotation speed increases, the current in the liquid metal is expected to decrease due to the v × B electromotive force. This rotating motion in the poloidal plane will reduce the divertor heat load significantly. Another important benefit of the convected liquid metal divertor is the fast recovery from unmitigated disruptions. Also, the liquid metal divertor concept eliminates the erosion problem.

  20. Mineral phases and metals in baghouse dust from secondary ...

    EPA Pesticide Factsheets

    Baghouse dust (BHD) is a solid waste generated by air pollution control systems during secondary aluminum processing (SAP). Management and disposal of BHD can be challenging in the U.S. and elsewhere. In this study, the mineral phases, metal content and metal leachability of 78 BHD samples collected from 13 different SAP facilities across the U.S. were investigated. The XRD semi-quantitative analysis of BHD samples suggests the presence of metallic aluminum, aluminum oxide, aluminum nitride and its oxides, spinel, elpasolite as well as diaspora. BHD also contains halite, sylvite and fluorite, which are used as fluxes in SAP activities. Total aluminum (Al) in the BHD samples averaged 18% by weight. Elevated concentrations of trace metals (>100 µgL-1 As; >1000 µgL-1 Cu, Mn, Se, Pb, Mn and Zn) were also detected in the leachate. The U.S. toxicity characteristic leaching procedure (TCLP) results showed that some samples leached above the toxicity limit for Cd, Pb and Se. Exceeding the TCLP limits in all sample is independent of facilities generating the BHD. From the metal content perspective only, it appears that BHD has a higher potential to exhibit toxicity characteristics than salt cake (the largest waste stream generated by SAP facilities). The objective of this study was to investigate BHD from SAP facilities in the U.S. by determining the mineral phases and the metal (Al, As, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Pb, Se and Zn) content of the sample

  1. Switchable Metal-Insulator Phase Transition Metamaterials.

    PubMed

    Hajisalem, Ghazal; Nezami, Mohammadreza S; Gordon, Reuven

    2017-04-06

    We investigate the switching of a gap plasmon tunnel junction between conducting and insulating states. Hysteresis is observed in the second and the third harmonic generation power dependence, which arises by thermally induced disorder ("melting") of a two-carbon self-assembled monolayer between an ultraflat gold surface and metal nanoparticles. The hysteresis is observed for a variety of nanoparticle sizes, but not for larger tunnel junctions where there is no appreciable tunneling. By combining quantum corrected finite-difference time-domain simulations with nonlinear scattering theory, we calculate the changes in the harmonic generation between the tunneling and the insulating states, and good agreement is found with the experiments. This paves the way to a new class of metal-insulator phase transition switchable metamaterials, which may provide next-generation information processing technologies.

  2. Studying Activity Series of Metals.

    ERIC Educational Resources Information Center

    Hoon, Tien-Ghun; And Others

    1995-01-01

    Presents teaching strategies that illustrate the linking together of numerous chemical concepts involving the activity of metals (quantitative analysis, corrosion, and electrolysis) through the use of deep-level processing strategies. Concludes that making explicit links in the process of teaching chemistry can lead effectively to meaningful…

  3. Mechanics of Metals with Phase Changes

    SciTech Connect

    Lashley, Jason C.

    2001-01-01

    New experimental data is presented on some exotic metals that exhibit phase changes at cryogenic temperatures. The types of phase changes that were detected in the specific heat data range from martensitic (diffusion less) transitions to superconducting transitions. In addition, the charge density wave (CDW) state in uranium metal was detected in the specific heat. Specific-heat measurements were made in zero-magnetic field using an apparatus capable of obtaining temperatures as low as 0.4 K. Calibration performed on this apparatus, using a single-crystal copper sample, show its accuracy to be 0.50%, while the resolution was better than 0.1%. Our measurements demonstrate that similar high precision and accurate specific-heat measurements can be obtained on milligram-scale samples. In Chapters 2 and 3, specific-heat measurements are presented for the B2 (CsCl structure) alloy AuZn and for α-uranium (orthorhombic symmetry). The AuZn alloy exhibits a continuous transition at 64.75 K and an entropy of transition of (ΔStr) 2.02 J K-1 mol-1. Calculation of the Debye temperature, by extrapolating of the high temperature phase elastic constants to T = 0 K yields a value of 207 K (±2 K), in favorable agreement with the calorimetric value of 219 K (±0.50 K), despite the intervening martensitic transition. Reported results for single-crystal α-U show a low-temperature limiting θD of 256 K (±0.50 K) and four low-temperature anomalies: a superconducting transition below 1 K, an electronic transition at 22 K, and two anomalies at 38 K and at 42 K indicative of the CDW state. In order to continue the study of the actinide series of elements, a program was initiated to first purify and then grow single crystals of plutonium. Accordingly, the focus of Chapters 4 through 6 will be a description of plutonium sample preparation. In this program plutonium metal was purified via zone refining, using a levitated molten zone to minimize

  4. Aqueous-phase hydrogenation of acetic acid over transition metal catalysts

    SciTech Connect

    Olcay, Hakan; Xu, Lijun; Xu, Ye; Huber, George

    2010-01-01

    Catalytic hydrogenation of acetic acid to ethanol has been carried out in aqueous phase on several metals, with ruthenium being the most active and selective. DFT calculations suggest that the initial CO bond scission yielding acetyl is the key step and that the intrinsic reactivity of the metals accounts for the observed activity.

  5. Active membrane phased array radar

    NASA Technical Reports Server (NTRS)

    Moussessian, Alina; Del Castillo, Linda; Huang, John; Sadowy, Greg; Hoffman, James; Smith, Phil; Hatake, Toshiro; Derksen, Chuck; Lopez, Bernardo; Caro, Ed

    2005-01-01

    We have developed the first membrane-based active phased array in L-band (1.26GHz). The array uses membrane compatible Transmit/Receive (T/R) modules (membrane T/R) for each antenna element. We use phase shifters within each T/R module for electronic beam steering. We will discuss the T/R module design and integration with the membrane, We will also present transmit and receive beam-steering results for the array.

  6. Multiscale correlations of iron phases and heavy metals in technogenic magnetic particles from contaminated soils.

    PubMed

    Yu, Xiuling; Lu, Shenggao

    2016-12-01

    Technogenic magnetic particles (TMPs) are carriers of heavy metals and organic contaminants, which derived from anthropogenic activities. However, little information on the relationship between heavy metals and TMP carrier phases at the micrometer scale is available. This study determined the distribution and association of heavy metals and magnetic phases in TMPs in three contaminated soils at the micrometer scale using micro-X-ray fluorescence (μ-XRF) and micro-X-ray absorption near-edge structure (μ-XANES) spectroscopy. Multiscale correlations of heavy metals in TMPs were elucidated using wavelet transform analysis. μ-XRF mapping showed that Fe was enriched and closely correlated with Co, Cr, and Pb in TMPs from steel industrial areas. Fluorescence mapping and wavelet analysis showed that ferroalloy was a major magnetic signature and heavy metal carrier in TMPs, because most heavy metals were highly associated with ferroalloy at all size scales. Multiscale analysis revealed that heavy metals in the TMPs were from multiple sources. Iron K-edge μ-XANES spectra revealed that metallic iron, ferroalloy, and magnetite were the main iron magnetic phases in the TMPs. The relative percentage of these magnetic phases depended on their emission sources. Heatmap analysis revealed that Co, Pb, Cu, Cr, and Ni were mainly derived from ferroalloy particles, while As was derived from both ferroalloy and metallic iron phases. Our results indicated the scale-dependent correlations of magnetic phases and heavy metals in TMPs. The combination of synchrotron based X-ray microprobe techniques and multiscale analysis provides a powerful tool for identifying the magnetic phases from different sources and quantifying the association of iron phases and heavy metals at micrometer scale.

  7. Geochemical phases of metals in Hudson River estuary sediments

    SciTech Connect

    Stamoulis, S.; Gibbs, R.J.; Menon, M.G.

    1996-08-01

    Bottom sediment samples were collected from six location along a section of the Hudson River Estuary, 5.3 to 82.7 km from the ocean. These samples were analyzed for particle and, due to the bimodal distribution of the sediment, were seperated into two size fractions, fine (<7.8 um) and coarse (7.8-62 um). These fractions were subject to a sequential chemical phase extraction procedure to differenciate the ion exchangeable, carbonate, metallic oxide coating, and organic phases. The extracted phases were analyzed with an inductively coupled plasma atomic emission spectrophotometer for Cd, Co, Cc, Cu, Fe, Ni, Pb, and Zn. Metals were found to be associated largely with fine particle-size fraction. The concentration of fine particles (especially the <2 um size mode within the fine fraction) is a crucial in influencing overall metal content. This is evidenced by strong correlations between the <2 {mu}m or clay mode and concentrations in the metallic-oxide coating phase. Various metal/metal relationships exist among the phases and fractions studied and are highlighted by strong correlations, such as Ni and Zn, and Cu and Cd. The trends associated among the metal and mud concentrations are significant in terms of assessing the bioavailability of heavy metals within the river and estuary system, and as a result, provide valuable insight into the ultimate fate of pollutants which are introduced to this unique environment. 24 refs., 5 figs., 2 tabs.

  8. Dynamical conductivity at the dirty superconductor-metal quantum phase transition.

    PubMed

    Del Maestro, Adrian; Rosenow, Bernd; Hoyos, José A; Vojta, Thomas

    2010-10-01

    We study the transport properties of ultrathin disordered nanowires in the neighborhood of the superconductor-metal quantum phase transition. To this end we combine numerical calculations with analytical strong-disorder renormalization group results. The quantum critical conductivity at zero temperature diverges logarithmically as a function of frequency. In the metallic phase, it obeys activated scaling associated with an infinite-randomness quantum critical point. We extend the scaling theory to higher dimensions and discuss implications for experiments.

  9. Antimicrobial activity of the metals and metal oxide nanoparticles.

    PubMed

    Dizaj, Solmaz Maleki; Lotfipour, Farzaneh; Barzegar-Jalali, Mohammad; Zarrintan, Mohammad Hossein; Adibkia, Khosro

    2014-11-01

    The ever increasing resistance of pathogens towards antibiotics has caused serious health problems in the recent years. It has been shown that by combining modern technologies such as nanotechnology and material science with intrinsic antimicrobial activity of the metals, novel applications for these substances could be identified. According to the reports, metal and metal oxide nanoparticles represent a group of materials which were investigated in respect to their antimicrobial effects. In the present review, we focused on the recent research works concerning antimicrobial activity of metal and metal oxide nanoparticles together with their mechanism of action. Reviewed literature indicated that the particle size was the essential parameter which determined the antimicrobial effectiveness of the metal nanoparticles. Combination therapy with the metal nanoparticles might be one of the possible strategies to overcome the current bacterial resistance to the antibacterial agents. However, further studies should be performed to minimize the toxicity of metal and metal oxide nanoparticles to apply as proper alternatives for antibiotics and disinfectants especially in biomedical applications.

  10. Novel gamma-phase of titanium metal at megabar pressures.

    PubMed

    Vohra, Y K; Spencer, P T

    2001-04-02

    Group IV transition metals titanium, zirconium, and hafnium are expected to transform from an ambient hexagonal close packed (hcp, alpha-phase) to a body centered cubic (bcc, beta-phase) at high pressures. This transition path is usually facilitated by the occurrence of an intermediate hexagonal phase (distorted bcc, omega-phase). The existence of a bcc phase in zirconium and hafnium at high pressures has been known for the past ten years; however, its occurrence in titanium has been theoretically predicted but never observed. We report a novel unexpected transformation in titanium metal from an omega phase to an orthorhombic phase (distorted hcp, gamma-phase) at a pressure of 116+/-4 GPa.

  11. Characterization of Delta Phase Plutonium Metal

    SciTech Connect

    Rudisill, T.S.

    2000-09-21

    The FB-Line facility has developed the capability to recast plutonium metal using an M-18 reduction furnace with a new casting chamber. Plutonium metal is recast by charging a standard FB-Line magnesia crucible and placing the charge in the casting chamber. The loaded casting chamber is raised into the M-18 reduction furnace and sealed against the furnace head using a copper gasket following the same procedure used for a bomb reduction run. The interior volume of the chamber is evacuated and backfilled with argon gas. The M-18 motor-generator set is used to heat the surface of the casting chamber to nominally 750 Degrees C. Within about 2 hr, the plutonium metal reaches its melting temperature of approximately 640 Degrees C.

  12. Nanoscale electrodeposition of low-dimensional metal phases and clusters.

    PubMed

    Staikov, Georgi

    2016-08-07

    The present status of the problem of electrochemical formation of low-dimensional metal phases is reviewed. The progress in this field achieved in the last two decades is discussed on the basis of experimental results obtained in selected electrochemical systems with well defined single crystal substrates. The influence of crystallographic orientation and surface inhomogeneities of foreign substrates on the mechanism of formation and the atomic structure of two-dimensional (2D) metal phases in the underpotential deposition range is considered. The localized electrodeposition of metal nanoclusters on solid state surfaces applying the STM-tip as a nanoelectrode is demonstrated.

  13. Nanoscale electrodeposition of low-dimensional metal phases and clusters

    NASA Astrophysics Data System (ADS)

    Staikov, Georgi

    2016-07-01

    The present status of the problem of electrochemical formation of low-dimensional metal phases is reviewed. The progress in this field achieved in the last two decades is discussed on the basis of experimental results obtained in selected electrochemical systems with well defined single crystal substrates. The influence of crystallographic orientation and surface inhomogeneities of foreign substrates on the mechanism of formation and the atomic structure of two-dimensional (2D) metal phases in the underpotential deposition range is considered. The localized electrodeposition of metal nanoclusters on solid state surfaces applying the STM-tip as a nanoelectrode is demonstrated.

  14. Bi-phase transition diagrams of metallic thin multilayers

    SciTech Connect

    Li, J.C.; Liu, W.; Jiang, Q. . E-mail: jiangq@jlu.edu.cn

    2005-02-01

    Phase transitions of metallic multilayers induced by differences in interface energy are considered thermodynamically, based on a thermodynamic model for interface energy and the Goldschmidt premise for lattice contraction. Bi-phase transition diagrams of Co/Cr, Zr/Nb, Ti/Nb and Ti/Al multilayers are constructed, which are in agreement with experimental results.

  15. Phase estimation for magnetic resonance imaging near metal prostheses

    NASA Astrophysics Data System (ADS)

    Bones, Philip J.; King, Laura J.; Millane, Rick P.

    2015-09-01

    Magnetic resonance imaging (MRI) has the potential to be the best technique for assessing complications in patients with metal orthopedic implants. The presence of fat can obscure definition of the other soft tissues in MRI images, so fat suppression is often required. However, the performance of existing fat suppression techniques is inadequate near implants, due to very significant magnetic field perturbations induced by the metal. The three-point Dixon technique is potentially a method of choice as it is able to suppress fat in the presence of inhomogeneities, but the success of this technique depends on being able to accurately calculate the phase shift. This is generally done using phase unwrapping and/or iterative reconstruction algorithms. Most current phase unwrapping techniques assume that the phase function is slowly varying and phase differences between adjacent points are limited to less than π radians in magnitude. Much greater phase differences can be present near metal implants. We present our experience with two phase unwrapping techniques which have been adapted to use prior knowledge of the implant. The first method identifies phase discontinuities before recovering the phase along paths through the image. The second method employs a transform to find the least squares solution to the unwrapped phase. Simulation results indicate that the methods show promise.

  16. For cermet inert anode containing oxide and metal phases useful for the electrolytic production of metals

    DOEpatents

    Ray, Siba P.; Liu, Xinghua; Weirauch, Douglas A.

    2002-01-01

    A cermet inert anode for the electrolytic production of metals such as aluminum is disclosed. The inert anode comprises a ceramic phase including an oxide of Ni, Fe and M, where M is at least one metal selected from Zn, Co, Al, Li, Cu, Ti, V, Cr, Zr, Nb, Ta, W, Mo, Hf and rare earths, preferably Zn and/or Co. Preferred ceramic compositions comprise Fe.sub.2 O.sub.3, NiO and ZnO or CoO. The cermet inert anode also comprises a metal phase such as Cu, Ag, Pd, Pt, Au, Rh, Ru, Ir and/or Os. A preferred metal phase comprises Cu and Ag. The cermet inert anodes may be used in electrolytic reduction cells for the production of commercial purity aluminum as well as other metals.

  17. Electrocrystallization: A Synthetic Method for Intermetallic Phases with Polar Metal-Metal Bonding.

    PubMed

    Tambornino, Frank; Sappl, Jonathan; Pultar, Felix; Cong, Trung Minh; Hübner, Sabine; Giftthaler, Tobias; Hoch, Constantin

    2016-11-07

    Isothermal electrolysis is a convenient preparation technique for a large number of intermetallic phases. A solution of the salt of a less-noble metal is electrolyzed on a cathode consisting of a liquid metal or intermetallic system. This yields crystalline products at mild reaction conditions in a few hours. We show the aptness and the limitations of this approach. First, we give an introduction into the relevance of electrolytic synthesis for chemistry. Then we present materials and techniques our group has developed for electrocrystallization that are useful for electrochemical syntheses in general. Subsequently, we discuss different phase formation eventualities and propose basic rationalization concepts, illustrated with examples from our work. The scope of this report is to present electrocrystallization as a well-known yet underestimated synthetic process, especially in intermetallic chemistry. For this purpose we adduce literature examples (Li3Ga14, NaGa4, K8Ga8Sn38), technical advice, basic concepts, and new crystal structures only available by this method: Li3Ga13Sn and CsIn12. Electrocrystallization has recently proven especially helpful in our work concerning synthesis of intermetallic phases with polar metal-metal bonding, especially Hg-rich amalgams of less-noble metals. With the term "polar metal-metal bonding" we describe phases where the constituting elements have large electronegativity difference and yet show incomplete electron transfer from the less-noble to the nobler metal. This distinguishes polar intermetallic phases from classical Zintl phases where the electron transfer is virtually complete. Polar metallic phases can show "bad metal behavior" and interesting combinations of ionic and metallic properties. Amalgams of less-noble metals are preeminent representatives for this class of intermetallic phases as Hg is the only noble metal with endothermic electron affinity and thus a very low tendency toward anion formation. To illustrate both

  18. Three-phase metal kinetics in terrestrial invertebrates exposed to high metal concentrations.

    PubMed

    Laskowski, Ryszard; Bednarska, Agnieszka J; Spurgeon, David; Svendsen, Claus; van Gestel, Cornelis A M

    2010-08-15

    Models of metal toxicokinetics are critically evaluated using both newly generated data in the NoMiracle project as well as those originating from older studies. The analysis showed that the most frequently used one-compartment two-phase toxicokinetic model, with one assimilation and one elimination rate constant, does not describe correctly certain data sets pertaining particularly to the pattern of assimilation of trace elements. Using nickel toxicokinetics in carabid beetles and earthworms as examples, we showed that Ni in fact exhibits a three-phase kinetics with a short phase of fast metal accumulation immediately after exposure, followed by partial elimination to an equilibrium concentration at a later stage of a metal exposure phase, and by final elimination upon transfer to an uncontaminated food/soil. A similar phenomenon was also found for data on cadmium kinetics in ground beetles and copper kinetics in earthworms in data already published in the literature that was not accounted for in the earlier analysis of the data. The three-phase model suggests that the physiology of controlling body metal concentrations can change shortly after exposure, at least in some cases, by increasing the elimination rate and/or decreasing metal assimilation. Hence, the three-phase model, that allows for different assimilation and/or elimination rates in different phases of exposure to a toxicant, may provide insight into temporal changes in the physiology of metal handling. Consequently, this alternative model should always be tested when describing metal toxicokinetics when temporal patterns of internal metal concentration exhibit an initial "overshoot" in body metal concentrations.

  19. Calculation of Gallium-metal-Arsenic phase diagrams

    NASA Technical Reports Server (NTRS)

    Scofield, J. D.; Davison, J. E.; Ray, A. E.; Smith, S. R.

    1991-01-01

    Electrical contacts and metallization to GaAs solar cells must survive at high temperatures for several minutes under specific mission scenarios. The determination of which metallizations or alloy systems that are able to withstand extreme thermal excursions with minimum degradation to solar cell performance can be predicted by properly calculated temperature constitution phase diagrams. A method for calculating a ternary diagram and its three constituent binary phase diagrams is briefly outlined and ternary phase diagrams for three Ga-As-X alloy systems are presented. Free energy functions of the liquid and solid phase are approximated by the regular solution theory. Phase diagrams calculated using this method are presented for the Ga-As-Ge and Ga-As-Ag systems.

  20. Solid–solid phase transitions via melting in metals

    PubMed Central

    Pogatscher, S.; Leutenegger, D.; Schawe, J. E. K.; Uggowitzer, P. J.; Löffler, J. F.

    2016-01-01

    Observing solid–solid phase transitions in-situ with sufficient temporal and spatial resolution is a great challenge, and is often only possible via computer simulations or in model systems. Recently, a study of polymeric colloidal particles, where the particles mimic atoms, revealed an intermediate liquid state in the transition from one solid to another. While not yet observed there, this finding suggests that such phenomena may also occur in metals and alloys. Here we present experimental evidence for a solid–solid transition via the formation of a metastable liquid in a ‘real' atomic system. We observe this transition in a bulk glass-forming metallic system in-situ using fast differential scanning calorimetry. We investigate the corresponding transformation kinetics and discuss the underlying thermodynamics. The mechanism is likely to be a feature of many metallic glasses and metals in general, and may provide further insight into phase transition theory. PMID:27103085

  1. Covalent functionalization of monolayered transition metal dichalcogenides by phase engineering.

    PubMed

    Voiry, Damien; Goswami, Anandarup; Kappera, Rajesh; e Silva, Cecilia de Carvalho Castro; Kaplan, Daniel; Fujita, Takeshi; Chen, Mingwei; Asefa, Tewodros; Chhowalla, Manish

    2015-01-01

    Chemical functionalization of low-dimensional materials such as nanotubes, nanowires and graphene leads to profound changes in their properties and is essential for solubilizing them in common solvents. Covalent attachment of functional groups is generally achieved at defect sites, which facilitate electron transfer. Here, we describe a simple and general method for covalent functionalization of two-dimensional transition metal dichalcogenide nanosheets (MoS₂, WS₂ and MoSe₂), which does not rely on defect engineering. The functionalization reaction is instead facilitated by electron transfer between the electron-rich metallic 1T phase and an organohalide reactant, resulting in functional groups that are covalently attached to the chalcogen atoms of the transition metal dichalcogenide. The attachment of functional groups leads to dramatic changes in the optoelectronic properties of the material. For example, we show that it renders the metallic 1T phase semiconducting, and gives it strong and tunable photoluminescence and gate modulation in field-effect transistors.

  2. Elevated temperature creep properties for selected active metal braze alloys

    SciTech Connect

    Stephens, J.J.

    1997-02-01

    Active metal braze alloys reduce the number of processes required for the joining of metal to ceramic components by eliminating the need for metallization and/or Ni plating of the ceramic surfaces. Titanium (Ti), V, and Zr are examples of active element additions which have been used successfully in such braze alloys. Since the braze alloy is expected to accommodate thermal expansion mismatch strains between the metal and ceramic materials, a knowledge of its elevated temperature mechanical properties is important. In particular, the issue of whether or not the creep strength of an active metal braze alloy is increased or decreased relative to its non-activated counterpart is important when designing new brazing processes and alloy systems. This paper presents a survey of high temperature mechanical properties for two pairs of conventional braze alloys and their active metal counterparts: (a) the conventional 72Ag-28Cu (Cusil) alloy, and the active braze alloy 62.2Ag- 36.2Cu-1.6Ti (Cusil ABA), and (b) the 82Au-18Ni (Nioro) alloy and the active braze alloy Mu-15.5M-0.75Mo-1.75V (Nioro ABA). For the case of the Cusil/Cusil ABA pair, the active metal addition contributes to solid solution strengthening of the braze alloy, resulting in a higher creep strength as compared to the non-active alloy. In the case of the Nioro/Nioro ABA pair, the Mo and V additions cause the active braze alloy to have a two-phase microstructure, which results in a reduced creep strength than the conventional braze alloy. The Garofalo sinh equation has been used to quantitatively describe the stress and temperature dependence of the deformation behavior. It will be observed that the effective stress exponent in the Garofalo sinh equation is a function of the instantaneous value of the stress argument.

  3. A superconductor to superfluid phase transition in liquid metallic hydrogen.

    PubMed

    Babaev, Egor; Sudbø, Asle; Ashcroft, N W

    2004-10-07

    Although hydrogen is the simplest of atoms, it does not form the simplest of solids or liquids. Quantum effects in these phases are considerable (a consequence of the light proton mass) and they have a demonstrable and often puzzling influence on many physical properties, including spatial order. To date, the structure of dense hydrogen remains experimentally elusive. Recent studies of the melting curve of hydrogen indicate that at high (but experimentally accessible) pressures, compressed hydrogen will adopt a liquid state, even at low temperatures. In reaching this phase, hydrogen is also projected to pass through an insulator-to-metal transition. This raises the possibility of new state of matter: a near ground-state liquid metal, and its ordered states in the quantum domain. Ordered quantum fluids are traditionally categorized as superconductors or superfluids; these respective systems feature dissipationless electrical currents or mass flow. Here we report a topological analysis of the projected phase of liquid metallic hydrogen, finding that it may represent a new type of ordered quantum fluid. Specifically, we show that liquid metallic hydrogen cannot be categorized exclusively as a superconductor or superfluid. We predict that, in the presence of a magnetic field, liquid metallic hydrogen will exhibit several phase transitions to ordered states, ranging from superconductors to superfluids.

  4. Crystal Phases in Hybrid Metal-Semiconductor Nanowire Devices.

    PubMed

    David, J; Rossella, F; Rocci, M; Ercolani, D; Sorba, L; Beltram, F; Gemmi, M; Roddaro, S

    2017-04-12

    We investigate the metallic phases observed in hybrid metal-GaAs nanowire devices obtained by controlled thermal annealing of Ni/Au electrodes. Devices are fabricated onto a SiN membrane compatible with transmission electron microscopy studies. Energy dispersive X-ray spectroscopy allows us to show that the nanowire body includes two Ni-rich phases that thanks to an innovative use of electron diffraction tomography can be unambiguously identified as Ni3GaAs and Ni5As2 crystals. The mechanisms of Ni incorporation leading to the observed phenomenology are discussed.

  5. Reversible metal-hydride phase transformation in epitaxial films.

    PubMed

    Roytburd, Alexander L; Boyerinas, Brad M; Bruck, Hugh A

    2015-03-11

    Metal-hydride phase transformations in solids commonly proceed with hysteresis. The extrinsic component of hysteresis is the result of the dissipation of energy of internal stress due to plastic deformation and fracture. It can be mitigated on the nanoscale, where plastic deformation and fracture are suppressed and the transformation proceeds through formation and evolution of coherent phases. However, the phase coherency introduces intrinsic thermodynamic hysteresis, preventing reversible transformation. In this paper, it is shown that thermodynamic hysteresis of coherent metal-hydride transformation can be eliminated in epitaxial film due to substrate constraint. Film-substrate interaction leads to formation of heterophase polydomain nanostructure with variable phase fraction which can change reversibly by varying temperature in a closed system or chemical potential in an open system.

  6. Reversible metal-hydride phase transformation in epitaxial films

    NASA Astrophysics Data System (ADS)

    Roytburd, Alexander L.; Boyerinas, Brad M.; Bruck, Hugh A.

    2015-03-01

    Metal-hydride phase transformations in solids commonly proceed with hysteresis. The extrinsic component of hysteresis is the result of the dissipation of energy of internal stress due to plastic deformation and fracture. It can be mitigated on the nanoscale, where plastic deformation and fracture are suppressed and the transformation proceeds through formation and evolution of coherent phases. However, the phase coherency introduces intrinsic thermodynamic hysteresis, preventing reversible transformation. In this paper, it is shown that thermodynamic hysteresis of coherent metal-hydride transformation can be eliminated in epitaxial film due to substrate constraint. Film-substrate interaction leads to formation of heterophase polydomain nanostructure with variable phase fraction which can change reversibly by varying temperature in a closed system or chemical potential in an open system.

  7. Full electroresistance modulation in a mixed-phase metallic alloy

    DOE PAGES

    Liu, Zhiqi; Li, L.; Gai, Zheng; ...

    2016-03-03

    We report a giant, ~22%, electroresistance modulation for a metallic alloy above room temperature. It is achieved by a small electric field of 2 kV/cm via piezoelectric strain-mediated magnetoelectric coupling and the resulting magnetic phase transition in epitaxial FeRh/BaTiO3 heterostructures. This work presents detailed experimental evidence for an isothermal magnetic phase transition driven by tetragonality modulation in FeRh thin films, which is in contrast to the large volume expansion in the conventional temperature-driven magnetic phase transition in FeRh. Furthermore, all the experimental results in this work illustrate FeRh as a mixed-phase model system well similar to phase-separated colossal magnetoresistance systemsmore » with phase instability therein.« less

  8. Full electroresistance modulation in a mixed-phase metallic alloy

    SciTech Connect

    Liu, Zhiqi; Li, L.; Gai, Zheng; Clarkson, J. D.; Hsu, S. L.; Wong, Anthony T.; Fan, L. S.; Lin, Ming -Wei; Rouleau, Christopher M.; Ward, Thomas Zac; Lee, Ho Nyung; Sefat, Athena Safa; Christen, Hans M.; Ramesh, Ramamoorthy

    2016-03-03

    We report a giant, ~22%, electroresistance modulation for a metallic alloy above room temperature. It is achieved by a small electric field of 2 kV/cm via piezoelectric strain-mediated magnetoelectric coupling and the resulting magnetic phase transition in epitaxial FeRh/BaTiO3 heterostructures. This work presents detailed experimental evidence for an isothermal magnetic phase transition driven by tetragonality modulation in FeRh thin films, which is in contrast to the large volume expansion in the conventional temperature-driven magnetic phase transition in FeRh. Furthermore, all the experimental results in this work illustrate FeRh as a mixed-phase model system well similar to phase-separated colossal magnetoresistance systems with phase instability therein.

  9. Phase Behavior of Pseudobinary Precious Metal-Carbide Systems

    SciTech Connect

    Gregoire, John M.; Tague, Michele E.; Smith, Eva H.; Dale, Darren; DiSalvo, Francis J.; Abruña, Héctor D.; Hennig, Richard G.; van Dover, R. Bruce

    2010-11-15

    Transition metal carbides exhibit a variety of interesting material properties, including electrochemical stability. When combined with precious metals, Ta and W carbides have shown promise as fuel cell electrode materials; yet, the phase behavior of these precious metal-carbide systems is largely unexplored. We investigated P-M-C phase behavior with P = Pt, Pd, and Ru and M = Ta and W using composition spread thin films. We attained limited control of the deposited carbide phase through variation of the sputter atmosphere and demonstrated decreased corrosion of W-C materials with increasing C content. A high-throughput X-ray diffraction and X-ray fluorescence experiment was employed for thin film characterization, which revealed solubility of Pt, Pd, and Ru in cubic WC. Density functional calculations of the lattice parameter dependence on carbon concentration enabled the determination of carbon concentration from the X-ray data as a function of transition metal stoichiometry. Our measurement of variations in the C stoichiometry and evolution of thin film texture with transition metal composition yielded surprising results. We detail how the combination of the composition spread technique, the high-throughput thin film characterization, and the density functional modeling of ternary carbide alloys provided a deep understanding of the chemical systems.

  10. Metal and phosphide phases in Luna 24 soil fragments

    NASA Astrophysics Data System (ADS)

    Axon, H. J.; Nasir, M. J.; Knowles, F.

    1980-06-01

    Soil fragments in the 106-150 and 150-250 micron size ranges were selected for metallographic and microprobe examination on the basis of their magnetic properties. Serial sections of the mounted fragments were examined. One fragment proved to be a compositionally zoned crystal of phosphide with no metal phase but partly embedded in glass. Another was a coarse-grained association of silica with ilmenite and fayalite with a 5-micron particle of metallic iron in troilite. One splinter of oxide contained a central spine of metallic iron. The remaining six fragments contained 10-micron particles of iron-nickel-cobalt alloy with compositions in either the 'meteoritic' or the low Ni-low Co sub-meteoritic composition ranges of Ni, Co content. In some fragments separate particles of alloy had different Ni, Co contents. No particles of high Co metal were encountered.

  11. Surface effects and phase stability in metal oxides nanoparticles under visible irradiation

    SciTech Connect

    Ricci, Pier Carlo Carbonaro, C. M. Corpino, R. Chiriu, D. Stagi, L.

    2014-10-21

    The light induced phase transformation between stable phases of metal oxides nanoparticles is analyzed. The surrounding atmosphere as well as the defect density at the surface play a fundamental role. It has been found that in oxygen poor chamber atmosphere the phase transformation is favored, while the phase transition cannot be achieved if the defects at the surface are properly passivated. The phase transition is activated by intragap irradiation, able to activate the F- center at the surface connected to oxygen vacancies, and promoting the activation of the surface and the nucleation of neighboring crystallites. The phase transition was studied in Titanium oxide (TiO{sub 2}) and in Iron oxide (Fe{sub 2}O{sub 3}): Maghemite is subjected to a phase transformation to α−Fe{sub 2}O{sub 3} (hematite), Anatase nanoparticles converts to Rutile. The general mechanism of the phase transition and, more in general, the possibility to optically control the surface activity of metal oxides is discussed.

  12. Thermal battery. [solid metal halide electrolytes with enhanced electrical conductance after a phase transition

    DOEpatents

    Carlsten, R.W.; Nissen, D.A.

    1973-03-06

    The patent describes an improved thermal battery whose novel design eliminates various disadvantages of previous such devices. Its major features include a halide cathode, a solid metal halide electrolyte which has a substantially greater electrical conductance after a phase transition at some temperature, and a means for heating its electrochemical cells to activation temperature.

  13. Kondo Screening and Fermi Surface in the Antiferromagnetic Metal Phase

    NASA Astrophysics Data System (ADS)

    Yamamoto, Seiji; Si, Qimiao

    2006-03-01

    We address the Kondo effect deep inside the antiferromagnetic metal phase of a Kondo lattice Hamiltonian with SU(2) invariance. The local- moment component is described in terms of a non-linear sigma model. The Fermi surface of the conduction electron component is taken to be sufficiently small, so that it is not spanned by the antiferromagnetic wavevector. The effective low energy form of the Kondo coupling simplifies drastically, corresponding to the uniform component of the magnetization that forward-scatters the conduction electrons on their own Fermi surface. We use a combined bosonic and fermionic (Shankar) renormalization group procedure to analyze this effective theory and study the Kondo screening and Fermi surface in the antiferromagnetic phase. The implications for the global magnetic phase diagram, as well as quantum critical points, of heavy fermion metals are discussed.

  14. Role of phonons in the metal-insulator phase transition.

    NASA Technical Reports Server (NTRS)

    Langer, W. D.

    1972-01-01

    Review, for the transition series oxides, of the Mattis and Lander model, which is one of electrons interacting with lattice vibrations (electron and phonon interaction). The model displays superconducting, insulating, and metallic phases. Its basic properties evolve from a finite crystallographic distortion associated with a dominant phonon mode and the splitting of the Brillouin zone into two subzones, a property of simple cubic and body centered cubic lattices. The order of the metal-insulator phase transition is examined. The basic model has a second-order phase transition and the effects of additional mechanisms on the model are calculated. The way in which these mechanisms affect the magnetically ordered transition series oxides as described by the Hubbard model is discussed.

  15. Dynamical conductivity at the dirty superconductor-metal quantum phase transition

    NASA Astrophysics Data System (ADS)

    Hoyos, J. A.; Del Maestro, Adrian; Rosenow, Bernd; Vojta, Thomas

    2011-03-01

    We study the transport properties of ultrathin disordered nanowires in the neighborhood of the superconductor-metal quantum phase transition. To this end we combine numerical calculations with analytical strong-disorder renormalization group results. The quantum critical conductivity at zero temperature diverges logarithmically as a function of frequency. In the metallic phase, it obeys activated scaling associated with an infinite-randomness quantum critical point. We extend the scaling theory to higher dimensions and discuss implications for experiments. Financial support: Fapesp, CNPq, NSF, and Research Corporation.

  16. Compensation for Phase Anisotropy of a Metal Reflector

    NASA Technical Reports Server (NTRS)

    Hong, John

    2007-01-01

    A method of compensation for the polarization- dependent phase anisotropy of a metal reflector has been proposed. The essence of the method is to coat the reflector with multiple thin alternating layers of two dielectrics that have different indices of refraction, so as to introduce an opposing polarization-dependent phase anisotropy. The anisotropy in question is a phenomenon that occurs in reflection of light at other than normal incidence: For a given plane wave having components polarized parallel (p) and perpendicular (s) to the plane of incidence, the phase of s-polarized reflected light differs from the phase p-polarized light by an amount that depends on the angle of incidence and the complex index of refraction of the metal. The magnitude of the phase difference is zero at zero angle of incidence (normal incidence) and increases with the angle of incidence. This anisotropy is analogous to a phase anisotropy that occurs in propagation of light through a uniaxial dielectric crystal. In such a case, another uniaxial crystal that has the same orientation but opposite birefringence can be used to cancel the phase anisotropy. Although it would be difficult to prepare a birefringent material in a form suitable for application to the curved surface of a typical metal reflector in an optical instrument, it should be possible to effect the desired cancellation of phase anisotropy by exploiting the form birefringence of multiple thin dielectric layers. (The term "form birefringence" can be defined loosely as birefringence arising, in part, from a regular array of alternating subwavelength regions having different indices of refraction.)

  17. Influence of Filler Metals in Welding Wires on the Phase and Chemical Composition of Weld Metal

    NASA Astrophysics Data System (ADS)

    Kozyrev, N. A.; Osetkovskiy, I. V.; Kozyreva, O. A.; Zernin, E. A.; Kartsev, D. S.

    2016-04-01

    The influence of filler metals used in welding wires on the phase and chemical composition of the metal, which is surfaced to mining equipment exposed to abrasive wear, has been investigated. Under a laboratory environment, samples of Mo-V-B and Cr-Mn-Mo-V wires were made. The performed experiments have revealed that fillers of the Cr-Mn-Mo-V system used in powder wire show better wear resistance of the weld metal than that of the Mn-Mo-V-B system; the absence of boron, which promotes grain refinement in the Mn-Mo-V-B system, significantly reduces wear resistance; the Mn-Mo-V-B weld metal has a finer structure than the Cr-Mn-Mo-V weld metal.

  18. Ecotoxicology of heavy metals: Liquid-phase extraction by nanosorbents

    NASA Astrophysics Data System (ADS)

    Burakov, A.; Romantsova, I.; Babkin, A.; Neskoromnaya, E.; Kucherova, A.; Kashevich, Z.

    2015-11-01

    The paper considers the problem of extreme toxicity heavy metal compounds dissolved in wastewater and liquid emissions of industrial enterprises to living organisms and environment as a whole. The possibility of increasing extraction efficiency of heavy metal ions by sorption materials was demonstrated. The porous space of the latter was modified by carbon nanotubes (CNTs) during process of the chemical vapour deposition (CVD) of carbon on metal oxide catalysts. The increasing of the sorption capacity (10-30%) and the sorption rate of nanomodified activated carbons in comparison with standard materials in the example of absorption of Co2+ and Ni2+ ions from aqueous solutions was proven.

  19. Prediction of new crystal structure phases in metal borides

    NASA Astrophysics Data System (ADS)

    Kolmogorov, Aleksey

    2006-03-01

    Identification of novel crystal structures is an important step for predicting new stable compounds in alloys, since most theoretical search algorithms are restricted to a given prototype library or a lattice type. Performing ab initio data mining [1] of intermetallic compounds we have discovered that even in such a well-studied class of systems as metal borides there are previously unknown phases comparable in energy to the existing ones [2]. We demonstrate that even though the new structures are relatively simple, their identification is not straightforward. We systematically investigate the stability and electronic properties of the new metal boride phases. Our calculations show that some phases exhibit electronic features similar to those in the famous MgB2 and could be good superconductors. The new phases are likely to have random stacking faults, so they might not be detected with standard x-ray methods. Our results could thus be used as an important guide in the search for new superconducting metal borides. [1] S. Curtarolo et al., Phys. Rev. Lett. 91, 135503 (2003). [2] A.N. Kolmogorov et al., submitted (2005).

  20. Partitioning of metals in different binding phases of tropical estuarine sediments: importance of metal chemistry.

    PubMed

    Chakraborty, Parthasarathi; Chakraborty, Sucharita; Vudamala, Krushna; Sarkar, Arindam; Nath, B Nagender

    2016-02-01

    Distribution of metals in different binding phases of estuarine sediments provides chemically significant description of metal-sediment interactions. This study describes the influences of ligand field stabilization energy (LFSE), Jahn-Teller effect, and water exchange rate (k-w) on metal distribution in different binding phases of estuarine sediments. It was found that Cu had highest affinity for organic binding phases in the studied sediments followed by Ni and Pb. However, Pb showed strong association with Fe/Mn oxide phases followed by Ni and Cu. Faster k-w of Cu (II) (1 × 10(9) s(-1)) increased the rate of complex formation of Cu(2+) ion with ligand in the organic phases. The Cu-ligand (from organic phase) complexes gained extra stability by the Jahn-Teller effect. The combined effects of these two phenomena and high ionic potential increased the association of Cu with the organic phases of the sediments than Ni and Pb. The smaller ionic radii of Ni(2+) (0.72 Å) than Pb(2+) (1.20 Å) increase the stability of Ni-ligand complexes in the organic phase of the sediments. High LFSE of Ni(II) (compared with Pb(2+) ions) also make Ni-organic complexes increasingly stable than Pb. High k-w (7 × 10(9) s(-1)) of Pb did not help it to associate with organic phases in the sediments. The high concentration of Pb in the Fe/Mn oxyhydroxide binding phase was probably due to co-precipitation of Pb(2+) and Fe(3+). High surface area or site availability for Pb(2+) ion on Fe oxyhydroxide phase was probably responsible for the high concentration of Pb in Fe/Mn oxyhydroxide phase. Increasing concentrations of Cu in organic phases with the increasing Cu loading suggest that enough binding sites were available for Cu in the organic binding phases of the sediments. This study also describes the influence of nature of sedimentary organic carbon (terrestrial and marine derived OC) in controlling these metal distribution and speciation in marine sediment.

  1. Gas-phase synthesis of magnetic metal/polymer nanocomposites.

    PubMed

    Starsich, Fabian H L; Hirt, Ann M; Stark, Wendelin J; Grass, Robert N

    2014-12-19

    Highly magnetic metal Co nanoparticles were produced via reducing flame spray pyrolysis, and directly coated with an epoxy polymer in flight. The polymer content in the samples varied between 14 and 56 wt% of nominal content. A homogenous dispersion of Co nanoparticles in the resulting nanocomposites was visualized by electron microscopy. The size and crystallinity of the metallic fillers was not affected by the polymer, as shown by XRD and magnetic hysteresis measurements. The good control of the polymer content in the product nanocomposite was shown by elemental analysis. Further, the successful polymerization in the gas phase was demonstrated by electron microscopy and size measurements. The presented effective, dry and scalable one-step synthesis method for highly magnetic metal nanoparticle/polymer composites presented here may drastically decrease production costs and increase industrial yields.

  2. Gas-phase synthesis of magnetic metal/polymer nanocomposites

    NASA Astrophysics Data System (ADS)

    Starsich, Fabian H. L.; Hirt, Ann M.; Stark, Wendelin J.; Grass, Robert N.

    2014-12-01

    Highly magnetic metal Co nanoparticles were produced via reducing flame spray pyrolysis, and directly coated with an epoxy polymer in flight. The polymer content in the samples varied between 14 and 56 wt% of nominal content. A homogenous dispersion of Co nanoparticles in the resulting nanocomposites was visualized by electron microscopy. The size and crystallinity of the metallic fillers was not affected by the polymer, as shown by XRD and magnetic hysteresis measurements. The good control of the polymer content in the product nanocomposite was shown by elemental analysis. Further, the successful polymerization in the gas phase was demonstrated by electron microscopy and size measurements. The presented effective, dry and scalable one-step synthesis method for highly magnetic metal nanoparticle/polymer composites presented here may drastically decrease production costs and increase industrial yields.

  3. Polytypic phase transitions in metal intercalated Bi2Se3

    NASA Astrophysics Data System (ADS)

    Wang, Mengjing; Koski, Kristie J.

    2016-12-01

    The temperature and concentration dependent phase diagrams of zero-valent copper, cobalt, and iron intercalated bismuth selenide are investigated using in situ transmission electron microscopy. Polytypic phase transitions associated with superlattice formation along with order-disorder transitions of the guest intercalant are determined. Dual-element intercalants of CuCo, CuFe, and CoFe-Bi2Se3 are also investigated. Hexagonal and striped domain formation consistent with two-dimensional ordering of the intercalant and Pokrovksy-Talapov theory is identified as a function of concentration. These studies provide a complete picture of the structural behavior of zero-valent metal intercalated Bi2Se3.

  4. Scattering of ultrasound by minority phases in polycrystalline metals

    NASA Astrophysics Data System (ADS)

    Sayers, C. M.

    1984-01-01

    The scattering of ultrasound by minority phases in polycrystalline metals is discussed. For discrete inclusions, the scattering theory of Ying and Truell describes the attenuation of longitudinal waves. This is demonstrated by comparison with experiments of Papadakis for graphite particles in modular cast iron. To treat the scattering by a second phase formed by segregation at a grain boundary, the scattering by a spherical shell with density and elastic constants different from those of the surrounding medium is developed. Reflection of ultrasound at this boundary is found to enhance the attenuation at low frequencies. Application is made to the scattering by manganese sulphide in free machining steel.

  5. Reversible Semiconducting-to-Metallic Phase Transition in Chemical Vapor Deposition Grown Monolayer WSe2 and Applications for Devices

    NASA Astrophysics Data System (ADS)

    Ma, Yuqiang; Liu, Bilu; Zhang, Anyi; Chen, Liang; Fathi, Mohammad; Shen, Chenfei; Abbas, Ahmad; Ge, Mingyuan; Mecklenburg, Matthew; Zhou, Chongwu; Usc Nanolab Team

    Two-dimensional (2D) semiconducting monolayer transition metal dichalcogenides (TMDCs) have stimulated lots of interest because they are direct bandgap materials that have reasonably good mobility values. However, contact between most metals and semiconducting TMDCs like 2H phase WSe2 is highly resistive, thus degrading the performance of field effect transistors (FETs) fabricated with WSe2 as active channel materials. We applied a phase engineering method to chemical vapor deposition (CVD) grown monolayer 2H-WSe2 and demonstrated semiconducting-to-metallic phase transition in atomically thin WSe2. We have also shown that metallic phase WSe2 can be converted back to semiconducting phase, demonstrating the reversibility of this phase transition. In addition, we fabricated FETs based on these CVD-grown WSe2 flakes with phase-engineered metallic 1T-WSe2 as contact regions and intact semiconducting 2H-WSe2 as active channel materials. The device performance is substantially improved with metallic phase source/drain electrodes, showing on/off current ratios of 107 and mobilities up to 66 cm2/Vs for monolayer WSe2. PI name: Chongwu Zhou.

  6. On the thermodynamics of phase transitions in metal hydrides

    NASA Astrophysics Data System (ADS)

    Vita, Andrea

    2012-02-01

    Metal hydrides are solutions of hydrogen in a metal, where phase transitions may occur depending on temperature, pressure etc. We apply Le Chatelier's principle of thermodynamics to a particular phase transition in TiHx, which can approximately be described as a second-order phase transition. We show that the fluctuations of the order parameter correspond to fluctuations both of the density of H+ ions and of the distance between adjacent H+ ions. Moreover, as the system approaches the transition and the correlation radius increases, we show -with the help of statistical mechanics-that the statistical weight of modes involving a large number of H+ ions (`collective modes') increases sharply, in spite of the fact that the Boltzmann factor of each collective mode is exponentially small. As a result, the interaction of the H+ ions with collective modes makes a tiny suprathermal fraction of the H+ population appear. Our results hold for similar transitions in metal deuterides, too. A violation of an -insofar undisputed-upper bound on hydrogen loading follows.

  7. On the thermodynamics of phase transitions in metal hydrides

    NASA Astrophysics Data System (ADS)

    di Vita, Andrea

    2012-02-01

    Metal hydrides are solutions of hydrogen in a metal, where phase transitions may occur depending on temperature, pressure etc. We apply Le Chatelier's principle of thermodynamics to a particular phase transition in TiH x , which can approximately be described as a second-order phase transition. We show that the fluctuations of the order parameter correspond to fluctuations both of the density of H+ ions and of the distance between adjacent H+ ions. Moreover, as the system approaches the transition and the correlation radius increases, we show -with the help of statistical mechanics-that the statistical weight of modes involving a large number of H+ ions (`collective modes') increases sharply, in spite of the fact that the Boltzmann factor of each collective mode is exponentially small. As a result, the interaction of the H+ ions with collective modes makes a tiny suprathermal fraction of the H+ population appear. Our results hold for similar transitions in metal deuterides, too. A violation of an -insofar undisputed-upper bound on hydrogen loading follows.

  8. What Coexists with the Ferromagnetic Metallic Phase in Manganites?

    SciTech Connect

    Burkhardt, Mark H; Hossain, M A; Sarkar, S; Achkar, A J; Hawthorn, D G; Sutarto, R; Chuang, 5 Y.-D.; Gonzalez, A G Cruz; Choi, Y J; Cheong, S -W; Durr, H A; Stohr, J

    2012-07-25

    Colossal magnetoresistance, whereby the application of a magnetic field reduces the resistivity of a manganite by orders of magnitude, is generally believed to occur because of coexisting phases. Development of a complete theory to explain the phenomenon requires that the exact nature of these phases be known. We used resonant elastic soft x-ray scattering to examine the superlattice order that exists in La{sub 0.35}Pr{sub 0.275}Ca{sub 0.375}MnO{sub 3} above and below the Curie temperature. By measuring the resonance profile of the scattered x-rays at different values of q, we disentangle the contributions of orbital order and antiferromagnetism to the scattering signal above the Curie temperature. Below the Curie temperature, we see no signal from orbital order, and only antiferromagnetism coexists with the dominant ferromagnetic metallic phase.

  9. Immobilized metal ion affinity partitioning, a method combining metal-protein interaction and partitioning of proteins in aqueous two-phase systems.

    PubMed

    Birkenmeier, G; Vijayalakshmi, M A; Stigbrand, T; Kopperschläger, G

    1991-02-22

    Immobilized metal ions were used for the affinity extraction of proteins in aqueous two-phase systems composed of polyethylene glycol (PEG) and dextran or PEG and salt. Soluble chelating polymers were prepared by covalent attachment of metal-chelating groups to PEG. The effect on the partitioning of proteins of such chelating PEG derivatives coordinated with different metal ions is demonstrated. The proteins studied were alpha 2-macroglobulin, tissue plasminogen activator, superoxide dismutase and monoclonal antibodies. The results indicate that immobilized metal ion affinity partitioning provides excellent potential for the extraction of proteins.

  10. Selective Metallization Induced by Laser Activation: Fabricating Metallized Patterns on Polymer via Metal Oxide Composite.

    PubMed

    Zhang, Jihai; Zhou, Tao; Wen, Liang

    2017-02-28

    Recently, metallization on polymer substrates has been given more attention due to its outstanding properties of both plastics and metals. In this study, the metal oxide composite of copper-chromium oxide (CuO·Cr2O3) was incorporated into the polymer matrix to design a good laser direct structuring (LDS) material, and the well-defined copper pattern (thickness =10 μm) was successfully fabricated through selective metallization based on 1064 nm near-infrared pulsed laser activation and electroless copper plating. We also prepared polymer composites incorporated with CuO and Cr2O3; however, these two polymer composites both had very poor capacity of selective metallization, which has no practical value for LDS technology. In our work, the key reasons causing the above results were systematically studied and elucidated using XPS, UV-vis-IR, optical microscopy, SEM, contact angle, ATR FTIR, and so on. The results showed that 54.0% Cu(2+) in the polymer composite of CuO·Cr2O3 (the amount =5 wt %) is reduced to Cu(0) (elemental copper) after laser activation (irradiation); however, this value is only 26.8% for the polymer composite of CuO (the amount =5 wt %). It was confirmed that to achieve a successful selective metallization after laser activation, not only was the new formed Cu(0) (the catalytic seeds) the crucial factor, but the number of generated Cu(0) catalytic seeds was also important. These two factors codetermined the final results of the selective metallization. The CuO·Cr2O3 is very suitable for applications of fabricating metallic patterns (e.g., metal decoration, circuit) on the inherent pure black or bright black polymer materials via LDS technology, which has a prospect of large-scale industrial applications.

  11. Reflectance Changes during Shock-induced Phase Transformations in Metals

    SciTech Connect

    Stevens, G. D.; Turley, W. D.; Veeser, L. R.; Jensen, B. J.; Rigg, P. A.

    2010-06-01

    In performing shock wave experiments to study the characteristics of metals at high pressures, wave profiles (i.e., velocity measurements of the surface of the sample) are an established and useful way to study phase transformations. For example, a sudden change in the velocity or its slope can occur when the phase transformation induces a large volume change leading to a change in particle velocity. Allowing the shock to release into a transparent window that is in contact with the sample surface allows the study of conditions away from the shock Hugoniot. However, in cases where the wave profile is not definitive an additional phase-transformation diagnostic would be useful. Changes in the electronic structure of the atoms in the crystal offer opportunities to develop new phase-change diagnostics. We have studied optical reflectance changes for several phase transformations to see whether reflectance changes might be a generally applicable phase-transformation diagnostic. Shocks were produced by direct contact with explosives or with impacts from guns. Optical wavelengths for the reflectance measurements ranged from 355 to 700 nm. We studied samples of tin, iron, gallium, and cerium as each passed through a phase transformation during shock loading and, if observable, a reversion upon unloading. For solid-solid phase changes in tin and iron we saw small changes in the surface scattering characteristics, perhaps from voids or rough areas frozen into the surface of the sample as it transformed to a new crystal structure. For melt in gallium and cerium we saw changes in the wavelength dependence of the reflectance, and we surmise that these changes may result from changes in the crystal electronic structure. It appears that reflectance measurements can be a significant part of a larger suite of diagnostics to search for difficult-to-detect phase transformations.

  12. Topological Phase Transition in Metallic Single-Wall Carbon Nanotube

    NASA Astrophysics Data System (ADS)

    Okuyama, Rin; Izumida, Wataru; Eto, Mikio

    2017-01-01

    The topological phase transition is theoretically studied in a metallic single-wall carbon nanotube (SWNT) by applying a magnetic field B parallel to the tube. The Z topological invariant, winding number, is changed discontinuously when a small band gap is closed at a critical value of B, which can be observed as a change in the number of edge states owing to the bulk-edge correspondence. This is confirmed by numerical calculations for finite SWNTs of ˜1 µm length, using a one-dimensional lattice model to effectively describe the mixing between σ and π orbitals and spin-orbit interaction, which are relevant to the formation of the band gap in metallic SWNTs.

  13. Antitumor Activities of Metal Oxide Nanoparticles

    PubMed Central

    Vinardell, Maria Pilar; Mitjans, Montserrat

    2015-01-01

    Nanoparticles have received much attention recently due to their use in cancer therapy. Studies have shown that different metal oxide nanoparticles induce cytotoxicity in cancer cells, but not in normal cells. In some cases, such anticancer activity has been demonstrated to hold for the nanoparticle alone or in combination with different therapies, such as photocatalytic therapy or some anticancer drugs. Zinc oxide nanoparticles have been shown to have this activity alone or when loaded with an anticancer drug, such as doxorubicin. Other nanoparticles that show cytotoxic effects on cancer cells include cobalt oxide, iron oxide and copper oxide. The antitumor mechanism could work through the generation of reactive oxygen species or apoptosis and necrosis, among other possibilities. Here, we review the most significant antitumor results obtained with different metal oxide nanoparticles.

  14. Large resistivity modulation in mixed-phase metallic systems

    NASA Astrophysics Data System (ADS)

    Lee, Yeonbae; Liu, Z. Q.; Heron, J. T.; Clarkson, J. D.; Hong, J.; Ko, C.; Biegalski, M. D.; Aschauer, U.; Hsu, S. L.; Nowakowski, M. E.; Wu, J.; Christen, H. M.; Salahuddin, S.; Bokor, J. B.; Spaldin, N. A.; Schlom, D. G.; Ramesh, R.

    2015-01-01

    In numerous systems, giant physical responses have been discovered when two phases coexist; for example, near a phase transition. An intermetallic FeRh system undergoes a first-order antiferromagnetic to ferromagnetic transition above room temperature and shows two-phase coexistence near the transition. Here we have investigated the effect of an electric field to FeRh/PMN-PT heterostructures and report 8% change in the electrical resistivity of FeRh films. Such a ‘giant’ electroresistance (GER) response is striking in metallic systems, in which external electric fields are screened, and thus only weakly influence the carrier concentrations and mobilities. We show that our FeRh films comprise coexisting ferromagnetic and antiferromagnetic phases with different resistivities and the origin of the GER effect is the strain-mediated change in their relative proportions. The observed behaviour is reminiscent of colossal magnetoresistance in perovskite manganites and illustrates the role of mixed-phase coexistence in achieving large changes in physical properties with low-energy external perturbation.

  15. Satellite thermal storage systems using metallic phase-change materials

    SciTech Connect

    Lauf, R.J.; Hamby, C.

    1989-01-01

    Solar (thermal) dynamic power systems for satellites require a heat storage system capable of operating the engine during eclipse. This paper describes a system in which the phase-change material (PCM) is a metal rather than the more conventional fluoride salts. Thermal storage modules consisting of germanium contained in graphite have good thermal conductivity, low parasitic mass, and are physically and chemically stable. We describe the result of thermal cycle testing of graphite capsules containing germanium and several germanium- and silicon-based alloys, as well as some initial tests of the compatibility of graphite with Nb-1%Zr structural materials. 7 refs., 7 figs., 3 tabs.

  16. Phase Transitions in Model Active Systems

    NASA Astrophysics Data System (ADS)

    Redner, Gabriel S.

    The amazing collective behaviors of active systems such as bird flocks, schools of fish, and colonies of microorganisms have long amazed scientists and laypeople alike. Understanding the physics of such systems is challenging due to their far-from-equilibrium dynamics, as well as the extreme diversity in their ingredients, relevant time- and length-scales, and emergent phenomenology. To make progress, one can categorize active systems by the symmetries of their constituent particles, as well as how activity is expressed. In this work, we examine two categories of active systems, and explore their phase behavior in detail. First, we study systems of self-propelled spherical particles moving in two dimensions. Despite the absence of an aligning interaction, this system displays complex emergent dynamics, including phase separation into a dense active solid and dilute gas. Using simulations and analytic modeling, we quantify the phase diagram and separation kinetics. We show that this nonequilibrium phase transition is analogous to an equilibrium vapor-liquid system, with binodal and spinodal curves and a critical point. We also characterize the dense active solid phase, a unique material which exhibits the structural signatures of a crystalline solid near the crystal-hexatic transition point, as well as anomalous dynamics including superdiffusive motion on intermediate timescales. We also explore the role of interparticle attraction in this system. We demonstrate that attraction drastically changes the phase diagram, which contains two distinct phase-separated regions and is reentrant as a function of propulsion speed. We interpret this complex situation with a simple kinetic model, which builds from the observed microdynamics of individual particles to a full description of the macroscopic phase behavior. We also study active nematics, liquid crystals driven out of equilibrium by energy-dissipating active stresses. The equilibrium nematic state is unstable in these

  17. Breast milk metal ion levels in a young and active patient with a metal-on-metal hip prosthesis.

    PubMed

    Nelis, Raymond; de Waal Malefijt, Jan; Gosens, Taco

    2013-01-01

    Metal-on-metal resurfacing arthroplasty of the hip has been used increasingly over the last 10 years in younger active patients. The dissolution of the metal wear particles results in measurable increases in cobalt and chromium ions in the serum and urine of patients with a metal-on-metal bearing. We measured the cobalt, chromium, and molybdenum ion levels in urine; serum; and breast milk in a young and active patient with a metal-on-metal hip prosthesis after a pathologic fracture of the femoral neck. Metal-on-metal hip prosthesis leads to increasing levels of molybdenum in breast milk in the short-term follow-up. There are no increasing levels of chromium and cobalt ions in breast milk. Besides the already known elevated concentrations in serum of chromium and cobalt after implantation of a metal-on-metal hip prosthesis, we found no increasing levels of chromium and cobalt in urine.

  18. Phase separation of metallic hydrogen-helium alloys

    NASA Technical Reports Server (NTRS)

    Straus, D. M.; Ashcroft, N. W.; Beck, H.

    1977-01-01

    Calculations are presented for the thermodynamic functions and phase-separation boundaries of solid metallic hydrogen-helium alloys at temperatures between zero and 19,000 K and at pressures between 15 and 90 Mbar. Expressions for the band-structure energy of a randomly disordered alloy (including third order in the electron-ion interaction) are derived and evaluated. Short- and long-range orders are included by the quasi-chemical method, and lattice dynamics in the virtual-crystal harmonic approximation. It is concluded that at temperatures below 4000 K, there is essentially complete phase separation of hydrogen-helium alloys and that a miscibility gap remains at the highest temperatures and pressures considered. The relevance of these results to models of the deep interior of Jupiter is briefly discussed.

  19. Phase separation of metallic hydrogen-helium alloys

    NASA Technical Reports Server (NTRS)

    Straus, D. M.; Ashcroft, N. W.; Beck, H.

    1976-01-01

    Calculations are presented for the thermodynamic functions and phase separation boundaries of solid metallic hydrogen helium alloys at temperatures between 0 K and 19,000 K and at pressures between 15 and 90 megabars. Expressions for the band structure energy of a randomly disordered alloy (including third order in the electron ion interaction) are derived and evaluated. Short and long range order are included by the quasi-chemical method, and lattice dynamics in the virtual crystal harmonic approximation. We conclude that at temperatures below 4,000 K there is complete phase separation of hydrogen helium alloys, and that a miscibility gap remains at the highest temperatures and pressures considered. The relevance of these results to models of the deep interior of Jupiter is briefly discussed.

  20. Large resistivity modulation in mixed-phase metallic systems

    NASA Astrophysics Data System (ADS)

    Lee, Yeonbae; Liu, Zhiqi; Heron, John; Clarkson, James; Hong, Jeongmin; Ko, Changhyun; Biegalski, Michael; Aschauer, Ulrich; Hsu, Shang-Lin; Nowakowski, Mark; Wu, Junqiao; Christen, Hans; Salahuddin, Sayeef; Bokor, Jeffrey; Spaldin, Nicola; Schlom, Darrell; Ramesh, Ramamoorthy

    2015-03-01

    We have investigated the effect of an electric field to FeRh/PMN-PT heterostructures and report 8% change in the electrical resistivity of FeRh films. Such a ``giant'' electroresistance (GER) response is striking in metallic systems, in which external electric fields are screened and thus only weakly influence the carrier concentrations and mobilities. We show that our FeRh films comprise coexisting ferromagnetic and antiferromagnetic phases with different resistivities, and the origin of the GER effect is the strain-mediated change in their relative proportions. The observed behavior is reminiscent of colossal magnetoresistance in perovskite manganites, and illustrates the role of mixed-phase coexistence in achieving large changes in physical properties with low-energy external perturbation.

  1. Chemically and temperature-induced phase transformations of metal vanadates

    NASA Astrophysics Data System (ADS)

    Patridge, Christopher James

    Metal vanadates contain a diverse family of compounds due to the facile accessibility of different vanadium oxidation states and local coordination environments. Though these systems present a number of applications in catalysis and electronics, there may exist untapped physical phenomena that only reveal themselves when scaling these materials to nanoscale dimensions. Finite-size effects result from a number of factors including surface energy structural instabilities, nanostructure "self-purification," and physical constraints on mechanistic or conductive pathways. The MxV2O 5 bronze materials possess non-stoichiometry and this interesting property has hindered synthetic techniques to procure perfect crystalline material which is needed to expose the true physical properties. Through hydrothermal synthesis methods, pseudo one---dimensional nanostructures of Mx V2O5 display fascinating new properties and may be model systems for studying fundamentals associated with correlated electron dynamics in solid-state physics. Electron microscopy and powder X-ray diffraction reveal the near-perfect crystalline nanostructures. X-ray absorption spectroscopy studies show strong evidence for the localization of electron density and long-range crystal structure alignment of the nanowires. Single-nanowire electron transport measurements for the beta'-CuxV2O5 and the delta-KxV2O5 data shows novel temperature-induced reversible metal---insulator transition (MIT) near room temperature. The unprecedented magnitude (˜105) and discontinuous nature of the MIT suggests a mechanism closely associated with correlated electron motion. Additionally, the MIT can be induced by voltage ramping. The simultaneous temperature/voltage studies of single-nanowire transport support the existence of a critical threshold to overcome in order to facilitate instability in the insulating phase and transition to a metallic phase for the delta-KxV2O5 bronze. The MIT transition magnitudes of several

  2. Phase transformations and thermodynamics of aluminum-based metallic glasses

    NASA Astrophysics Data System (ADS)

    Gao, Changhua (Michael)

    This thesis examines the thermodynamics and associated kinetics and phase transformations of the glass forming Al-Ni-Gd and Al-Fe-Gd systems. In order to fully understand the unique glass forming ability (GFA) of Al-based metallic glasses, the ternary Al-Fe-Gd and Al-Ni-Gd systems in their Al-rich corners were examined experimentally to assist in a thermodynamic assessment. The solid-state phase equilibria are determined using XRD and TEM-EDS techniques. While this work basically confirms the solid-state equilibria in Al-Fe-Gd reported previously, the ternary phase in Al-Ni-Gd system has been identified to be Al15Ni3Gd2 rather than Al16Ni 3Gd reported in the literature. DTA analysis of 24 alloys in the Al-Fe-Gd system and 42 alloys in the Al-Ni-Gd system have yielded critical temperatures pertaining to the solid-liquid transition. Based on these data and information from the literature, a self-consistent thermodynamic database for these systems has been developed using the CALPHAD technique. Parameters describing the Gibbs free energy for various phases of the Al-Gd, Al-Fe-Gd and Al-Ni-Gd systems are manually optimized in this study. Once constructed, the database is used to calculate driving forces for nucleation of crystalline phases which can qualitatively explain the phase formation sequence during crystallization at low temperatures. It was also confirmed that alloy compositions with the lowest Gibbs free energy difference between the equilibrium state and undercooled liquid state exhibit better GFA than other chemistries. Based on 250°C isothermal devitrification phase transformations of 17 Al-Ni-Gd alloys, a phase formation sequence map is constructed. Fcc-Al nanocrystals are formed first in most of the alloys studied, but eutectic crystallization of a metastable phase and fcc-Al is also observed. Addition of Al or Ni promotes fcc-Al phase formation, while increasing Gd suppresses it. The continuous heating DSC scans revealed that crystallization in Al

  3. Magnetic liquid metal two-phase flow research. Phase 1. Final report

    SciTech Connect

    Graves, R.D.

    1983-04-01

    The Phase I research demonstrates the feasibility of the magnetic liquid metal (MLM) two-phase flow concept. A dispersion analysis is presented based on a complete set of two-phase-flow equations augmented to include stresses due to magnetic polarization of the fluid. The analysis shows that the stability of the MLM two-phase flow is determined by the magnetic Mach number, the slip ratio, geometry of the flow relative to the applied magnetic field, and by the voidage dependence of the interfacial forces. Results of a set of experiments concerned with magnetic effects on the dynamics of single bubble motion in an aqueous-based, viscous, conducting magnetic fluid are presented. Predictions in the theoretical literature are qualitatively verified using a bench-top experimental apparatus. In particular, applied magnetic fields are seen to lead to reduced bubble size at fixed generating orifice pressure.

  4. Metallic phase change material thermal storage for Dish Stirling

    DOE PAGES

    Andraka, C. E.; Kruizenga, A. M.; Hernandez-Sanchez, B. A.; ...

    2015-06-05

    Dish-Stirling systems provide high-efficiency solar-only electrical generation and currently hold the world record at 31.25%. This high efficiency results in a system with a high possibility of meeting the DOE SunShot goal of $0.06/kWh. However, current dish-Stirling systems do not incorporate thermal storage. For the next generation of non-intermittent and cost-competitive solar power plants, we propose adding a thermal energy storage system that combines latent (phase-change) energy transport and latent energy storage in order to match the isothermal input requirements of Stirling engines while also maximizing the exergetic efficiency of the entire system. This paper reports current findings in themore » area of selection, synthesis and evaluation of a suitable high performance metallic phase change material (PCM) as well as potential interactions with containment alloy materials. The metallic PCM's, while more expensive than salts, have been identified as having substantial performance advantages primarily due to high thermal conductivity, leading to high exergetic efficiency. Systems modeling has indicated, based on high dish Stirling system performance, an allowable cost of the PCM storage system that is substantially higher than SunShot goals for storage cost on tower systems. Several PCM's are identified with suitable melting temperature, cost, and performance.« less

  5. Dynamic Phase Engineering of Bendable Transition Metal Dichalcogenide Monolayers.

    PubMed

    Berry, Joel; Zhou, Songsong; Han, Jian; Srolovitz, David J; Haataja, Mikko P

    2017-03-14

    Current interest in two-dimensional (2D) materials is driven in part by the ability to dramatically alter their optoelectronic properties through strain and phase engineering. A combination of these approaches can be applied in quasi-2D transition metal dichalcogenide (TMD) monolayers to induce displacive structural transformations between semiconducting (H) and metallic/semimetallic (T') phases. We classify such transformations in Group VI TMDs, and formulate a multiscale, first-principles-informed modeling framework to describe evolution of microstructural domain morphologies in elastically bendable 2D monolayers. We demonstrate that morphology and mechanical response can be controlled via application of strain either uniformly or through local probes to generate functionally patterned conductive T' domains. Such systems form dynamically programmable electromechanical 2D materials, capable of rapid local switching between domains with qualitatively different transport properties. This enables dynamic "drawing" of localized conducting regions in an otherwise semiconducting TMD monolayer, opening several interesting device-relevant functionalities such as the ability to dynamically "rewire" a device in real time.

  6. Metallic phase change material thermal storage for Dish Stirling

    SciTech Connect

    Andraka, C. E.; Kruizenga, A. M.; Hernandez-Sanchez, B. A.; Coker, E. N.

    2015-06-05

    Dish-Stirling systems provide high-efficiency solar-only electrical generation and currently hold the world record at 31.25%. This high efficiency results in a system with a high possibility of meeting the DOE SunShot goal of $0.06/kWh. However, current dish-Stirling systems do not incorporate thermal storage. For the next generation of non-intermittent and cost-competitive solar power plants, we propose adding a thermal energy storage system that combines latent (phase-change) energy transport and latent energy storage in order to match the isothermal input requirements of Stirling engines while also maximizing the exergetic efficiency of the entire system. This paper reports current findings in the area of selection, synthesis and evaluation of a suitable high performance metallic phase change material (PCM) as well as potential interactions with containment alloy materials. The metallic PCM's, while more expensive than salts, have been identified as having substantial performance advantages primarily due to high thermal conductivity, leading to high exergetic efficiency. Systems modeling has indicated, based on high dish Stirling system performance, an allowable cost of the PCM storage system that is substantially higher than SunShot goals for storage cost on tower systems. Several PCM's are identified with suitable melting temperature, cost, and performance.

  7. Methane activation on supported transition metal catalysts

    NASA Astrophysics Data System (ADS)

    Carstens, Jason Ned

    At present, there is considerable interest in utilizing methane more efficiently as both a fuel source and as a starting material for the production of other, more valuable products. However, methane is a very stable molecule with strong C-H bonds that are difficult to break. This makes methane combustion or the formation of carbon-carbon bonds quite difficult. The present work focuses on the use of supported transition metal catalysts as a means of activating methane (i.e. breaking C-H bonds) at low temperatures to produce valuable products or energy. The conversion of methane into higher hydrocarbons. A low temperature (<750 K), direct process to effectively convert methane into higher hydrocarbons would be quite desirable. Such a process is thermodynamically feasible if the reaction is broken up into two separate steps. The first step is the adsorption of methane onto a transition metal catalyst at temperatures above about 600 K to produce a surface carbon species. The second step is a low temperature (<373 K) hydrogenation to convert the carbon species into higher hydrocarbons. T. Koerts et al. have pursued this approach by dissociatively absorbing methane onto silica supported transition metal catalysts at temperatures ranging between 573 K and 773 K. The result was a surface carbonaceous species and hydrogen. In the second step, the carbonaceous intermediates produced small alkanes upon hydrogenation around 373 K. A maximum yield to higher hydrocarbons of 13% was obtained on a ruthenium catalyst. The present study was conducted to further investigate the nature of the carbonaceous species reported by Koerts. Methane combustion. This investigation was conducted in an effort to better understand the mechanism of methane combustion on Pd catalysts. In the first part of this study, temperature programmed reduction (TPR) was used to investigate the oxidation and reduction dynamics of a 10 wt% Pd/ZrOsb2 catalyst used for methane combustion. TPR experiments indicate

  8. Thermodynamic considerations of the vapor phase reactions in III–nitride metal organic vapor phase epitaxy

    NASA Astrophysics Data System (ADS)

    Sekiguchi, Kazuki; Shirakawa, Hiroki; Chokawa, Kenta; Araidai, Masaaki; Kangawa, Yoshihiro; Kakimoto, Koichi; Shiraishi, Kenji

    2017-04-01

    We analyzed the metal organic vapor phase epitaxial growth mechanism of the III–nitride semiconductors GaN, AlN, and InN by first-principles calculations and thermodynamic analyses. In these analyses, we investigated the decomposition processes of the group III source gases X(CH3)3 (X = Ga, Al, In) at finite temperatures and determined whether the (CH3)2GaNH2 adduct can be formed or not. The results of our calculations show that the (CH3)2GaNH2 adduct cannot be formed in the gas phase in GaN metal organic vapor phase epitaxy (MOVPE), whereas, in AlN MOVPE, the formation of the (CH3)2AlNH2 adduct in the gas phase is exclusive. In the case of GaN MOVPE, trimethylgallium (TMG, [Ga(CH3)3]) decomposition into Ga gas on the growth surface with the assistance of H2 carrier gas, instead of the formation of the (CH3)2GaNH2 adduct, occurs almost exclusively. Moreover, in the case of InN MOVPE, the formation of the (CH3)2InNH2 adduct does not occur and it is relatively easy to produce In gas even without H2 in the carrier gas.

  9. Phase identification in dental porcelains for ceramo-metallic restorations.

    PubMed

    Barreiro, M M; Riesgo, O; Vicente, E E

    1989-01-01

    Most commercial dental porcelains designed for ceramo-metallic restorations are partially crystallized feldspathic glasses (glass-ceramics) that consist of low (tetragonal) leucite (K2O.Al2O3.4SiO2) crystals embedded in a glassy matrix. In this work, we have identified the crystalline phases in eight commercial dental porcelains (four enamels and four dentin bodies) in both powder (unfired) and sintered forms, by x-ray diffraction, emission spectroscopy analysis, reflection optical microscopy, and scanning electron microscopy. Besides low leucite and glass, we have found a second crystalline phase in the sintered and slow-cooled porcelains that we propose to be potash feldspar (K2O.Al2O3.6SiO2). It was impossible to ascertain whether these synthetic crystals may be sanidine, orthoclase, or microcline. The precipitation of feldspar during cooling is explained in terms of the crystallization behavior of typical body compositions in the ternary-phase diagram K2O-Al2O3-SiO2. Ceramography confirms the martensitic (displacive) nature of the transformation from high (cubic) to low (tetragonal) leucite upon cooling.

  10. A spectroscopic and catalytic investigation of active phase-support interactions

    SciTech Connect

    Haller, G.L.

    1991-01-01

    Active catalytic phases (metal, mixed metals, oxide or mixed oxides) interacting with oxide support on which the active phase is dispersed can affect the percentage exposed, the morphology of supported particles, the degree of reducibility of cations, etc., in a variety of ways. Our objective is to characterize the physical chemistry of the active phase-oxide support by spectroscopic methods and to correlate this structure with catalytic function. The three systems discussed in this progress report are Ag/TiO{sub 2}, Ru-Cu/SiO{sub 2} and SiO{sub 2}/Al{sub 2}O{sub 3}. 24 refs., 3 figs., 2 tabs.

  11. Tailorable chiroptical activity of metallic nanospiral arrays

    NASA Astrophysics Data System (ADS)

    Deng, Junhong; Fu, Junxue; Ng, Jack; Huang, Zhifeng

    2016-02-01

    The engineering of the chiroptical activity of the emerging chiral metamaterial, metallic nanospirals, is in its infancy. We utilize glancing angle deposition (GLAD) to facilely sculpture the helical structure of silver nanospirals (AgNSs), so that the scope of chiroptical engineering factors is broadened to include the spiral growth of homochiral AgNSs, the combination of left- and right-handed helical chirality to create heterochiral AgNSs, and the coil-axis alignment of the heterochiral AgNSs. It leads to flexible control over the chiroptical activity of AgNS arrays with respect to the sign, resonance wavelength and amplitude of circular dichroism (CD) in the UV and visible regime. The UV chiroptical mode has a distinct response from the visible mode. Finite element simulation together with LC circuit theory illustrates that the UV irradiation is mainly adsorbed in the metal and the visible is preferentially scattered by the AgNSs, accounting for the wavelength-related chiroptical distinction. This work contributes to broadening the horizons in understanding and engineering chiroptical responses, primarily desired for developing a wide range of potential chiroplasmonic applications.The engineering of the chiroptical activity of the emerging chiral metamaterial, metallic nanospirals, is in its infancy. We utilize glancing angle deposition (GLAD) to facilely sculpture the helical structure of silver nanospirals (AgNSs), so that the scope of chiroptical engineering factors is broadened to include the spiral growth of homochiral AgNSs, the combination of left- and right-handed helical chirality to create heterochiral AgNSs, and the coil-axis alignment of the heterochiral AgNSs. It leads to flexible control over the chiroptical activity of AgNS arrays with respect to the sign, resonance wavelength and amplitude of circular dichroism (CD) in the UV and visible regime. The UV chiroptical mode has a distinct response from the visible mode. Finite element simulation

  12. Metal-ligand redox reactions in gas-phase quaternary peptide-metal complexes by electrospray ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Vaisar, T.; Gatlin, C. L.; Turecek, F.

    1997-03-01

    The dipeptides Phe-Leu, Leu-Phe, Leu-Ala, and Ala-Leu form quaternary complexes of the type [Cu(II)(peptide - 2H+M)bpy]+ in the gas phase when electrosprayed in the presence of Cu(II) salts, 2.2'-bipyridyl (bpy), and an alkali hydroxide (MOH). The gas-phase complexes decarboxylate on collisional activation at low ion kinetic energies. The resulting ions undergo unusual eliminations of neutral Na, K, and Rb, which depend on the peptide structure. The ionization energy of the decarboxylated Phe-Leu-Cu-bpy complex was bracketed at 4.2 eV. Other collision-induced dissociations also depend on the alkali metal ion and the peptide structure. Ab initio calculations on a model system are reported and used to discuss the electronic properties of the peptide complexes.

  13. Magnetic phases in lunar fines - Metallic Fe or ferric oxides.

    NASA Technical Reports Server (NTRS)

    Tsay, F.-D.; Manatt, S. L.; Chan, S. I.

    1973-01-01

    The ferromagnetic resonance observed for the Apollo 11 and 12 lunar fines is characterized by an asymmetric lineshape with a narrower appearance on the high field side. This asymmetry together with an anisotropy energy which varies from +640 to +500 G over the temperature range of 80 to 298 K indicate that the ferromagnetic resonance arises from metallic Fe having the body-centered cubic structure and not from hematite, magnetite or other Fe(3+) ions in magnetite-like phases. The g-value, the lineshape asymmetry, and the temperature dependence of the linewidth for the Apollo 14 and 15 fines as reported by other workers are found to be essentially similar to those observed for the Apollo 11 and 12 fines.

  14. Transient liquid-phase bonding using coated metal powders

    SciTech Connect

    Zhuang, W.D.; Eagar, T.W.

    1997-04-01

    Powder particles coated with a small amount of melting point depressant (MPD) reveal different sintering behavior in comparison to an uncoated powder mixture of the same composition. Interlayers consisting of the coated powder particles were used in the transient liquid-phase (TLP) bonding process. The coating material and the thickness of the deposit are important parameters that influence shrinkage. The amount of MPD was controlled such that the volume fraction of the liquid was very small but existed at all contacts, thus improving densification of the interlayer. Ni-20Cr and 304L stainless steel powders coated with Ni-10P were applied to join 304 stainless steels. Fully dense joints with mechanical properties comparable to those of the base metals were obtained with Ni-20Cr powder interlayers, whereas joints with 304L stainless steel powder interlayers showed inferior mechanical properties due to residual porosity in the joints.

  15. Electron phase coherence in mesoscopic normal metal wires

    NASA Astrophysics Data System (ADS)

    Trionfi, Aaron James

    Corrections to the classically predicted electrical conductivity in normal metals arise due to the quantum mechanical properties of the conduction electrons. These corrections provide multiple experimental tests of the conduction electrons' quantum phase coherence. I consider if independent measurements of the phase coherence via different corrections are quantitatively consistent, particularly in systems with spin-orbit or magnetic impurity scattering. More precisely, do independent quantum corrections to the classically predicted conductivity depend identically on the ubiquitous dephasing mechanisms in normal metals? I have inferred the coherence lengths from the weak localization magnetoresistance, magnetic field-dependence of time-dependent universal conductance fluctuations, and magnetic field-dependent universal conductance fluctuations, three observable quantum corrections, in quasi one- and two-dimensional AuPd wires and quasi-1D Ag and Au wires between 2 and 20 K. While the coherence lengths inferred from weak localization and time-dependent universal conductance fluctuations are in excellent quantitative agreement in AuPd, the strong quantitative agreement is apparently lost below a critical temperature in both Ag and Au. Such a disagreement is inconsistent with current theory and must be explained. I developed a hypothesis attributing the coherence length discrepancy seen in Ag and Au to a crossover from the saturated to unsaturated time-dependent conductance fluctuation regime. Two experimental tests were then employed to test this hypothesis. One test examined the effects of a changing spin-flip scattering rate in Au while the second examined how passivation of the two level systems responsible for time-dependent conductance fluctuations at the surface of a Au nanowire affects the inferred coherence lengths. The results of the two tests strongly indicate that the observed disagreement in Au (and likely Ag) is indeed due to a crossover from saturated to

  16. A 1-dodecanethiol-based phase transfer protocol for the highly efficient extraction of noble metal ions from aqueous phase.

    PubMed

    Chen, Dong; Cui, Penglei; Cao, Hongbin; Yang, Jun

    2015-03-01

    A 1-dodecanethiol-based phase-transfer protocol is developed for the extraction of noble metal ions from aqueous solution to a hydrocarbon phase, which calls for first mixing the aqueous metal ion solution with an ethanolic solution of 1-dodecanethiol, and then extracting the coordination compounds formed between noble metal ions and 1-dodecanethiol into a non-polar organic solvent. A number of characterization techniques, including inductively coupled plasma atomic emission spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis demonstrate that this protocol could be applied to extract a wide variety of noble metal ions from water to dichloromethane with an efficiency of >96%, and has high selectivity for the separation of the noble metal ions from other transition metals. It is therefore an attractive alternative for the extraction of noble metals from water, soil, or waste printed circuit boards.

  17. Heavy metals testing in active pharmaceutical ingredients: an alternate approach.

    PubMed

    Raghuram, P; Soma Raju, I V; Sriramulu, J

    2010-01-01

    The principle of the pharmacopoeial heavy metals test is detection and estimation of the metallic impurities colored by sulfide ion by comparison against lead standard. The test suffers from a loss of analytes upon ashing and from having varied responses for various metals. An inductively coupled plasma-optical emission spectroscopy (ICP-OES) for estimating 23 metals in active pharmaceutical ingredients is being proposed. The method covers the metals listed in USP, Ph. Eur and EMEA guidance on "Residues of Metal Catalysts or Metal Reagents".

  18. Diffusion analysis for two-phase metal-matrix composite

    NASA Technical Reports Server (NTRS)

    Tenney, D. R.

    1976-01-01

    Diffusion controlled filament matrix interaction in a metal matrix composite, where the filaments and matrix comprise a two phase binary alloy system, was mathematically modeled. The problem of a diffusion controlled, two phase moving interface by means of a one dimensional, variable grid, finite difference technique was analyzed. Concentration dependent diffusion coefficients and equilibrium solubility limits were used, and the change in filament diameter and compositional changes in the matrix were calculated as a function of exposure time at elevated temperatures. With the tungsten nickel (W-Ni) system as a model composite system, unidirectional composites containing from 0.06 to 0.44 initial filament volume fraction were modeled. Compositional changes in the matrix were calculated by superposition of the contributions from neighboring filaments. Alternate methods for determining compositional changes between first and second nearest neighbor filaments were also considered. The results show the relative importance of filament volume fraction, filament diameter, exposure temperature, and exposure time as they affect the rate and extent of filament matrix interaction.

  19. Low temperature phase transformations in the metallic phases of iron and stony-iron meteorites

    NASA Astrophysics Data System (ADS)

    Reuter, K. B.; Williams, D. B.; Goldstein, J. I.

    1988-03-01

    The nickel content and the structure of kamacite and decomposed taenite (clear taenite 1, CT-1; the cloudy zone, CZ; and clear taenite 2, CT-2) in the metallic phases of meteorites were determined using X-ray microanalysis techniques in the AEM. The kamacite near the CT-1 interface was found to contain about 4 wt pct Ni. The CT-1 structure contains 51.4-45.6 wt pct Ni; it is ordered FeNi with the L1(0) superstructure. The CZ structure consists of two phases: a globular phase (ordered FeNi containing 50.9 wt pct Ni) and a surrounding honeycomb martensitic phase containing 11.7 wt pct Ni. The CT-2 was found in all of the iron meteorite groups studied and in the pallasites, but not in the mesosiderites. Based on the preliminary evidence, this region is believed to be ordered Fe3Ni. Possible mechanisms for the decomposition of taenite are discussed.

  20. Low temperature phase transformations in the metallic phases of iron and stony-iron meteorites

    NASA Technical Reports Server (NTRS)

    Reuter, K. B.; Williams, D. B.; Goldstein, J. I.

    1988-01-01

    The nickel content and the structure of kamacite and decomposed taenite (clear taenite 1, CT-1; the cloudy zone, CZ; and clear taenite 2, CT-2) in the metallic phases of meteorites were determined using X-ray microanalysis techniques in the AEM. The kamacite near the CT-1 interface was found to contain about 4 wt pct Ni. The CT-1 structure contains 51.4-45.6 wt pct Ni; it is ordered FeNi with the L1(0) superstructure. The CZ structure consists of two phases: a globular phase (ordered FeNi containing 50.9 wt pct Ni) and a surrounding honeycomb martensitic phase containing 11.7 wt pct Ni. The CT-2 was found in all of the iron meteorite groups studied and in the pallasites, but not in the mesosiderites. Based on the preliminary evidence, this region is believed to be ordered Fe3Ni. Possible mechanisms for the decomposition of taenite are discussed.

  1. Partition of actinides and fission products between metal and molten salt phases: Theory, measurement, and application to IFR pyroprocess development

    SciTech Connect

    Ackerman, J.P.; Johnson, T.R.

    1993-10-01

    The chemical basis of Integral Fast Reactor fuel reprocessing (pyroprocessing) is partition of fuel, cladding, and fission product elements between molten LiCl-KCl and either a solid metal phase or a liquid cadmium phase. The partition reactions are described herein, and the thermodynamic basis for predicting distributions of actinides and fission products in the pyroprocess is discussed. The critical role of metal-phase activity coefficients, especially those of rare earth and the transuranic elements, is described. Measured separation factors, which are analogous to equilibrium constants but which involve concentrations rather than activities, are presented. The uses of thermodynamic calculations in process development are described, as are computer codes developed for calculating material flows and phase compositions in pyroprocessing.

  2. Quantum phase transitions in ultrathin films of metal

    NASA Astrophysics Data System (ADS)

    Mack, Anthony Michael

    1997-11-01

    Conductance measurements of ultrathin films of amorphous bismuth are presented. The measurements were performed at temperatures down to 0.15K as a function of temperature and film thickness. Such films are known to become superconducting when the conductance reaches ˜4esp2/h. Careful analysis of the insulating state reveals a crossover near esp2/h, with hopping conduction below and weak localization above. A corresponding change in behavior is also evident in plots of G vs. d at esp2/h. A crossover conductance, Gsbcr ˜ (30 ± 1kOmega)sp{-1}, was extracted by examining the derivative of the G vs. d curves. A scaling analysis is performed yielding an excellent collapse of the data with critical exponents nu z = 6.9 ± 0.7. Ultrathin films of Pd (which is not superconducting) also show a crossover, but at Gsbcr ˜ (56 ± 6kOmega)sp{-1}. The Bi and Pd data sets are collapsed together onto the same curve yielding nu z = 7.2 ± 1.0 for Pd. The success of the scaling analysis supports the view that the crossover is the finite temperature signature of a quantum phase transition occurring at T = 0. The transition is between phases identified as (weakly localized) metal and insulator, which may make this the first observation of a metal-insulator transition in a two-dimensional system. The scaling analysis developed for the crossover at esp2/h was applied to the superconductor-insulator transition as well. While the collapse of the data is poor, the analysis yields a single value of the critical exponent nu z = 1.99 ± 0.09. A previous analysis yielded two separate (and inconsistent) values of nu z on the insulating and superconducting sides. The analysis was also applied to the case of the field-driven superconductor-insulator transition. The resulting collapse is excellent yielding a critical exponent nu z = 0.637 ± 0.010. The scaling parameter deviates from a power law in T above 0.7K. Since the data presented only extends down to 0.5K, the critical region accessed is

  3. Induction of several acute-phase protein genes by heavy metals: A new class of metal-responsive genes

    SciTech Connect

    Yiangou, Minas; Ge, Xin; Carter, K.C.; Papaconstantinou, J. Shriners Burns Institute, Galveston, TX )

    1991-04-16

    Acute-phase reactants, metallothioneins, and heat-shock proteins are the products of three families of genes that respond to glucocorticoids and cytokines. Metallothioneins and heat-shock proteins, however, are also stimulated by heavy metals whereas very little is known about the effect of heavy metals on acute-phase-reactant genes. The authors have studied the effect of heavy metals (Hg, Cd, Pb, Cu, Ni, and Zn) and Mg on the acute-phase reactants {alpha}{sub 1}-acid glycoprotein, C-reactive protein, {alpha}{sub 1}-antitrypsin and {alpha}{sub 1}-antichymotrypsin. {alpha}{sub 1}-Acid glycoprotein and C-reactive protein mRNA levels were increased severalfold in livers of heavy-metal-treated Balb/c mice. The strongest induction was mediated by Hg, followed in order of response by Cd > Pb > Cu > Ni > Zn > Mg. None of the metals affected the mRNA levels of albumin, {alpha}{sub 1}-antitrypsin, and {alpha}{sub 1}-antichymotrypsin. Furthermore, failure to repress albumin, a negative acute-phase reactant, indicated that the induction of these genes was not due to a metal-mediated inflammatory response. The metals also induced {alpha}{sub 1}-acid glycoprotein and C-reactive protein in adrenalectomized animals, indicating that induction by the heavy metals is not mediated by the glucocorticoid induction pathway. Sequence analysis has revealed a region of homology to metal-responsive elements in the {alpha}{sub 1}-acid glycoprotein and C-reactive protein promoters. The studies indicate that the induction of {alpha}{sub 1}-acid glycoprotein and C-reactive protein by heavy metals may be regulated by these metal-responsive elements at the level of transcription.

  4. Molecular recognition properties of tartrates and metal-tartrates in solution and gas phase.

    PubMed

    Wijeratne, Aruna B; Schug, Kevin A

    2009-05-01

    Solution phase and gas phase chiral molecular recognition properties of tartrates (salts or esters of tartaric acid) and metal tartrates (binuclear tartrato(4-)-metal-bridged complexes) are reviewed in conjunction with their applications in enantiomeric separation science and their mass spectrometric chiral discrimination properties.

  5. Stability and isomerization of complexes formed by metal ions and cytosine isomers in aqueous phase.

    PubMed

    Ai, Hongqi; Liu, Jingjing; Chan, Kwaichow

    2013-08-01

    We present a systematic study of the stability of the formation of complexes produced by four metal ions (M(+/2+)) and 14 cytosine isomers (Cn). This work predicts theoretically that predominant product complexes are associated with higher-energy C4M(+/2+) and C5M(+/2+) rather than the most stable C1M(+/2+). The prediction resolves successfully several experimental facts puzzling two research groups. Meanwhile, in-depth studies further reveal that direct isomerization of C1↔C4 is almost impossible, and also that the isomerization induced by either metalation or hydration, or by a combination of the two unfavorable. It is the single water molecule locating between the H1(-N1) and O2 of the cytosine that plays the dual roles of being a bridge and an activator that consequently improves the isomerization greatly. Moreover, the cooperation of divalent metal ion and such a monohydration actually leads to an energy-free C1←C4 isomerization in the gas phase. Henceforth, we are able to propose schemes inhibiting the free C1←C4 isomerization, based purely on extended hydration at the divalent metal ion.

  6. Thermochemistry and Geometries for Transition-Metal Chemistry from the Random Phase Approximation.

    PubMed

    Waitt, Craig; Ferrara, Nashali M; Eshuis, Henk

    2016-11-08

    Performance of the random phase approximation (RPA) is tested for thermochemistry and geometries of transition-metal chemistry using various benchmarks obtained either computationally or experimentally. Comparison is made to popular (semi)local meta- and hybrid density functionals as well as to the second-order Møller-Plesset perturbation theory (MP2) and its spin-component-scaled derivatives. The benchmark sets include reaction energies, barrier heights, and dissociation energies of prototype bond-activation reactions, dissociation energies for a set of large transition-metal complexes, bond lengths and dissociation energies of metal hydride ions, and bond lengths and angles of a set of closed-shell first-row transition-metal complexes. The emphasis is on first-row transition-metal chemistry, though for energies, elements beyond the first-row are included. Attention is paid to the basis set convergence of RPA. For thermochemistry, RPA performs on par or better than the density functional theory (DFT) functionals presented and is significantly more accurate than MP2. The largest errors are observed in dissociation energies where the electronic environment is altered substantially. For structural parameters, very good results were obtained, and RPA meets the high quality of structures from DFT. In most cases, well-converged structures are obtained with basis sets of triple-zeta quality. MP2 optimized values can often not be obtained and are on average of inferior quality. Though chemical accuracy is not reached, the RPA method is a step forward toward a systematic, parameter-free, all-round method to describe transition-metal chemistry.

  7. Distinct Metal Isoforms Underlie Promiscuous Activity Profiles of Metalloenzymes.

    PubMed

    Baier, Florian; Chen, John; Solomonson, Matthew; Strynadka, Natalie C J; Tokuriki, Nobuhiko

    2015-07-17

    Within a superfamily, functionally diverged metalloenzymes often favor different metals as cofactors for catalysis. One hypothesis is that incorporation of alternative metals expands the catalytic repertoire of metalloenzymes and provides evolutionary springboards toward new catalytic functions. However, there is little experimental evidence that incorporation of alternative metals changes the activity profile of metalloenzymes. Here, we systematically investigate how metals alter the activity profiles of five functionally diverged enzymes of the metallo-β-lactamase (MBL) superfamily. Each enzyme was reconstituted in vitro with six different metals, Cd(2+), Co(2+), Fe(2+), Mn(2+), Ni(2+), and Zn(2+), and assayed against eight catalytically distinct hydrolytic reactions (representing native functions of MBL enzymes). We reveal that each enzyme metal isoform has a significantly different activity level for native and promiscuous reactions. Moreover, metal preferences for native versus promiscuous activities are not correlated and, in some cases, are mutually exclusive; only particular metal isoforms disclose cryptic promiscuous activities but often at the expense of the native activity. For example, the L1 B3 β-lactamase displays a 1000-fold catalytic preference for Zn(2+) over Ni(2+) for its native activity but exhibits promiscuous thioester, phosphodiester, phosphotriester, and lactonase activity only with Ni(2+). Furthermore, we find that the five MBL enzymes exist as an ensemble of various metal isoforms in vivo, and this heterogeneity results in an expanded activity profile compared to a single metal isoform. Our study suggests that promiscuous activities of metalloenzymes can stem from an ensemble of metal isoforms in the cell, which could facilitate the functional divergence of metalloenzymes.

  8. Pharmacological activity of metal binding agents that alter copper bioavailability

    PubMed Central

    Helsel, Marian E.

    2015-01-01

    Iron, copper and zinc are required nutrients for many organisms but also potent toxins if misappropriated. An overload of any of these metals can be cytotoxic and ultimately lead to organ failure, whereas deficiencies can result in anemia, weakened immune system function, and other medical conditions. Cellular metal imbalances have been implicated in neurodegenerative diseases, cancer and infection. It is therefore critical for living organisms to maintain careful control of both the total levels and subcellular distributions of these metals to maintain healthy function. This perspective explores several strategies envisioned to alter the bioavailability of metal ions by using synthetic metal-binding agents targeted for diseases where misappropriated metal ions are suspected of exacerbating cellular damage. Specifically, we discuss chemical properties that influence the pharmacological outcome of a subset of metal-binding agents known as ionophores, and review several examples that have shown multiple pharmacological activities in metal-related diseases, with a specific focus on copper. PMID:25797044

  9. The gas-phase metallicity of central and satellite galaxies in the Sloan Digital Sky Survey

    NASA Astrophysics Data System (ADS)

    Pasquali, Anna; Gallazzi, Anna; van den Bosch, Frank C.

    2012-09-01

    We exploit the galaxy groups catalogue of Yang et al. and the galaxy properties measured in the Sloan Digital Sky Survey Data Releases 4 and 7 to study how the gas-phase metallicities of star-forming galaxies depend on environment. We find that satellite and central galaxies follow a qualitatively similar stellar mass (M★)-gas-phase metallicity relation, whereby their gas-phase metallicity increases with M★. Satellites, though, have higher gas-phase metallicities than equally massive centrals, and this difference increases with decreasing stellar mass. We find a maximum offset of 0.06 dex at log(M★/h-2 M⊙) ≃ 8.25. At fixed halo mass, centrals are more metal rich than satellites by ˜0.5 dex on average. This is simply due to the fact that, by definition, centrals are the most massive galaxies in their groups, and the fact that gas-phase metallicity increases with stellar mass. More interestingly, we also find that the gas-phase metallicity of satellites increases with halo mass (Mh) at fixed stellar mass. This increment is more pronounced for less massive galaxies, and, at M★ ≃ 109 h-2 M⊙, corresponds to ˜0.15 dex across the range 11 < log (Mh/h-1 M⊙) < 14. We also show that low-mass satellite galaxies have higher gas-phase metallicities than central galaxies of the same stellar metallicity. This difference becomes negligible for more massive galaxies of roughly solar metallicity. We demonstrate that the observed differences in gas-phase metallicity between centrals and satellites at fixed M★ are not a consequence of stellar mass stripping (advocated by Pasquali et al. in order to explain similar differences but in stellar metallicity), nor to the past star formation history of these galaxies as quantified by their surface mass density or gas mass fraction. Rather, we argue that these trends probably originate from a combination of three environmental effects: (i) strangulation, which prevents satellite galaxies from accreting new, low-metallicity

  10. Onset conditions for gas phase reaction and nucleation in the CVD of transition metal oxides

    NASA Technical Reports Server (NTRS)

    Collins, J.; Rosner, D. E.; Castillo, J.

    1992-01-01

    A combined experimental/theoretical study is presented of the onset conditions for gas phase reaction and particle nucleation in hot substrate/cold gas CVD of transition metal oxides. Homogeneous reaction onset conditions are predicted using a simple high activation energy reacting gas film theory. Experimental tests of the basic theory are underway using an axisymmetric impinging jet CVD reactor. No vapor phase ignition has yet been observed in the TiCl4/O2 system under accessible operating conditions (below substrate temperature Tw = 1700 K). The goal of this research is to provide CVD reactor design and operation guidelines for achieving acceptable deposit microstructures at the maximum deposition rate while simultaneously avoiding homogeneous reaction/nucleation and diffusional limitations.

  11. Gas-phase catalysis by atomic and cluster metal ions: the ultimate single-site catalysts.

    PubMed

    Böhme, Diethard K; Schwarz, Helmut

    2005-04-15

    Gas-phase experiments with state-of-the-art techniques of mass spectrometry provide detailed insights into numerous elementary processes. The focus of this Review is on elementary reactions of ions that achieve complete catalytic cycles under thermal conditions. The examples chosen cover aspects of catalysis pertinent to areas as diverse as atmospheric chemistry and surface chemistry. We describe how transfer of oxygen atoms, bond activation, and coupling of fragments can be mediated by atomic or cluster metal ions. In some cases truly unexpected analogies of the idealized gas-phase ion catalysis can be drawn with related chemical transformations in solution or the solid state, and so improve our understanding of the intrinsic operation of a practical catalyst at a strictly molecular level.

  12. A micromachined thermo-optical light modulator based on semiconductor-to-metal phase transition

    NASA Astrophysics Data System (ADS)

    Jiang, Lijun

    In this research, a micromachined thermo-optical light modulator was realized based on the semiconductor-to-metal phase transition of vanadium dioxide (VO2) thin film. VO2 undergoes a reversible phase transition at approximately 68°C, which is accompanied with drastic changes in its electrical and optical properties. The sharp electrical resistivity change can be as great as five orders. Optically, VO2 film will switch from a transparent semiconductor phase to a reflective metal phase upon the phase transition. The light modulator in this research exploits this phase transition related optical switching by using surface micromachined low-thermal-mass pixels to achieve good thermal isolations, which ensures that each pixel can be individually switched without cross talking. In operation, the pixel temperature was controlled by integrated resistor on each pixel or spatially addressed thermal radiation sources. Active VO2 thin film was synthesized by thermal oxidation of e-beam evaporated vanadium metal film. The oxidized film exhibits a phase transition at ˜65°C with a hysteresis of about 15°C. A transmittance switching from ˜90% to ˜30% in the near infrared and a reflectance switching from ˜50% to ˜15% in the visible have been achieved. The surface microstructure was studied and correlated to its optical properties. A study on the hysteresis loop reveals that the VO2 can be repetitively switched between the "on" and "off" states. The micromachined thermal isolation pixel was a bridge-like silicon dioxide platform suspended with narrow supporting legs. The pixel design was optimized with both thermal and optical simulations. The VO2 light modulator was fabricated by surface micromachining based on dry processing. Silicon dioxide was deposited on a polyimide sacrificial layer by PECVD and patterned to form the structural pixel. Vanadium film was e-beam evaporated and patterned with lift-off process. It was thermally oxidized into VO2 at 390°C. The thermal

  13. Characterization and activity of cephalosporin metal complexes.

    PubMed

    Auda, S H; Mrestani, Y; Fetouh, M I; Neubert, R H H

    2008-08-01

    Semi-synthetic cephalosporin antibiotics have structures similar to that of penicillins, and both groups of compounds are characterized by similar properties and determined by the same methods. Most antibiotics, including cephalosporins and their decomposition products, contain electron donor groups that can bind naturally occurring metal ions in vivo. Cephalosporin antibiotics exhibit a change in their toxicological properties and biological performance when they were tested as metal complexes. The proposed reason for such a behavior is the capability of chelate binding of the cephalosporins to the metals. In an attempt to understand the coordination mode of metals with cephalosporins, different spectroscopic techniques such as IR, UV-visible, NMR spectroscopy and voltammetric measurements were carried out to elucidate the structure of the metal-cephalosporin complexes. Synthesis, characterization and biological screening of the cephalosporins and of the cephalosporin-metal complexes are discussed in this review. However, little information is available on the influence of the metal ions on the pharmacokinetics of the cephalosporin derivatives.

  14. Electronically Active Cyclocarborane-Metal-Arene Assemblies

    DTIC Science & Technology

    1992-07-31

    Boron," Organometallics, 1990, 9, 1177. J. H. Davis, Jr., M. A. Benvenuto , and R. N. Grimes, "Organotransition-Metal Metalla- carboranes. 18. rY6, nl...3061. M. A. Benvenuto and R. N. Grimes, "Organotransition-Metal Metallacarboranes. 20. Bu 4N*F Fluoride-Catalyzed C-Si Bond Cleavage in Cp*Co(MeSi...Organometallic Synthesis", Chem. Rev. 1992, 92 251. M. A. Benvenuto and R. N. Grimes, "Organotransition-Metal Metallacarboranes. 28. Controlled Substitution at

  15. Dynamic phase coexistence and non-Gaussian resistance fluctuations in VO2 near the metal-insulator transition

    NASA Astrophysics Data System (ADS)

    Samanta, Sudeshna; Raychaudhuri, A. K.; Zhong, Xing; Gupta, A.

    2015-11-01

    We have carried out an extensive investigation on the resistance fluctuations (noise) in an epitaxial thin film of VO2 encompassing the metal-insulator transition (MIT) region to investigate the dynamic phase coexistence of metal and insulating phases. Both flicker noise as well as the Nyquist noise (thermal noise) were measured. The experiments showed that flicker noise, which has a 1 /f spectral power dependence, evolves with temperature in the transition region following the evolution of the phase fractions and is governed by activated kinetics. Importantly, closer to the insulating end of the transition, when the metallic phase fraction is low, the magnitude of the noise shows an anomaly and a strong non-Gaussian component of noise develops. In this region, the local electron temperature (as measured through the Nyquist noise thermometry) shows a deviation from the equilibrium bath temperature. It is proposed that this behavior arises due to current crowding where a substantial amount of the current is carried through well separated small metallic islands leading to a dynamic correlated current path redistribution and an enhanced effective local current density. This leads to a non-Gaussian component to the resistance fluctuation and an associated local deviation of the electron temperature from the bath. Our experiment establishes that phase coexistence leads to a strong inhomogeneity in the region of MIT that makes the current transport strongly inhomogeneous and correlated.

  16. MMIC devices for active phased array antennas

    NASA Technical Reports Server (NTRS)

    Mittra, R.

    1984-01-01

    The study of printed circuit discontinuities is necessary in order to design, for example, transitions between rectangular waveguides and printed circuits. New developments with respect to the analytical approaches to this problem are discussed. A summary of the progress in the experimental approach is presented. The accurate solution for the modes in various millimeter-wave waveguides is essential in the analysis of many integrated circuit components, such as filters and impedance transformers. Problems associated with the numerical computation of these modes in two frequently used waveguide forms, namely, the finline and microstrip, are presented. The spectral domain method of formulation, with a moment method solution, is considered. This approach can be readily extended to analyze an arbitrary configuration of dielectric and metallized regions in a shielded enclosure. Galerkin's method is used, where the testing and basic functions are the same. It is shown that the mode functions, or eigenfunctions, are more sensitive to errors than the phase constants, or eigenvalues. The approximate mode functions do not satisfy the orthogonality relationship well, resulting in difficulties when these modal solutions are used to form an approximate Green's function or are used in a mode matching analysis.

  17. Solid-Phase Equilibria for Metal-Silicon-Oxygen Ternary Systems. II. Sc, Y, and La

    DTIC Science & Technology

    1991-02-28

    Organization: Regents of the University of California TECHNICAL REPORT No. 9 SOLID- PHASE EQUILIBRIA FOR METAL-SILICON-OXYGEN TERNARY SYSTEMS: 11: Sc, Y, AND La...34’ SOLID- PHASE EQUILIBRIA FOR METAL-SILICON-OXYGEN TERNARY SYSTEMS: 11: Sc, Y, AND 1a 13 0911OtiA AUTHORCS) Haojie Yuan and R. Stanley Williams lI" TV...0660te tCLhSSWI=) Solid phase equilibria for metal-silicon-oxygen ternary systems I1: Sc, Y and La Haojie Yuan and R. Stanley Williams Department of

  18. The superconductor-metal quantum phase transition in ultra-narrow wires

    NASA Astrophysics Data System (ADS)

    Del Maestro, Adrian Giuseppe

    We present a complete description of a zero temperature phase transition between superconducting and diffusive metallic states in very thin wires due to a Cooper pair breaking mechanism originating from a number of possible sources. These include impurities localized to the surface of the wire, a magnetic field orientated parallel to the wire or, disorder in an unconventional superconductor. The order parameter describing pairing is strongly overdamped by its coupling to an effectively infinite bath of unpaired electrons imagined to reside in the transverse conduction channels of the wire. The dissipative critical theory thus contains current reducing fluctuations in the guise of both quantum and thermally activated phase slips. A full cross-over phase diagram is computed via an expansion in the inverse number of complex components of the superconducting order parameter (equal to one in the physical case). The fluctuation corrections to the electrical and thermal conductivities are determined, and we find that the zero frequency electrical transport has a non-monotonic temperature dependence when moving from the quantum critical to low temperature metallic phase, which may be consistent with recent experimental results on ultra-narrow MoGe wires. Near criticality, the ratio of the thermal to electrical conductivity displays a linear temperature dependence and thus the Wiedemann-Franz law is obeyed. We compute the constant of proportionality in a systematic expansion and find a universal and experimentally verifiable fluctuation correction to the Lorenz number. In the presence of quenched disorder, a novel algorithm is developed to solve the self-consistency condition arising when the number of complex order parameter components is taken to be large. In this limit, we find striking evidence for the flow to infinite randomness, and observe dynamically activated scaling consistent with predictions from the strong disorder renormalization group. Moreover, the infinite

  19. Solution-phase synthesis of metal and/or semiconductor homojunction/heterojunction nanomaterials.

    PubMed

    Feng, Xiumei; Hu, Guanqi; Hu, Jianqiang

    2011-05-01

    The design and architecture of programmable metal-semiconductor nanostructures with excellent optoelectronic properties from metal and semiconductor building blocks with nanoscale dimensions have been a key aim of material scientists due to their central roles in the fabrication of electronic, optical, and optoelectronic nanodevices. This review focuses on the latest advances in the solution-phase synthesis of metal and/or semiconductor homojunction/heterojunction nanomaterials. It begins with the simplest construction of metal/metal and semiconductor/semiconductor homojunctions, and then highlights the synthetic design of metal/metal and semiconductor/semiconductor heterojunction nanostructures with different building blocks. Special emphasis is placed on metal/semiconductor heterojunction nanomaterials, which are the most challenging and promising nanomaterials for future applications in optoelectronic nanodevices. Finally, this review concludes with personal perspectives on the directions for future research in this field.

  20. [Biological activity of selenorganic compounds at heavy metal salts intoxication].

    PubMed

    Rusetskaya, N Y; Borodulin, V B

    2015-01-01

    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.

  1. Metal-VO2 hybrid grating structure for a terahertz active switchable linear polarizer.

    PubMed

    Shin, Jun-Hwan; Moon, Kiwon; Lee, Eui Su; Lee, Il-Min; Park, Kyung Hyun

    2015-08-07

    An active terahertz (THz) wave hybrid grating structure of Au/Ti metallic grating on VO2/Al2O3 (0001) was fabricated and evaluated. In our structure, it is shown that the metallic gratings on the VO2 layer strengthen the metallic characteristics to enhance the contrast of the metallic and dielectric phases of a VO2-based device. Especially, the metal grating-induced optical conductivity of the device is greatly enhanced, three times more than that of a metallic phase of bare VO2 films in the 0.1-2.0 THz spectral range. As an illustrative example, we fabricated an actively on/off switchable THz linear polarizer. The fabricated device has shown commercially comparable values in degree of polarization (DOP) and extinction ratio (ER). A high value of 0.89 in the modulation depth (MD) for the transmission field amplitude, superior to other THz wave modulators, is achieved. The experimental results show that the fabricated device can be highly useful in many applications, including active THz linear polarizers, THz wave modulators and variable THz attenuators.

  2. Real-time active MR-tracking of metallic stylets in MR-guided radiation therapy

    PubMed Central

    Wang, Wei; Dumoulin, Charles L.; Viswanathan, Akila N.; Tse, Zion T. H.; Mehrtash, Alireza; Loew, Wolfgang; Norton, Isaiah; Tokuda, Junichi; Seethamraju, Ravi T.; Kapur, Tina; Damato, Antonio L.; Cormack, Robert A.; Schmidt, Ehud J.

    2014-01-01

    Purpose To develop an active MR-tracking system to guide placement of metallic devices for radiation therapy. Methods An actively tracked metallic stylet for brachytherapy was constructed by adding printed-circuit micro-coils to a commercial stylet. The coil design was optimized by electromagnetic simulation, and has a radio-frequency lobe pattern extending ~5 mm beyond the strong B0 inhomogeneity region near the metal surface. An MR-tracking sequence with phase-field dithering was used to overcome residual effects of B0 and B1 inhomogeneities caused by the metal, as well as from inductive coupling to surrounding metallic stylets. The tracking system was integrated with a graphical workstation for real-time visualization. 3T MRI catheter-insertion procedures were tested in phantoms and ex-vivo animal tissue, and then performed in three patients during interstitial brachytherapy. Results The tracking system provided high-resolution (0.6 × 0.6 × 0.6 mm3) and rapid (16 to 40 frames per second, with three to one phase-field dithering directions) catheter localization in phantoms, animals, and three gynecologic cancer patients. Conclusion This is the first demonstration of active tracking of the shaft of metallic stylet in MR-guided brachytherapy. It holds the promise of assisting physicians to achieve better targeting and improving outcomes in interstitial brachytherapy. PMID:24903165

  3. Pure and stable metallic phase molybdenum disulfide nanosheets for hydrogen evolution reaction.

    PubMed

    Geng, Xiumei; Sun, Weiwei; Wu, Wei; Chen, Benjamin; Al-Hilo, Alaa; Benamara, Mourad; Zhu, Hongli; Watanabe, Fumiya; Cui, Jingbiao; Chen, Tar-Pin

    2016-02-10

    Metallic-phase MoS2 (M-MoS2) is metastable and does not exist in nature. Pure and stable M-MoS2 has not been previously prepared by chemical synthesis, to the best of our knowledge. Here we report a hydrothermal process for synthesizing stable two-dimensional M-MoS2 nanosheets in water. The metal-metal Raman stretching mode at 146 cm(-1) in the M-MoS2 structure, as predicted by theoretical calculations, is experimentally observed. The stability of the M-MoS2 is associated with the adsorption of a monolayer of water molecules on both sides of the nanosheets, which reduce restacking and prevent aggregation in water. The obtained M-MoS2 exhibits excellent stability in water and superior activity for the hydrogen evolution reaction, with a current density of 10 mA cm(-2) at a low potential of -175 mV and a Tafel slope of 41 mV per decade.

  4. Pure and stable metallic phase molybdenum disulfide nanosheets for hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Geng, Xiumei; Sun, Weiwei; Wu, Wei; Chen, Benjamin; Al-Hilo, Alaa; Benamara, Mourad; Zhu, Hongli; Watanabe, Fumiya; Cui, Jingbiao; Chen, Tar-Pin

    2016-02-01

    Metallic-phase MoS2 (M-MoS2) is metastable and does not exist in nature. Pure and stable M-MoS2 has not been previously prepared by chemical synthesis, to the best of our knowledge. Here we report a hydrothermal process for synthesizing stable two-dimensional M-MoS2 nanosheets in water. The metal-metal Raman stretching mode at 146 cm-1 in the M-MoS2 structure, as predicted by theoretical calculations, is experimentally observed. The stability of the M-MoS2 is associated with the adsorption of a monolayer of water molecules on both sides of the nanosheets, which reduce restacking and prevent aggregation in water. The obtained M-MoS2 exhibits excellent stability in water and superior activity for the hydrogen evolution reaction, with a current density of 10 mA cm-2 at a low potential of -175 mV and a Tafel slope of 41 mV per decade.

  5. Chiral phase transition in lattice QCD as a metal-insulator transition

    SciTech Connect

    Garcia-Garcia, Antonio M.; Osborn, James C.

    2007-02-01

    We investigate the lattice QCD Dirac operator with staggered fermions at temperatures around the chiral phase transition. We present evidence of a metal-insulator transition in the low lying modes of the Dirac operator around the same temperature as the chiral phase transition. This strongly suggests the phenomenon of Anderson localization drives the QCD vacuum to the chirally symmetric phase in a way similar to a metal-insulator transition in a disordered conductor. We also discuss how Anderson localization affects the usual phenomenological treatment of phase transitions a la Ginzburg-Landau.

  6. Electronically Active Cyclocarborane-Metal-Arene Assemblies

    DTIC Science & Technology

    1992-07-31

    Benvenuto , and R. N. Grimes, "Organotransition-Metal Metalla- carboranes. 18. Y16, _q5-Benzyltetramethylcyclopentadieneide(1-) as a Bridging Ligand in...Polyhedral Expansion of (Arene)Fe(Et 2CB 4 H4) Clusters", J. Am. Chem. Soc., 1991, 113 3061. M. A. Benvenuto and R. N. Grimes, "Organotransition-Metal...34, Organometallics 1992, 11, 2404. R. N. Grimes, "Boron-Carbon Ring Ligands in Organometallic Synthesis", Chem. Rev. 1992, 92. 251. M. A. Benvenuto and R

  7. Fragility, Intermediate Phase and Polaronic conductivity in heavy metal oxides

    NASA Astrophysics Data System (ADS)

    Chakraborty, Shibalik; Gunasekera, Kapila; Boolchand, Punit; Malki, Mohammed; Micoulaut, Matthieu

    2013-03-01

    The (B2O3)5 (TeO2)95-x (V2O5)x ternary forms bulk glasses over a wide range of compositions, 18% < x < 35%. Complex Cp(x) measurements as a function of modulation frequency reveal that melt fragility (m) show a global minimum (m = 52(2)) in the 23% < x < 26% range with m > 65 outside that window. These results suggest more stable network structure in the window than outside it. The fragility window coincides with a global minimum of the non-reversing enthalpy of relaxation at Tg, the reversibility window (23% < x < 27%), a behavior also found in chalcogenide glasses. Conductivity (σ) data show three regimes of variation; a low σ at x < 23%, a plateau in 23% < x < 27%, and an exponential increase at x > 27%. The reduced activation energy for conductivity at x > 27% is consistent with increased polaronic mobility as the network becomes flexible. These findings show glasses at x < 23% are stressed-rigid, in 23% < x < 27% range in the Intermediate Phase, and at x > 27% to be flexible. Supported by NSF grant DMR 08-53957.

  8. Infrared Spectroscopy of Transition Metal-Molecular interactions in the Gas Phase

    SciTech Connect

    Duncan, Michael A.

    2008-11-14

    Transition metal-molecular complexes produced in a molecular beam are mass-selected and studied with infrared laser photodissociation spectroscopy. Metal complexes with carbon monoxide, carbon dioxide, nitrogen, water, acetylene or benzene are studied for a variety of metals. The number and intensity of infrared active bands are compared to the predictions of density functional theory calculations to derive structures, spin states and coordination numbers in these systems. These studied provide new insights into subtle details of metal-molecular interactions important in heterogeneous catalysis, metal-ligand bonding and metal ion solvation.

  9. Modified GRAY: An Improved Three-Phase Equation of State for Metals

    DTIC Science & Technology

    1976-04-01

    An improved version of the GRAY three-phase equation of state for metals is presented in this report. The Grover model for liquid metals is modified...representation is incorporated into the modified van der Waals equation of state for the vapor region yielding a model which is physically realistic at

  10. Mineral phases and metals in baghouse dust from secondary aluminum production

    EPA Science Inventory

    Baghouse dust (BHD) is a solid waste generated by air pollution control systems during secondary aluminum processing (SAP). Management and disposal of BHD can be challenging in the U.S. and elsewhere. In this study, the mineral phases, metal content and metal leachability of 78...

  11. PHASE ANALYSIS AND CRYSTAL STRUCTURE STUDIES ON BINARY ALLOYS OF ALUMINUM WITH TRANSITION METALS.

    DTIC Science & Technology

    In order to provide the necessary background for detailed crystal-chemistry studies in the field of binary aluminum - transition metal systems, extensive investigations have been carried out on the phase relations of a large number of such systems. The results of these studies are briefly summarized, as are also the results of crystal structure determinations of a few alumi num - transition metal phases. (Author)

  12. Metal interactions with voltage- and receptor-activated ion channels.

    PubMed Central

    Vijverberg, H P; Oortgiesen, M; Leinders, T; van Kleef, R G

    1994-01-01

    Effects of Pb and several other metal ions on various distinct types of voltage-, receptor- and Ca-activated ion channels have been investigated in cultured N1E-115 mouse neuroblastoma cells. Experiments were performed using the whole-cell voltage clamp and single-channel patch clamp techniques. External superfusion of nanomolar to submillimolar concentrations of Pb causes multiple effects on ion channels. Barium current through voltage-activated Ca channels is blocked by micromolar concentrations of Pb, whereas voltage-activated Na current appears insensitive. Neuronal type nicotinic acetylcholine receptor-activated ion current is blocked by nanomolar concentrations of Pb and this block is reversed at micromolar concentrations. Serotonin 5-HT3 receptor-activated ion current is much less sensitive to Pb. In addition, external superfusion with micromolar concentrations of Pb as well as of Cd and aluminum induces inward current, associated with the direct activation of nonselective cation channels by these metal ions. In excised inside-out membrane patches of neuroblastoma cells, micromolar concentrations of Ca activate small (SK) and big (BK) Ca-activated K channels. Internally applied Pb activates SK and BK channels more potently than Ca, whereas Cd is approximately equipotent to Pb with respect to SK channel activation, but fails to activate BK channels. The results show that metal ions cause distinct, selective effects on the various types of ion channels and that metal ion interaction sites of ion channels may be highly selective for particular metal ions. PMID:7531139

  13. Crystal phase competition by addition of a second metal cation in solid solution metal-organic frameworks.

    PubMed

    Castillo-Blas, C; Snejko, N; de la Peña-O'Shea, V A; Gallardo, J; Gutiérrez-Puebla, E; Monge, M A; Gándara, F

    2016-03-14

    Herein we report a synthetic study focused on the preparation of solid-solution metal-organic frameworks, MOFs, with the use of two kinds of linkers. In particular, we have explored the system composed by zinc, cobalt, 1,2,4-triazole and 4,4′-hexafluoroisopropylidenebisbenzoic acid (H2hfipbb). During this study, four new MOFs have been isolated, denoted TMPF-88 [M3(hfipbb)2(triazole)2(H2O)], TMPF-90 [M2(triazole)3(OCH2CH3)], TMPF-91 [M2(hfipbb)(triazole)2(H2O)] and TMPF-95 [M5(hfipbb)4(triazole)2(H2O)] (TMPF = transition metal polymeric framework, M = Zn, Co, or mixture of them). The study demonstrates that the addition of a second metal element during the MOF synthesis has a major effect in the formation of new phases, even at very high Zn/Co metal ratios. Furthermore, we show that during the MOF formation reaction, there is a competition among different crystal phases, where kinetically favoured phases of various compositions crystallize in short reaction times, precluding the formation of the pure solid-solution phases of other energetically more stable MOFs.

  14. Activation of carbon dioxide on metal and metal oxide surfaces

    SciTech Connect

    Tan, C.D.; Chuang, S.S.C.

    1995-12-31

    The environmental concern about the impact of CO{sub 2} has grown recently due to its rapidly increasing concentration. Deforestation strongly affects the natural reduction of CO{sub 2} by water into carbohydrates by photosynthesis. Industrial utilization of CO{sub 2} by heterogeneous catalytic reactions can be one of the effective ways to cut the CO{sub 2} level. The first step in catalytic reaction of CO{sub 2} is the adsorption. The objective of this study is to investigate the adsorption of CO{sub 2} on the Rh/Al{sub 2}O{sub 3} surfaces. Rh is selected for this study because of its unique activity to catalyze a number of CO{sub 2} related reactions. In situ infrared results show that CO{sub 2} adsorbed on the alumina oxide support as bidentate carbonate and non-coordinated carbon which are the dominant species during the CO{sub 2} adsorption.

  15. Vapor-phase catalytic oxidesulfurization (ODS) of organosulfur compounds over supported metal oxide catalysts

    NASA Astrophysics Data System (ADS)

    Choi, Sukwon

    Sulfur in transportation fuels remains a leading source of SOx emissions from vehicle engines and is a major source of air pollution. The very low levels of sulfur globally mandated for transportation fuels in the near future cannot be achieved by current practices of hydrodesulfurization (HDS) for sulfur removal, which operate under severe conditions (high T, P) and use valuable H2. Novel vapor-phase catalytic oxidesulfurization (ODS) processes of selectively oxidizing various organosulfur compounds (carbonyl sulfide, carbon disulfide, methanethiol, dimethyl sulfide (DMS), dimethyl disulfide (DMDS), thiophene, 2,5-dimenthylthiophene) typically found in various industrial streams (e.g., petroleum refining, pulp and paper) into valuable chemical intermediates (H 2CO, CO, H2, maleic anhydride and concentrated SO2) has been extensively studied. This research has primarily focused on establishing the fundamental kinetics and mechanisms of these selective oxidation reactions over well-defined supported metal oxide catalysts. The selective oxidation reactions of COS + O2 → CO + SO2; 2CS2 + 5O2 → 2CO + 4SO2; CH3SH + 2O 2 → H2CO + SO2 + H2O; C4 H4S + 3O2 → C4H2O 3 + H2O + SO2; were studied. Raman spectroscopy revealed that the supported metal oxide phases were 100% dispersed on the oxide substrate. All the catalysts were highly active and selective for the oxidesulfurization of carbonyl sulfide, carbon disulfide, methanethiol, and thiophene between 290--330°C, 230--270°C, 350--400°C, and 250--400°C, respectively and did not deactivate. The TOFs (turnover frequency, normalized activity per active catalytic site) for all ODS reactions over supported vanadia catalysts, only containing molecularly dispersed surface vanadia species, varied within one order of magnitude and revealed the V-O-Support bridging bond was involved in the critical rate-determining kinetic steps. The surface reaction mechanism for each reaction was revealed by in situ IR (infrared) and

  16. Evidence for Photoinduced Insulator-to-Metal transition in B-phase vanadium dioxide

    PubMed Central

    Lourembam, James; Srivastava, Amar; La-o-vorakiat, Chan; Cheng, Liang; Venkatesan, T.; Chia, Elbert E. M.

    2016-01-01

    Ultrafast optical studies have been performed on epitaxial films of the novel B-phase of vanadium dioxide using temperature-dependent optical pump-probe technique. Signature of temperature-driven metal-to-insulator transition was distinctly observed in the ultrafast dynamics — the insulating phase showed two characteristic electronic relaxation times while the metallic phase showed only one. Beyond a threshold value of the pump fluence, the insulating state collapses into a ‘metallic-like’ phase which can be further subdivided into two regimes according to the lengths of the fast characteristic time. The first regime can be explained by lattice heating due to the optical pump; the other cannot be accounted by simple lattice heating effects alone, and thus offers evidence for a true photoinduced phase transition. PMID:27157532

  17. Transition metal interaction and Ni-Fe-Cu-Si phases in silicon

    NASA Astrophysics Data System (ADS)

    Heuer, M.; Buonassisi, T.; Istratov, A. A.; Pickett, M. D.; Marcus, M. A.; Minor, A. M.; Weber, E. R.

    2007-06-01

    In the present article we characterize several intermetallic phases of the Cu-Ni-Fe-Si system found as precipitates in the misfit dislocation layer of intentionally contaminated and slowly cooled Si1-xGex/Si-heterostructures. The clusters showed a characteristic phase speciation into a Cu-rich part similar to Cu3Si and an Fe-Ni-Cu-Si phase similar to NiSi2. It is suggested that the precipitate formation of the investigated intermetallic silicides involves a homogeneous precursor phase at higher temperatures that later decomposes into the observed phases. Our results indicate that chemical reactions between metals and silicon during precipitation may reduce the lattice mismatch compared to single-metal precipitates, rendering mixed-metal-silicide precipitates more stable and energetically favorable.

  18. Phase stability of transition metal dichalcogenide by competing ligand field stabilization and charge density wave

    NASA Astrophysics Data System (ADS)

    C, Santosh K.; Zhang, Chenxi; Hong, Suklyun; Wallace, Robert M.; Cho, Kyeongjae

    2015-09-01

    Transition metal dichalcogenides (TMDs) have been investigated extensively for potential application as device materials in recent years. TMDs are found to be stable in trigonal prismatic (H), octahedral (T), or distorted octahedral (Td) coordination of the transition metal. However, the detailed understanding of stabilities of TMDs in a particular phase is lacking. In this work, the detailed TMD phase stability using first-principles calculations based on density functional theory (DFT) has been investigated to clarify the mechanism of phase stabilities of TMDs, consistent with the experimental observation. Our results indicate that the phase stability of TMDs can be explained considering the relative strength of two competing mechanisms: ligand field stabilization of d-orbitals corresponding to transition metal coordination geometry, and charge density wave (CDW) instability accompanied by a periodic lattice distortion (PLD) causing the phase transition in particular TMDs.

  19. How absorbed hydrogen affects the catalytic activity of transition metals.

    PubMed

    Aleksandrov, Hristiyan A; Kozlov, Sergey M; Schauermann, Swetlana; Vayssilov, Georgi N; Neyman, Konstantin M

    2014-12-01

    Heterogeneous catalysis is commonly governed by surface active sites. Yet, areas just below the surface can also influence catalytic activity, for instance, when fragmentation products of catalytic feeds penetrate into catalysts. In particular, H absorbed below the surface is required for certain hydrogenation reactions on metals. Herein, we show that a sufficient concentration of subsurface hydrogen, H(sub) , may either significantly increase or decrease the bond energy and the reactivity of the adsorbed hydrogen, H(ad) , depending on the metal. We predict a representative reaction, ethyl hydrogenation, to speed up on Pd and Pt, but to slow down on Ni and Rh in the presence of H(sub) , especially on metal nanoparticles. The identified effects of subsurface H on surface reactivity are indispensable for an atomistic understanding of hydrogenation processes on transition metals and interactions of hydrogen with metals in general.

  20. Elucidating the magnetic and superconducting phases in the alkali metal intercalated iron chalcogenides

    SciTech Connect

    Wang, Meng; Yi, Ming; Tian, Wei; Bourret-Courchesne, Edith; Birgeneau, Robert J.

    2016-02-29

    Here, the complex interdigitated phases have greatly frustrated attempts to document the basic features of the superconductivity in the alkali metal intercalated iron chalcogenides. Here, using elastic neutron scattering, energy-dispersive x-ray spectroscopy, and resistivity measurements, we elucidate the relations of these phases in RbxFeySe2-zSz. We find (i) the iron content is crucial in stabilizing the stripe antiferromagnetic (AF) phase with rhombic iron vacancy order (y ≈ 1.5), the block AF phase with root 5 x root 5 iron vacancy order (y ≈ 1.6), and the iron vacancy-free phase (y ≈ 2); and (ii) the iron vacancy-free superconducting phase (z = 0) evolves into an iron vacancy-free metallic phase with sulfur substitution (z > 1.5) due to the progressive decrease of the electronic correlation strength. Both the stripe AF phase and the block AF phase are Mott insulators. The iron-rich compounds (y > 1.6) undergo a first order transition from an iron vacancy disordered phase at high temperatures into the √5 x √5 iron vacancy ordered phase and the iron vacancy-free phase below Ts. Our data demonstrate that there are miscibility gaps between these three phases. The existence of the miscibility gaps in the iron content is a key to understanding the relationship between these complicated phases.

  1. Elucidating the magnetic and superconducting phases in the alkali metal intercalated iron chalcogenides

    DOE PAGES

    Wang, Meng; Yi, Ming; Tian, Wei; ...

    2016-02-29

    Here, the complex interdigitated phases have greatly frustrated attempts to document the basic features of the superconductivity in the alkali metal intercalated iron chalcogenides. Here, using elastic neutron scattering, energy-dispersive x-ray spectroscopy, and resistivity measurements, we elucidate the relations of these phases in RbxFeySe2-zSz. We find (i) the iron content is crucial in stabilizing the stripe antiferromagnetic (AF) phase with rhombic iron vacancy order (y ≈ 1.5), the block AF phase with root 5 x root 5 iron vacancy order (y ≈ 1.6), and the iron vacancy-free phase (y ≈ 2); and (ii) the iron vacancy-free superconducting phase (z =more » 0) evolves into an iron vacancy-free metallic phase with sulfur substitution (z > 1.5) due to the progressive decrease of the electronic correlation strength. Both the stripe AF phase and the block AF phase are Mott insulators. The iron-rich compounds (y > 1.6) undergo a first order transition from an iron vacancy disordered phase at high temperatures into the √5 x √5 iron vacancy ordered phase and the iron vacancy-free phase below Ts. Our data demonstrate that there are miscibility gaps between these three phases. The existence of the miscibility gaps in the iron content is a key to understanding the relationship between these complicated phases.« less

  2. Electron-phonon coupling and structural phase transitions in early transition metal oxides and chalcogenides

    NASA Astrophysics Data System (ADS)

    Farley, Katie Elizabeth

    Pronounced nonlinear variation of electrical transport characteristics as a function of applied voltage, temperature, magnetic field, strain, or photo-excitation is usually underpinned by electronic instabilities that originate from the complex interplay of spin, orbital, and lattice degrees of freedom. This dissertation focuses on two canonical materials that show pronounced discontinuities in their temperature-dependent resistivity as a result of electron---phonon and electron---electron correlations: orthorhombic TaS3 and monoclinic VO2. Strong electron-phonon interactions in transition metal oxides and chalcogenides results in interesting structural and electronic phase transitions. The properties of the material can be changed drastically in response to external stimuli such as temperature, voltage, or light. Understanding the influence these interactions have on the electronic structure and ultimately transport characteristics is of utmost importance in order to take these materials from a fundamental aspect to prospective applications such as low-energy interconnects, steep-slope transistors, and synaptic neural networks. This dissertation describes synthetic routes to nanoscale TaS3 and VO2, develops mechanistic understanding of their electronic instabilities, and in the case of the latter system explores modulation of the electronic and structural phase transition via the incorporation of substitutional dopant atoms. We start in chapter 2 with a detailed study of the synthesis and electronic transport properties of TaS3, which undergoes a Peierls' distortion to form a charge density wave. Scaling this material down to the nanometer-sized regime allows for interrogation of single or discrete phase coherent domains. Using electrical transport and broad band noise measurements, the dynamics of pinning/depinning of the charge density wave is investigated. Chapter 3 provides a novel synthetic approach to produce high-edge-density MoS2 nanorods. MoS2 is a

  3. Quantum phases of the Shastry-Sutherland Kondo lattice: implications for the global phase diagram of heavy-fermion metals.

    PubMed

    Pixley, J H; Yu, Rong; Si, Qimiao

    2014-10-24

    Considerable recent theoretical and experimental effort has been devoted to the study of quantum criticality and novel phases of antiferromagnetic heavy-fermion metals. In particular, quantum phase transitions have been discovered in heavy-fermion compounds with geometrical frustration. These developments have motivated us to study the competition between the Ruderman-Kittel-Kasuya-Yosida and Kondo interactions on the Shastry-Sutherland lattice. We determine the zero-temperature phase diagram as a function of magnetic frustration and Kondo coupling within a slave-fermion approach. Pertinent phases include the valence bond solid and heavy Fermi liquid. In the presence of antiferromagnetic order, our zero-temperature phase diagram is remarkably similar to the global phase diagram proposed earlier based on general grounds. We discuss the implications of our results for the experiments on Yb2Pt2Pb and related compounds.

  4. Structural instability and phase co-existence driven non-Gaussian resistance fluctuations in metal nanowires at low temperatures

    NASA Astrophysics Data System (ADS)

    Bid, Aveek; Raychaudhuri, A. K.

    2016-11-01

    We report a detailed experimental study of the resistance fluctuations measured at low temperatures in high quality metal nanowires ranging in diameter from 15-200 nm. The wires exhibit co-existing face-centered-cubic and 4H hcp phases of varying degrees as determined from the x-ray diffraction data. We observe the appearance of a large non-Gaussian noise for nanowires of diameter smaller than 50 nm over a certain temperature range around ≈30 K. The diameter range ˜30 nm, where the noise has maxima coincides with the maximum volume fraction of the co-existing 4H hcp phase thus establishing a strong link between the fluctuation and the phase co-existence. The resistance fluctuation in the same temperature range also shows a deviation of 1/f behavior at low frequency with appearance of single frequency Lorentzian type contribution in the spectral power density. The fluctuations are thermally activated with an activation energy {E}{{a}}˜ 35 meV, which is of same order as the activation energy of creation of stacking fault in FCC metals that leads to the co-existing crystallographic phases. Combining the results of crystallographic studies of the nanowires and analysis of the resistance fluctuations we could establish the correlation between the appearance of the large resistance noise and the onset of phase co-existence in these nanowires.

  5. Structural instability and phase co-existence driven non-Gaussian resistance fluctuations in metal nanowires at low temperatures.

    PubMed

    Bid, Aveek; Raychaudhuri, A K

    2016-11-11

    We report a detailed experimental study of the resistance fluctuations measured at low temperatures in high quality metal nanowires ranging in diameter from 15-200 nm. The wires exhibit co-existing face-centered-cubic and 4H hcp phases of varying degrees as determined from the x-ray diffraction data. We observe the appearance of a large non-Gaussian noise for nanowires of diameter smaller than 50 nm over a certain temperature range around ≈30 K. The diameter range ∼30 nm, where the noise has maxima coincides with the maximum volume fraction of the co-existing 4H hcp phase thus establishing a strong link between the fluctuation and the phase co-existence. The resistance fluctuation in the same temperature range also shows a deviation of [Formula: see text] behavior at low frequency with appearance of single frequency Lorentzian type contribution in the spectral power density. The fluctuations are thermally activated with an activation energy [Formula: see text] meV, which is of same order as the activation energy of creation of stacking fault in FCC metals that leads to the co-existing crystallographic phases. Combining the results of crystallographic studies of the nanowires and analysis of the resistance fluctuations we could establish the correlation between the appearance of the large resistance noise and the onset of phase co-existence in these nanowires.

  6. Active limited-angle tomographic phase microscope.

    PubMed

    Kus, Arkadiusz; Krauze, Wojciech; Kujawinska, Malgorzata

    2015-01-01

    We demonstrate an active, holographic tomography system, working with limited angle of projections, realized by optical-only, diffraction-based beam steering. The system created for this purpose is a Mach–Zehnder interferometer modified to serve as a digital holographic microscope with a high numerical aperture illumination module and a spatial light modulator (SLM). Such a solution is fast and robust. Apart from providing an elegant solution to viewing angle shifting, it also adds new capabilities of the holographic microscope system. SLM, being an active optical element, allows wavefront correction in order to improve measurement accuracy. Integrated phase data captured with different illumination scenarios within a highly limited angular range are processed by a new tomographic reconstruction algorithm based on the compressed sensing technique: total variation minimization, which is applied here to reconstruct nonpiecewise constant samples. Finally, the accuracy of full measurement and the proposed processing path is tested for a calibrated three-dimensional micro-object as well as a biological object--C2C12 myoblast cell.

  7. Active limited-angle tomographic phase microscope

    NASA Astrophysics Data System (ADS)

    Kuś, Arkadiusz; Krauze, Wojciech; Kujawińska, Małgorzata

    2015-11-01

    We demonstrate an active, holographic tomography system, working with limited angle of projections, realized by optical-only, diffraction-based beam steering. The system created for this purpose is a Mach-Zehnder interferometer modified to serve as a digital holographic microscope with a high numerical aperture illumination module and a spatial light modulator (SLM). Such a solution is fast and robust. Apart from providing an elegant solution to viewing angle shifting, it also adds new capabilities of the holographic microscope system. SLM, being an active optical element, allows wavefront correction in order to improve measurement accuracy. Integrated phase data captured with different illumination scenarios within a highly limited angular range are processed by a new tomographic reconstruction algorithm based on the compressed sensing technique: total variation minimization, which is applied here to reconstruct nonpiecewise constant samples. Finally, the accuracy of full measurement and the proposed processing path is tested for a calibrated three-dimensional micro-object as well as a biological object-C2C12 myoblast cell.

  8. Efficiency of metal activators of accelerated sulfur vulcanization

    SciTech Connect

    Duchacek, V.; Kuta, A.; Pribyl, P. )

    1993-01-20

    The effects of copper, mercury, nickel, zinc, cadmium, indium, magnesium, and calcium stearates on the course of N-cyclohexyl-2-benzthiazylsulphenamide-accelerated sulfur vulcanization of natural rubber have been investigated on the basis of curemeter measurements at 145 C. The differences in the efficiencies of these metal activators of accelerated sulfur vulcanization have been discussed from the points of view of the electron configurations of the metals and their affinities to sulfur. The authors attempted to determine why zinc oxide is generally accepted as the best metal vulcanization activator.

  9. Studies of high temperature ternary phases in mixed-metal-rich early transition metal sulfide and phosphide systems

    SciTech Connect

    Marking, G.A.

    1994-01-04

    Investigations of ternary mixed early transition metal-rich sulfide and phosphide systems resulted in the discovery of new structures and new phases. A new series of Zr and Hf - group V transition metal - sulfur K-phases was synthesized and crystallographically characterized. When the group V transition metal was Nb or Ta, the unit cell volume was larger than any previously reported K-phase. The presence of adventitious oxygen was determined in two K-phases through a combination of neutron scattering and X-ray diffraction experiments. A compound Hf{sub 10}Ta{sub 3}S{sub 3} was found to crystallize in a new-structure type similar to the known gamma brasses. This structure is unique in that it is the only reported {open_quotes}stuffed{close_quotes} gamma-brass type structure. The metal components, Hf and Ta, are larger in size and more electropositive than the metals found in normal gamma brasses (e.g. Cu and Zn) and because of the larger metallic radii, sulfur can be incorporated into the structure where it plays an integral role in stabilizing this phase relative to others. X-ray single-crystal, X-ray powder and neutron powder refinements were performed on this structure. A new structure was found in the ternary Nb-Zr-P system which has characteristics in common with many known early transition metal-rich sulfides, selenides, and phosphides. This structure has the simplest known interconnection of the basic building blocks known for this structural class. Anomalous scattering was a powerful tool for differentiating between Zr and Nb when using Mo K{alpha} X-radiation. The compounds ZrNbP and HfNbP formed in the space group Prima with the simple Co{sub 2}Si structure which is among the most common structures found for crystalline solid materials. Solid solution compounds in the Ta-Nb-P, Ta-Zr-P, Nb-Zr-P, Hf-Nb-P, and Hf-Zr-S systems were crystallographically characterized. The structural information corroborated ideas about bonding in metal-rich compounds.

  10. Model of High Temperature Phase Transitions in Metals

    NASA Astrophysics Data System (ADS)

    Filippov, E. S.

    2016-04-01

    On the basis of the assumption of the electron density fluctuation at the band degradation, a calculation parameter (the radius R) of the half-width of the probability distribution over the coordinate R is identified at the level of the maximum electron density fluctuation (at a maximum of the Gaussian function). Based on an analysis of the crystallization process and high polymorphic transformations bcc → fcc, the reasons for the formation of bcc, fcc, hexagonal, and tetragonal structures from the liquid phase, as well as for the high temperature bcc → hcp transition in the solid phase are established using the calculated parameter (the radius R) in the solid and liquid phases.

  11. Realization of multifunctional shape-memory ferromagnets in all-d-metal Heusler phases

    SciTech Connect

    Wei, Z. Y.; Liu, E. K. Chen, J. H.; Xi, X. K.; Zhang, H. W.; Wang, W. H.; Wu, G. H.; Li, Y.; Liu, G. D.; Luo, H. Z.

    2015-07-13

    Heusler ferromagnetic shape-memory alloys (FSMAs) normally consist of transition-group d-metals and main-group p-elements. Here, we report the realization of FSMAs in Heusler phases that completely consist of d metals. By introducing the d-metal Ti into NiMn alloys, cubic B2-type Heusler phase is obtained and the martensitic transformation temperature is decreased efficiently. Strong ferromagnetism is established by further doping Co atoms into the B2-type antiferromagnetic Ni-Mn-Ti austenite. Based on the magnetic-field-induced martensitic transformations, collective multifunctional properties are observed in Ni(Co)-Mn-Ti alloys. The d metals not only facilitate the formation of B2-type Heusler phases but also establish strong ferromagnetic coupling and offer the possibility to tune the martensitic transformation.

  12. Compact silicon photonic waveguide modulator based on the vanadium dioxide metal-insulator phase transition.

    PubMed

    Briggs, Ryan M; Pryce, Imogen M; Atwater, Harry A

    2010-05-24

    We have integrated lithographically patterned VO2 thin films grown by pulsed laser deposition with silicon-on-insulator photonic waveguides to demonstrate a compact in-line absorption modulator for use in photonic circuits. Using single-mode waveguides at lambda=1550 nm, we show optical modulation of the guided transverse-electric mode of more than 6.5 dB with 2 dB insertion loss over a 2-microm active device length. Loss is determined for devices fabricated on waveguide ring resonators by measuring the resonator spectral response, and a sharp decrease in resonator quality factor is observed above 70 degrees C, consistent with switching of VO2 to its metallic phase. A computational study of device geometry is also presented, and we show that it is possible to more than double the modulation depth with modified device structures.

  13. Topological phases in oxide heterostructures with light and heavy transition metal ions (invited)

    SciTech Connect

    Fiete, Gregory A.; Rüegg, Andreas

    2015-05-07

    Using a combination of density functional theory, tight-binding models, and Hartree-Fock theory, we predict topological phases with and without time-reversal symmetry breaking in oxide heterostructures. We consider both heterostructures containing light transition metal ions and those containing heavy transition metal ions. We find that the (111) growth direction naturally leads to favorable conditions for topological phases in both perovskite structures and pyrochlore structures. For the case of light transition metal elements, Hartree-Fock theory predicts the spin-orbit coupling is effectively enhanced by on-site multiple-orbital interactions and may drive the system through a topological phase transition, while heavy elements with intrinsically large spin-orbit coupling require much weaker or even vanishing electron interactions to bring about a topological phase.

  14. Separation observation of metal-insulator transition and structural phase transition in VO2

    NASA Astrophysics Data System (ADS)

    Kim, Hyun-Tak; Kim, Bong-Jun; Lee, Yong Wook; Chae, Byung Gyu; Yun, Sun Jin; Oh, Soo-Young; Lim, Yong-Sik

    2007-03-01

    An intermediate monoclinic metal phase between the metal-insulator transition (MIT) and the structural phase transition (SPT) is observed with VO2-based two-terminal devices and can be explained in terms of the Mott MIT. The conductivity of this phase linearly increases with increasing temperature up to TSPT 68^oC and becomes maximum at TSPT. The SPT is confirmed by micro-Raman spectroscopy. Optical microscopic observation reveals the absence of a local current path in the metal phase. The current uniformly flows throughout the surface of the VO2 film when the MIT occurs. This device can be used as a programmable critical temperature sensor. (References: New J. Phys. 6 (1994) 52 (http://www.njp.org); Appl. Phys. Lett. 86 (2005) 24210); Physica B 369 (2005) 76; cond-mat/0607577; cond-mat/0608085; cond-mat/0609033).

  15. Hidden amorphous phase and reentrant supercooled liquid in Pd-Ni-P metallic glasses

    NASA Astrophysics Data System (ADS)

    Lan, S.; Ren, Y.; Wei, X. Y.; Wang, B.; Gilbert, E. P.; Shibayama, T.; Watanabe, S.; Ohnuma, M.; Wang, X.-L.

    2017-03-01

    An anomaly in differential scanning calorimetry has been reported in a number of metallic glass materials in which a broad exothermal peak was observed between the glass and crystallization temperatures. The mystery surrounding this calorimetric anomaly is epitomized by four decades long studies of Pd-Ni-P metallic glasses, arguably the best glass-forming alloys. Here we show, using a suite of in situ experimental techniques, that Pd-Ni-P alloys have a hidden amorphous phase in the supercooled liquid region. The anomalous exothermal peak is the consequence of a polyamorphous phase transition between two supercooled liquids, involving a change in the packing of atomic clusters over medium-range length scales as large as 18 Å. With further temperature increase, the alloy reenters the supercooled liquid phase, which forms the room-temperature glass phase on quenching. The outcome of this study raises a possibility to manipulate the structure and hence the stability of metallic glasses through heat treatment.

  16. Variable phase sine wave generator for active phased arrays

    NASA Astrophysics Data System (ADS)

    Waters, W. M.

    1992-09-01

    A waveform generator is provided for generating a high frequency waveform. A pulse generator provides a pulse train at a low frequency. A pulse converter converts the pulse train into an alternatingly positive and negative groups of pulses. A bandpass filter passes the alternatingly positive and negative groups of pulses in a frequency band centered at the high frequency to output the generated waveform at the high frequency. When the groups of pulses are a pair of pulses, a sine wave is output from the bandpass filter. A pulse delay circuit can be used to variably delay the pulse train and thereby cause a phase change in the generated waveform.

  17. Generation of copper rich metallic phases from waste printed circuit boards

    SciTech Connect

    Cayumil, R.; Khanna, R.; Ikram-Ul-Haq, M.; Rajarao, R.; Hill, A.; Sahajwalla, V.

    2014-10-15

    Highlights: • Recycling and material recovery from waste printed circuit boards is very complex. • Thermoset polymers, ceramics and metals are present simultaneously in waste PCBs. • Heat treatment of PCBs was carried out at 1150 °C under inert conditions. • Various metallic phases could be segregated out as copper based metallic droplets. • Carbon and ceramics residues can be further recycled in a range of applications. - Abstract: The rapid consumption and obsolescence of electronics have resulted in e-waste being one of the fastest growing waste streams worldwide. Printed circuit boards (PCBs) are among the most complex e-waste, containing significant quantities of hazardous and toxic materials leading to high levels of pollution if landfilled or processed inappropriately. However, PCBs are also an important resource of metals including copper, tin, lead and precious metals; their recycling is appealing especially as the concentration of these metals in PCBs is considerably higher than in their ores. This article is focused on a novel approach to recover copper rich phases from waste PCBs. Crushed PCBs were heat treated at 1150 °C under argon gas flowing at 1 L/min into a horizontal tube furnace. Samples were placed into an alumina crucible and positioned in the cold zone of the furnace for 5 min to avoid thermal shock, and then pushed into the hot zone, with specimens exposed to high temperatures for 10 and 20 min. After treatment, residues were pulled back to the cold zone and kept there for 5 min to avoid thermal cracking and re-oxidation. This process resulted in the generation of a metallic phase in the form of droplets and a carbonaceous residue. The metallic phase was formed of copper-rich red droplets and tin-rich white droplets along with the presence of several precious metals. The carbonaceous residue was found to consist of slag and ∼30% carbon. The process conditions led to the segregation of hazardous lead and tin clusters in the

  18. A model for understanding the formation energies of nanolamellar phases in transition metal carbides and nitrides

    NASA Astrophysics Data System (ADS)

    Yu, Hang; Guziewski, Matthew; Thompson, Gregory B.; Weinberger, Christopher R.

    2016-06-01

    In this paper we introduce a stacking-fault based model to understand the energetics of formation of the nanolamellar-based metal carbide and nitride structures. The model is able to reproduce the cohesive energies of the stacking fault phases from density functional theory calculations by fitting the energy of different stacking sequences of metal layers. The model demonstrates that the first and second nearest metal-metal neighbor interactions and the nearest metal-carbon/nitrogen interaction are the dominant terms in determining the cohesive energy of these structures. The model further demonstrates that above a metal to non-metal ratio of 75%, there is no energetic favorability for the stacking faults to form a long-range ordered structure. The model’s applicability is demonstrated using the Ta-C system as its case study from which we report that the interfacial energy between ζ-Ta4C3 and TaC or Ta2C is negligible. Our results suggest that the closed packed planes of these phases should be aligned and that precipitated phases should be thin, which is in agreement with experiments.

  19. Heat transfer enhancement for thermal energy storage using metal foams embedded within phase change materials (PCMs)

    SciTech Connect

    Zhao, C.Y.; Lu, W.; Tian, Y.

    2010-08-15

    In this paper the experimental investigation on the solid/liquid phase change (melting and solidification) processes have been carried out. Paraffin wax RT58 is used as phase change material (PCM), in which metal foams are embedded to enhance the heat transfer. During the melting process, the test samples are electrically heated on the bottom surface with a constant heat flux. The PCM with metal foams has been heated from the solid state to the pure liquid phase. The temperature differences between the heated wall and PCM have been analysed to examine the effects of heat flux and metal foam structure (pore size and relative density). Compared to the results of the pure PCM sample, the effect of metal foam on solid/liquid phase change heat transfer is very significant, particularly at the solid zone of PCMs. When the PCM starts melting, natural convection can improve the heat transfer performance, thereby reducing the temperature difference between the wall and PCM. The addition of metal foam can increase the overall heat transfer rate by 3-10 times (depending on the metal foam structures and materials) during the melting process (two-phase zone) and the pure liquid zone. The tests for investigating the solidification process under different cooling conditions (e.g. natural convection and forced convection) have been carried out. The results show that the use of metal foams can make the sample solidified much faster than pure PCM samples, evidenced by the solidification time being reduced by more than half. In addition, a two-dimensional numerical analysis has been carried out for heat transfer enhancement in PCMs by using metal foams, and the prediction results agree reasonably well with the experimental data. (author)

  20. Effects of metal ion adduction on the gas-phase conformations of protein ions.

    PubMed

    Flick, Tawnya G; Merenbloom, Samuel I; Williams, Evan R

    2013-11-01

    Changes in protein ion conformation as a result of nonspecific adduction of metal ions to the protein during electrospray ionization (ESI) from aqueous solutions were investigated using traveling wave ion mobility spectrometry (TWIMS). For all proteins examined, protein cations (and in most cases anions) with nonspecific metal ion adducts are more compact than the fully protonated (or deprotonated) ions with the same charge state. Compaction of protein cations upon nonspecific metal ion binding is most significant for intermediate charge state ions, and there is a greater reduction in collisional cross section with increasing number of metal ion adducts and increasing ion valency, consistent with an electrostatic interaction between the ions and the protein. Protein cations with the greatest number of adducted metal ions are no more compact than the lowest protonated ions formed from aqueous solutions. These results show that smaller collisional cross sections for metal-attached protein ions are not a good indicator of a specific metal-protein interaction in solution because nonspecific metal ion adduction also results in smaller gaseous protein cation cross sections. In contrast, the collisional cross section of α-lactalbumin, which specifically binds one Ca(2+), is larger for the holo-form compared with the apo-form, in agreement with solution-phase measurements. Because compaction of protein cations occurs when metal ion adduction is nonspecific, elongation of a protein cation may be a more reliable indicator that a specific metal ion-protein interaction occurs in solution.

  1. Metal chlorides loaded on activated carbon to capture elemental mercury.

    PubMed

    Shen, Zhemin; Ma, Jing; Mei, Zhijian; Zhang, Jianda

    2010-01-01

    Activated carbon (AC) was considered to be an effective sorbent to control mercury in combustion systems. However, its capture capacity was low and it required a high carbon-to-mercury mass ratio. AC loaded with catalyst showed a high elemental mercury (Hg0) capture capacity due to large surface area of AC and high oxidization ability of catalyst. In this study, several metal chlorides and metal oxides were used to promote the sorption capacity of AC. As a result, metal chlorides were better than metal oxides loaded on AC to remove gaseous mercury. X-ray diffractometer (XRD), thermogravimetric analyzer (TGA) and specific surface area by Brunauer-Emmett-Teller method (BET) analysis showed the main mechanisms: first, AC had an enormous surface area for loading enough MClx; second, Cl and MxOy were generated during pyrogenation of MClx; finally, there were lots of active elements such as Cl and MxOy which could react with elemental mercury and convert it to mercury oxide and mercury chloride. The HgO and HgCl2 might be released from AC's porous structure by thermo regeneration. A catalytic chemisorption mechanism predominates the sorption process of elemental mercury. As Co and Mn were valence variable metal elements, their catalytic effect on Hg0 oxidization may accelerate both oxidation and halogenation of Hg0. The sorbents loaded with metal chlorides possessed a synergistic function of catalytic effect of valence variable metal and chlorine oxidation.

  2. Electrical conductivity in oxygen-deficient phases of transition metal oxides from first-principles calculations.

    SciTech Connect

    Bondi, Robert James; Desjarlais, Michael Paul; Thompson, Aidan Patrick; Brennecka, Geoffrey L.; Marinella, Matthew

    2013-09-01

    Density-functional theory calculations, ab-initio molecular dynamics, and the Kubo-Greenwood formula are applied to predict electrical conductivity in Ta2Ox (0 x 5) as a function of composition, phase, and temperature, where additional focus is given to various oxidation states of the O monovacancy (VOn; n=0,1+,2+). Our calculations of DC conductivity at 300K agree well with experimental measurements taken on Ta2Ox thin films and bulk Ta2O5 powder-sintered pellets, although simulation accuracy can be improved for the most insulating, stoichiometric compositions. Our conductivity calculations and further interrogation of the O-deficient Ta2O5 electronic structure provide further theoretical basis to substantiate VO0 as a donor dopant in Ta2O5 and other metal oxides. Furthermore, this dopant-like behavior appears specific to neutral VO cases in both Ta2O5 and TiO2 and was not observed in other oxidation states. This suggests that reduction and oxidation reactions may effectively act as donor activation and deactivation mechanisms, respectively, for VO0 in transition metal oxides.

  3. Magnetron sputtering Si interlayer: a protocol to prepare solid phase microextraction coatings on metal-based fiber.

    PubMed

    Liu, Hongmei; Ji, Li; Li, Jubai; Liu, Shujuan; Liu, Xia; Jiang, Shengxiang

    2011-05-20

    Use of metal fibers in solid phase microextraction (SPME) can overcome the fragility drawback of conventional fused-silica ones. However, the surface modification of metal substrates is rather difficult, which largely prevents many mature traditional techniques, such as sol-gel and chemical bonding, being used in fabrication of SPME coating on metal-based fibers. This study demonstrates a protocol to resolve this problem by magnetron sputtering a firm Si interlayer on stainless steel fiber. The Si interlayer was easily modified active group, and attached with a multiwalled carbon nanotubes (MWCNTs) coating using the reported approach. The as-prepared MWCNTs/Si/stainless steel wire fiber not only preserved the excellent SPME behaviors of MWCNTs coatings, but also exhibited a number of advantages including high rigidity, long service life, and good stability at high temperature, in acid and alkali solutions. This new surface modification technique might provide a versatile approach to prepare sorbent coatings on unconfined substrates using traditional methods.

  4. Hydrocarbon-soluble nanocatalysts with no bulk phase: coplanar, two-coordinate arrays of the base metals.

    PubMed

    Camacho-Bunquin, Jeffrey; Ferguson, Michael J; Stryker, Jeffrey M

    2013-04-17

    A structurally unique class of hydrocarbon-soluble, ancillary-ligand-free, tetrametallic Co(I) and Ni(I) clusters is reported. The highly unsaturated complexes are supported by simple, sterically bulky phosphoranimide ligands, one per metal. The electron-rich nitrogen centers are strongly bridging but sterically limited to bimetallic interactions. The hydrocarbon-soluble clusters consist of four coplanar metal centers, mutually bridged by single nitrogen atoms. Each metal center is monovalent, rigorously linear, and two-coordinate. The clusters are in essence two-dimensional atomic-scale "molecular squares," a structural motif adapted from supramolecular chemistry. Both clusters exhibit high solution-phase magnetic susceptibility at room temperature, suggesting the potential for applications in molecular electronics. Designed to be catalyst precursors, both clusters exhibit high activity for catalytic hydrogenation of unsaturated hydrocarbons at low pressure and temperature.

  5. High resolution Hall measurements across the VO2 metal-insulator transition reveal impact of spatial phase separation

    PubMed Central

    Yamin, Tony; Strelniker, Yakov M.; Sharoni, Amos

    2016-01-01

    Many strongly correlated transition metal oxides exhibit a metal-insulator transition (MIT), the manipulation of which is essential for their application as active device elements. However, such manipulation is hindered by lack of microscopic understanding of mechanisms involved in these transitions. A prototypical example is VO2, where previous studies indicated that the MIT resistance change correlate with changes in carrier density and mobility. We studied the MIT using Hall measurements with unprecedented resolution and accuracy, simultaneously with resistance measurements. Contrast to prior reports, we find that the MIT is not correlated with a change in mobility, but rather, is a macroscopic manifestation of the spatial phase separation which accompanies the MIT. Our results demonstrate that, surprisingly, properties of the nano-scale spatially-separated metallic and semiconducting domains actually retain their bulk properties. This study highlights the importance of taking into account local fluctuations and correlations when interpreting transport measurements in highly correlated systems. PMID:26783076

  6. Ignition and combustion characteristics of metallized propellants, phase 2

    NASA Technical Reports Server (NTRS)

    Mueller, D. C.; Turns, S. R.

    1994-01-01

    Experimental and analytical investigations focusing on aluminum/hydrocarbon gel droplet secondary atomization and its effects on gel-fueled rocket engine performance are being conducted. A single laser sheet sizing/velocimetry diagnostic technique, which should eliminate sizing bias in the data collection process, has been designed and constructed to overcome limitations of the two-color forward-scatter technique used in previous work. Calibration of this system is in progress and the data acquisition/validation code is being written. Narrow-band measurements of radiant emission, discussed in previous reports, will be used to determine if aluminum ignition has occurred in a gel droplet. A one-dimensional model of a gel-fueled rocket combustion chamber, described in earlier reports, has been exercised in conjunction with a two-dimensional, two-phase nozzle code to predict the performance of an aluminum/hydrocarbon fueled engine. Estimated secondary atomization effects on propellant burnout distance, condensed particle radiation losses to the chamber walls, and nozzle two phase flow losses are also investigated. Calculations indicate that only modest secondary atomization is required to significantly reduce propellant burnout distances, aluminum oxide residual size, and radiation heat losses. Radiation losses equal to approximately 2-13 percent of the energy released during combustion were estimated, depending on secondary atomization intensity. A two-dimensional, two-phase nozzle code was employed to estimate radiation and nozzle two phase flow effects on overall engine performance. Radiation losses yielded a one percent decrease in engine Isp. Results also indicate that secondary atomization may have less effect on two-phase losses than it does on propellant burnout distance and no effect if oxide particle coagulation and shear induced droplet breakup govern oxide particle size. Engine Isp was found to decrease from 337.4 to 293.7 seconds as gel aluminum mass

  7. Valorization of BOF Steel Slag by Reduction and Phase Modification: Metal Recovery and Slag Valorization

    NASA Astrophysics Data System (ADS)

    Liu, Chunwei; Huang, Shuigen; Wollants, Patrick; Blanpain, Bart; Guo, Muxing

    2017-03-01

    Basic oxygen furnace (BOF) steel slag is a main byproduct in steelmaking, and its valorization is therefore of considerable interest, from a metal-recovery perspective and from a residue-utilization perspective. In the present study, the carbothermic reduction of BOF slag was investigated systematically. The reductions of Fe- and P-containing phases (i.e., oxide and compounds) are discussed. Effects of Al2O3 and SiO2 additions on the solidification microstructure and mineralogy associated with the reduction processes were also investigated. The formation and growth of the extracted metallic phase are discussed, and the mineralogy of the residue slag is determined. We conclude that by controlling the additions under a rapid cooling condition, it is possible to extract metallic iron as high-grade metal and simultaneously to utilize the remaining slag for construction applications.

  8. Application of Δ- and Λ-Isomerism of Octahedral Metal Complexes for Inducing Chiral Nematic Phases

    PubMed Central

    Sato, Hisako; Yamagishi, Akihiko

    2009-01-01

    The Δ- and Λ-isomerism of octahedral metal complexes is employed as a source of chirality for inducing chiral nematic phases. By applying a wide range of chiral metal complexes as a dopant, it has been found that tris(β-diketonato)metal(III) complexes exhibit an extremely high value of helical twisting power. The mechanism of induction of the chiral nematic phase is postulated on the basis of a surface chirality model. The strategy for designing an efficient dopant is described, together with the results using a number of examples of Co(III), Cr(III) and Ru(III) complexes with C2 symmetry. The development of photo-responsive dopants to achieve the photo-induced structural change of liquid crystal by use of photo-isomerization of chiral metal complexes is also described. PMID:20057959

  9. Phase-locked coherent modes in a patterned metal-organic microcavity

    NASA Astrophysics Data System (ADS)

    Brückner, R.; Zakhidov, A. A.; Scholz, R.; Sudzius, M.; Hintschich, S. I.; Fröb, H.; Lyssenko, V. G.; Leo, K.

    2012-05-01

    Organic microcavities offer tantalizing prospects for studying the interactions of light and matter. For electrical excitation of these processes, electrodes must be integrated. However, the large absorption properties of metals are generally considered fatal for optical coherence. With this in mind, we embedded a thin silver grating into an organic microcavity to generate periodic arrays of localized cavity modes and metal-based Tamm plasmon polaritons. These excited states are capable of phase coupling across the grating. At room temperature and under non-resonant pumping, we selectively stimulated coherent emission from in- and out-of-phase locked arrays. We show that an absorptive metal inside an optical cavity is compatible with coherent emission. Most importantly, the inherently low residual absorption of the organic layer enables coherence to spread over macroscopic distances, even at room temperature. Our strategy of embedding metal patterns into an organic microcavity yields a viable route towards electrically driven organic solid-state lasers.

  10. Nondestructive Characterization of Two-Phase Metal-Matrix Materials

    DTIC Science & Technology

    1991-12-01

    discontinuou SiC-reinforced aluminum alloys. The methods to be studied are based on the physical nonlinear elastic behavior of solids and utilized... behavior of solids and utilize measurements of the elastic as well as the acoustoelastic constants. The objectives are to establish both experimentally...volume fraction and the orientation of each phase influence the macroscopic behavior . In this study (1, 5, 6), an ultrasonic method is developed for the

  11. Two cases of lichen striatus with prolonged active phase.

    PubMed

    Feely, Meghan A; Silverberg, Nanette B

    2014-01-01

    Lichen striatus is a localized, eczematous disorder distributed along the lines of Blaschko, primarily affecting children. In the literature, lesions have been described as having an active phase of inflamed lesions for 6 to 12 months followed by flattening and persistent pigmentary alteration. We describe two girls who had prolonged active-phase lesions for 2.5 and 3.5 years, respectively. Practitioners should be aware that lesions of lichen striatus may have a prolonged active phase.

  12. Active impedance metasurface with full 360° reflection phase tuning

    PubMed Central

    Zhu, Bo O.; Zhao, Junming; Feng, Yijun

    2013-01-01

    Impedance metasurface is composed of electrical small scatters in two dimensional plane, of which the surface impedance can be designed to produce desired reflection phase. Tunable reflection phase can be achieved by incorporating active element into the scatters, but the tuning range of the reflection phase is limited. In this paper, an active impedance metasurface with full 360° reflection phase control is presented to remove the phase tuning deficiency in conventional approach. The unit cell of the metasurface is a multiple resonance structure with two resonance poles and one resonance zero, capable of providing 360° reflection phase variation and active tuning within a finite frequency band. Linear reflection phase tuning can also be obtained. Theoretical analysis and simulation are presented and validated by experiment at microwave frequency. The proposed approach can be applied to many cases where fine and full phase tuning is needed, such as beam steering in reflectarray antennas. PMID:24162366

  13. Method and apparatus for selective capture of gas phase analytes using metal .beta.-diketonate polymers

    DOEpatents

    Harvey, Scott D [Kennewick, WA

    2011-06-21

    A process and sensor device are disclosed that employ metal .beta.-diketonate polymers to selectively capture gas-phase explosives and weaponized chemical agents in a sampling area or volume. The metal .beta.-diketonate polymers can be applied to surfaces in various analytical formats for detection of: improvised explosive devices, unexploded ordinance, munitions hidden in cargo holds, explosives, and chemical weapons in public areas.

  14. Directed liquid phase assembly of highly ordered metallic nanoparticle arrays

    DOE PAGES

    Wu, Yueying; Dong, Nanyi; Fu, Shaofang; ...

    2014-04-01

    Directed assembly of nanomaterials is a promising route for the synthesis of advanced materials and devices. We demonstrate the directed-assembly of highly ordered two-dimensional arrays of hierarchical nanostructures with tunable size, spacing and composition. The directed assembly is achieved on lithographically patterned metal films that are subsequently pulse-laser melted; during the brief liquid lifetime, the pattened nanostructures assemble into highly ordered primary and secondary nanoparticles, with sizes below that which was originally patterned. Complementary fluid-dynamics simulations emulate the resultant patterns and show how the competition of capillary forces and liquid metal–solid substrate interaction potential drives the directed assembly. Lastly, asmore » an example of the enhanced functionality, a full-wave electromagnetic analysis has been performed to identify the nature of the supported plasmonic resonances.« less

  15. Directed liquid phase assembly of highly ordered metallic nanoparticle arrays

    SciTech Connect

    Wu, Yueying; Dong, Nanyi; Fu, Shaofang; Fowlkes, Jason D.; Kondic, Lou; Vincenti, Maria A.; de Ceglia, Domenico; Rack, Philip D.

    2014-04-01

    Directed assembly of nanomaterials is a promising route for the synthesis of advanced materials and devices. We demonstrate the directed-assembly of highly ordered two-dimensional arrays of hierarchical nanostructures with tunable size, spacing and composition. The directed assembly is achieved on lithographically patterned metal films that are subsequently pulse-laser melted; during the brief liquid lifetime, the pattened nanostructures assemble into highly ordered primary and secondary nanoparticles, with sizes below that which was originally patterned. Complementary fluid-dynamics simulations emulate the resultant patterns and show how the competition of capillary forces and liquid metal–solid substrate interaction potential drives the directed assembly. Lastly, as an example of the enhanced functionality, a full-wave electromagnetic analysis has been performed to identify the nature of the supported plasmonic resonances.

  16. Field-Induced Reversible Phase Manipulation in Metal-Insulator Transition using Scanning Tunneling Microscopy

    NASA Astrophysics Data System (ADS)

    Park, Se Jun

    2005-03-01

    Reversible electronic switching between insulating and metallic phases is a novel idea that may allow new types of field effect devices feasible.^1 Here we demonstrate the reversible manipulation between metallic and insulating phases in two-dimensional In nanowire arrays on Si(111) surface near the metal-insulator transition temperature (Tc). The electronic switching of phases was induced by local electric field applied by the probe tip of a scanning tunneling microscope. The field-dependent hysteresis behavior was also observed in tip height measurements as a function of the sample bias, under the constraint of constant tunneling current. A model including the intrinsic bi-stability of the nanometer-scale domains of In nanowire arrays will be discussed. ^1C. Ahn, J. Triscone, J. Mannhart, Nature 6952, 1015 (2003)

  17. Phase transitions and optical properties of the semiconducting and metallic phases of single-layer MoS₂.

    PubMed

    Fair, K M; Ford, M J

    2015-10-30

    We report density functional theory calculations for single layer MoS2 in its 2H, semiconducting and 1T metallic phases in order to understand the relative stability of these two phases and transition between them in the presence of adsorbed lithium atoms and under compressive strain. We have determined the diffusion barriers between the two phases and demonstrate how the presence of Li adatoms or strain can significantly reduce these barriers. We show that the 2H and 1T structures have the same energy under 15% biaxial, compressive strain. This is the same strain value posited by Lin et al (2014 Nat. Nanotechnology 9 391-396) for their intermediate α phase. Calculations of the 1T and 2H permittivity and electron energy loss spectrum are also performed and characterized.

  18. Encapsulating Cytochrome c in Silica Aerogel Nanoarchitectures without Metal Nanoparticles while Retaining Gas-phase Bioactivity

    PubMed Central

    Harper-Leatherman, Amanda S.; Pacer, Elizabeth R.; Kosciuszek, Nina D.

    2016-01-01

    Applications such as sensors, batteries, and fuel cells have been improved through the use of highly porous aerogels when functional compounds are encapsulated within the aerogels. However, few reports on encapsulating proteins within sol–gels that are processed to form aerogels exist. A procedure for encapsulating cytochrome c (cyt. c) in silica (SiO2) sol-gels that are supercritically processed to form bioaerogels with gas-phase activity for nitric oxide (NO) is presented. Cyt. c is added to a mixed silica sol under controlled protein concentration and buffer strength conditions. The sol mixture is then gelled and the liquid filling the gel pores is replaced through a series of solvent exchanges with liquid carbon dioxide. The carbon dioxide is brought to its critical point and vented off to form dry aerogels with cyt. c encapsulated inside. These bioaerogels are characterized with UV-visible spectroscopy and circular dichroism spectroscopy and can be used to detect the presence of gas-phase nitric oxide. The success of this procedure depends on regulating the cyt. c concentration and the buffer concentration and does not require other components such as metal nanoparticles. It may be possible to encapsulate other proteins using a similar approach making this procedure important for potential future bioanalytical device development. PMID:26967257

  19. Metal-Hydrogen Phase Diagrams in the Vicinity of Melting Temperatures

    SciTech Connect

    Shapovalov, V.I.

    1999-01-06

    Hydrogen-metal interaction phenomena belong to the most exciting challenges of today's physical metallurgy and physics of solids due to the uncommon behavior of hydrogen in condensed media and to the need for understanding hydrogen's strong negative impact on properties of some high-strength steels and.alloys. The paper cites and summarizes research data on fundamental thermodynamic characteristics of hydrogen in some metals that absorb it endothermally at elevated temperatures. For a number of metal-hydrogen systems, information on some phase diagrams previously not available to the English-speaking scientific community is presented.

  20. Frequency translating phase conjugation circuit for active retrodirective antenna array

    NASA Astrophysics Data System (ADS)

    Chernoff, R.

    1980-11-01

    An active retrodirective antenna array which has central phasing from a reference antenna element through a "tree" structured network of transmission lines utilizes a number of phase conjugate circuits (PCCs) at each node and a phase reference regeneration circuit (PRR) at each node except the initial node. Each node virtually coincides with an element of the array. A PCC generates the exact conjugate phase of an incident signal using a phase locked loop which combines the phases in an up converter, divides the sum by 2 and mixes the result with the phase in a down converter for phase detection. The PRR extracts the phase from the conjugate phase. Both the PCC and the PRR are not only exact but also free from mixer degeneracy.

  1. Electronic and Thermal Effects in the Insulator-Metal Phase Transition in VO2 Nano-Gap Junctions

    DTIC Science & Technology

    2014-11-27

    Electronic and thermal effects in the insulator -metal phase transition in VO2 nano-gap junctions Arash Joushaghani,1 Junho Jeong,1 Suzanne Paradis,2...voltage waveforms, the electronically induced insulator -metal phase transition is investigated in the adiabatic heating and transient carrier injection...the complete insulator -metal phase transition is limited by thermal redistribution times to hundreds of nanoseconds. The dynamics of the insulator

  2. Passive and active metasurface based on metal-insulator-metal structures

    NASA Astrophysics Data System (ADS)

    Takahara, Junichi; Liu, Tianji; Hatada, Hideaki; Nagasaki, Yusuke; Miyata, Masashi; Kaijima, Akira

    2016-11-01

    A metal-insulator-metal (MIM) structure is a fundamental plasmonic structure that has been studied widely since the early stage of plasmonics. It enables us to confine surface plasmon polariton (SPP) and concentrate light into nano-space beyond the diffraction limit. A finite-length MIM structure is considered to be a Fabry-Perot resonator of SPP as a nanocavity. Here, we review our recent studies about active metasurface based on a reconfigurable metal-air-metal (MAM) nanocavity which modify reflection or absorption spectra in scattering by changing a gap distance. Such reconfigurable MAM nanocavity becomes promising candidate for various applications such as plasmonic color or sky radiator from visible to infrared range.

  3. Fabrication of submicron metallic grids with interference and phase-mask holography

    SciTech Connect

    Park, Joong-Mok; Kim, Tae-Geun; Constant, Kristen; Ho, Kai-Ming

    2011-01-25

    Complex, submicron Cu metallic mesh nanostructures are made by electrochemical deposition using polymer templates made from photoresist. The polymer templates are fabricated with photoresist using two-beam interference holography and phase mask holography with three diffracted beams. Freestanding metallic mesh structures are made in two separate electrodepositions with perpendicular photoresist grating templates. Cu mesh square nanostructures having large (52.6%) open areas are also made by single electrodeposition with a photoresist template made with a phase mask. These structures have potential as electrodes in photonic devices.

  4. Composition of the metal phases in ordinary chondrites - Implications regarding classification and metamorphism

    NASA Technical Reports Server (NTRS)

    Afiattalab, F.; Wasson, J. T.

    1980-01-01

    The paper examines the composition of metal phases and metamorphism in ordinary chondrites. It is shown that below 550 C increasing Co decreases the equilibrium kamacite Ni concentration of an alpha to gamma system, and that the equilibrated L chondrites have kamacite and taenite Co concentrations in the L-group range. Metal-phase studies of petrologic type-3 ordinary chondrites with highly unequilibrated silicates showed a wide range in the degree of matrix kamacite equilibration; in the three most unequilibrated chondrites most taenite is clear, and the high Ni content shows that metamorphic temperatures were lower than 400 C in these meteorites.

  5. Metal organic chemical vapor deposition of phase change Ge1Sb2Te4 nanowires.

    PubMed

    Longo, Massimo; Fallica, Roberto; Wiemer, Claudia; Salicio, Olivier; Fanciulli, Marco; Rotunno, Enzo; Lazzarini, Laura

    2012-03-14

    The self-assembly of Ge(1)Sb(2)Te(4) nanowires (NWs) for phase change memories application was achieved by metal organic chemical vapor deposition, catalyzed by Au nanoislands in a narrow range of temperatures and deposition pressures. In the optimized conditions of 400 °C, 50 mbar, the NWs are Ge(1)Sb(2)Te(4) single hexagonal crystals. Phase change memory switching was reversibly induced by nanosecond current pulses through metal-contacted NWs with threshold voltage of about 1.35 V.

  6. Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal-nitrogen coordination.

    PubMed

    Strickland, Kara; Miner, Elise; Jia, Qingying; Tylus, Urszula; Ramaswamy, Nagappan; Liang, Wentao; Sougrati, Moulay-Tahar; Jaouen, Frédéric; Mukerjee, Sanjeev

    2015-06-10

    Replacement of noble metals in catalysts for cathodic oxygen reduction reaction with transition metals mostly create active sites based on a composite of nitrogen-coordinated transition metal in close concert with non-nitrogen-coordinated carbon-embedded metal atom clusters. Here we report a non-platinum group metal electrocatalyst with an active site devoid of any direct nitrogen coordination to iron that outperforms the benchmark platinum-based catalyst in alkaline media and is comparable to its best contemporaries in acidic media. In situ X-ray absorption spectroscopy in conjunction with ex situ microscopy clearly shows nitrided carbon fibres with embedded iron particles that are not directly involved in the oxygen reduction pathway. Instead, the reaction occurs primarily on the carbon-nitrogen structure in the outer skin of the nitrided carbon fibres. Implications include the potential of creating greater active site density and the potential elimination of any Fenton-type process involving exposed iron ions culminating in peroxide initiated free-radical formation.

  7. Tuned by metals: the TET peptidase activity is controlled by 3 metal binding sites.

    PubMed

    Colombo, Matteo; Girard, Eric; Franzetti, Bruno

    2016-02-08

    TET aminopeptidases are dodecameric particles shared in the three life domains involved in various biological processes, from carbon source provider in archaea to eye-pressure regulation in humans. Each subunit contains a dinuclear metal site (M1 and M2) responsible for the enzyme catalytic activity. However, the role of each metal ion is still uncharacterized. Noteworthy, while mesophilic TETs are activated by Mn(2+), hyperthermophilic TETs prefers Co(2+). Here, by means of anomalous x-ray crystallography and enzyme kinetics measurements of the TET3 aminopeptidase from the hyperthermophilic organism Pyrococcus furiosus (PfTET3), we show that M2 hosts the catalytic activity of the enzyme, while M1 stabilizes the TET3 quaternary structure and controls the active site flexibility in a temperature dependent manner. A new third metal site (M3) was found in the substrate binding pocket, modulating the PfTET3 substrate preferences. These data show that TET activity is tuned by the molecular interplay among three metal sites.

  8. Evidence of photo-induced dynamic competition of metallic and insulating phase in a layered manganite.

    PubMed

    Li, Yuelin; Walko, Donald A; Li, Qing'an; Liu, Yaohua; Rosenkranz, Stephan; Zheng, Hong; Mitchell, J F

    2015-12-16

    We show evidence that the competition between the antiferromagetic metallic phase and the charge- and orbital-ordered insulating phase at the reentrant phase boundary of a layered manganite, La0.99Sr2.01Mn2O7, can be manipulated using ultrafast optical excitation. The time-dependent evolution of the Jahn-Teller superlattice reflection, which indicates the formation of the charge and orbital order, was measured at different laser fluences. The laser-induced enhancement and reduction the Jahn-Teller reflection intensity shows a reversal of sign between earlier (~10 ns) and later (~150 ns) time delays during the relaxation after photo excitation. This effect is consistent with a scenario whereby the laser excitation modulates the local competition between the metallic and the insulating phases.

  9. Evidence of photo-induced dynamic competition of metallic and insulating phase in a layered manganite

    DOE PAGES

    Li, Yuelin; Walko, Daonld A.; Li, Qing'an; ...

    2015-11-17

    We show evidence that the competition between the antiferromagetic metallic phase and the charge- and orbital-ordered insulating phase at the reentrant phase boundary of a layered manganite, LaSr2Mn2O7, can be manipulated using ultrafast optical excitation. The time-dependent evolution of the Jahn-Teller superlattice reflection, which indicates the formation of the charge and orbital order, was measured at different laser fluences. The laser-induced enhancement and reduction the Jahn-Teller reflection intensity shows a reversal of sign between earlier (~10 ns) and later (~150 ns) time delays during the relaxation after photo excitation. This effect is consistent with a scenario whereby the laser excitationmore » modulates the local competition between the metallic and the insulating phases.« less

  10. Evidence of photo-induced dynamic competition of metallic and insulating phase in a layered manganite

    SciTech Connect

    Li, Yuelin; Walko, Daonld A.; Li, Qing'an; Liu, Yaohua; Rosenkranz, Stephen; Zheng, Hong; Mitchell, J. F.

    2015-11-17

    We show evidence that the competition between the antiferromagetic metallic phase and the charge- and orbital-ordered insulating phase at the reentrant phase boundary of a layered manganite, LaSr2Mn2O7, can be manipulated using ultrafast optical excitation. The time-dependent evolution of the Jahn-Teller superlattice reflection, which indicates the formation of the charge and orbital order, was measured at different laser fluences. The laser-induced enhancement and reduction the Jahn-Teller reflection intensity shows a reversal of sign between earlier (~10 ns) and later (~150 ns) time delays during the relaxation after photo excitation. This effect is consistent with a scenario whereby the laser excitation modulates the local competition between the metallic and the insulating phases.

  11. Evidence of Photo-induced Dynamic Competition of Metallic and Insulating Phase in a Layered Manganite.

    SciTech Connect

    Li, Yuelin; Walko, Donald A.; Li, Qing'an; Liu, Yaohua; Rosenkranz, Stephan; Zheng, Hong; Mitchell, J. F.

    2015-12-16

    We show evidence that the competition between the antiferromagetic metallic phase and the charge- and orbital-ordered insulating phase at the reentrant phase boundary of a layered manganite, LaSr2Mn2O7, can be manipulated using ultrafast optical excitation. The time- dependent evolution of the Jahn-Teller superlattice reflection, which indicates the formation of the charge and orbital order, was measured at different laser fluences. The laser-induced enhancement and reduction the Jahn-Teller reflection intensity shows a reversal of sign between earlier (~10 ns) and later (~150 ns) time delays during the relaxation after photo excitation. This effect is consistent with a scenario whereby the laser excitation modulates the local competition between the metallic and the insulating phases.

  12. Heavy metals and adsorbents effects on activated sludge microorganisms.

    PubMed

    Ong, S A; Lim, P E; Seng, C E

    2004-01-01

    The sorption of Cu(II) and Cd(II) from synthetic solution by powdered activated carbon (PAC), biomass, rice husk (RH) and activated rice husk (ARH) were investigate under batch conditions. After activated by concentrated nitric acid for 15 hours at 60-65 degrees C, the adsorption capacity for RH was increased. The adsorbents arranged in the increasing order of adsorption capacities to the Langmuir Q degree parameter were biomass > PAC > ARH > RH. The addition of adsorbents in base mix solution had increased the specific oxygen uptake rate (SOUR) activated sludge microorganisms with and without the presence of metals. The increased of SOUR were due to the ability of PAC and RH in reducing the inhibitory effect of metals on microorganisms and provide a reaction site between activated sludge microorganisms and substrates.

  13. Thermodynamics of bcc metals in phase-field-crystal models.

    PubMed

    Jaatinen, A; Achim, C V; Elder, K R; Ala-Nissila, T

    2009-09-01

    We examine the influence of different forms of the free-energy functionals used in the phase-field-crystal (PFC) model, and compare them with the second-order density-functional theory (DFT) of freezing, by using bcc iron as an example case. We show that there are large differences between the PFC and the DFT and it is difficult to obtain reasonable parameters for existing PFC models directly from the DFT. Therefore, we propose a way of expanding the correlation function in terms of gradients that allows us to incorporate the bulk modulus of the liquid as an additional parameter in the theory. We show that this functional reproduces reasonable values for both bulk and surface properties of bcc iron, and therefore it should be useful in modeling bcc materials. As a further demonstration, we also calculate the grain boundary energy as a function of misorientation for a symmetric tilt boundary close to the melting transition.

  14. Light-induced structural phase behaviour of metal nanoparticle materials

    NASA Astrophysics Data System (ADS)

    Plech, A.; Kotaidis, V.; Wulff, M.; Dahmen, C.; von Plessen, G.

    2005-01-01

    We have investigated the structural dynamics of gold nanoparticles induced by femtosecond light excitation. Structure evolution in both embedded particles (glass matrix or liquid water suspension) and quasi-free particles adsorbed on a solid surface is analyzed. By use of stroboscopic laser pump- x-ray probe techniques the structural relaxations have been resolved on the 100 ps time scale at the European Synchrotron Radiation Facility. Several methods including powder scattering, liquid scattering and small angle scattering serve to resolve microscopic and mesoscopic length scales of the composite system. The thermal response includes the heating, lattice melting, explosive solvent evaporation and solvent cooling subsequent to the laser flash excitation. Nonthermal effects are observed with femtosecond excitation. They are attributed to ablation from the particle and particle explosion at strong nonequilibrium conditions. The observations can form a complete picture of the energy dissipation and phase transitions involved in nanoscale composites.

  15. Electron Irradiation Induced Phase Transition of an Amorphous Phase and Face-Centered Cubic Solid Solutions in Zr66.7Pd33.3 Metallic Glass

    NASA Astrophysics Data System (ADS)

    Nagase, Takeshi; Hosokawa, Takashi; Umakoshi, Yukichi

    2007-02-01

    Both amorphization and crystallization were observed in Zr66.7Pd33.3 metallic glass under electron irradiation. The melt-spun amorphous phase was not stable under 2.0 MV electron irradiation and two kinds of fcc-solid solution were precipitated through electron irradiation induced crystallization at 103 and 298 K. The fcc-solid solution obtained by electron irradiation induced crystallization at 298 K transformed to an amorphous phase during irradiation at 103 K. Electron irradiation induced phase transformation behavior in Zr66.7Pd33.3 metallic glass can be explained by phase stability of an amorphous phase and crystalline phases against electron irradiation.

  16. Purification of papain by metal affinity partitioning in aqueous two-phase polyethylene glycol/sodium sulfate systems.

    PubMed

    Jiang, Zhi-Guo; Zhang, Hai-De; Wang, Wei-Tao

    2015-05-01

    A simple and inexpensive aqueous two-phase affinity partitioning system using metal ligands was introduced to improve the selectivity of commercial papain extraction. Polyethylene glycol 4000 was first activated using epichlorohydrin, then it was covalently linked to iminodiacetic acid. Finally, the specific metal ligand Cu(2+) was attached to the polyethylene glycol-iminodiacetic acid. The chelated Cu(2+) content was measured by atomic absorption spectrometry as 0.88 mol/mol (polyethylene glycol). The effects on the purification at different conditions, including polyethylene glycol molecular weight (2000, 4000, and 6000), concentration of phase-forming components (polyethylene glycol 12-20% w/w and sodium sulfate 12-20%, w/w), metal ligand type, and concentration, system pH and the commercial papain loading on papain extraction, were systematically studied. Under optimum conditions of the system, i.e. 18% w/w sodium sulfate, 18% w/w polyethylene glycol 4000, 1% w/w polyethylene glycol-iminodiacetic acid-Cu(2+) and pH 7, a maximum yield of 90.3% and a degree of purification of 3.6-fold were obtained. Compared to aqueous two phase extraction without ligands, affinity partitioning was found to be an effective technique for the purification of commercial papain with higher extraction efficiency and degree of purification.

  17. Electrolysis-induced protonation of VO2 thin film transistor for the metal-insulator phase modulation

    NASA Astrophysics Data System (ADS)

    Katase, Takayoshi; Endo, Kenji; Ohta, Hiromichi

    2016-02-01

    Compared to state-of-the-art modulation techniques, protonation is the most ideal to control the electrical and optical properties of transition metal oxides (TMOs) due to its intrinsic non-volatile operation. However, the protonation of TMOs is not typically utilized for solid-state devices because of imperative high-temperature annealing treatment in hydrogen source. Although one solution for room temperature (RT) protonation of TMOs is liquid-phase electrochemistry, it is unsuited for practical purposes due to liquid-leakage problem. Herein we demonstrate solid-state RT-protonation of vanadium dioxide (VO2), which is a well-known thermochromic TMO. We fabricated the three terminal thin-film-transistor structure on an insulating VO2 film using a water-infiltrated nanoporous glass, which serves as a solid electrolyte. For gate voltage application, water electrolysis and protonation/deprotonation of VO2 film surface occurred, leading to reversible metal-insulator phase conversion of ~11-nm-thick VO2 layer. The protonation was clearly accompanied by the structural change from an insulating monoclinic to a metallic tetragonal phase. Present results offer a new route for the development of electro-optically active solid-state devices with TMO materials by engineering RT protonation.

  18. Microalloying of transition metal silicides by mechanical activation and field-activated reaction

    DOEpatents

    Munir, Zuhair A.; Woolman, Joseph N.; Petrovic, John J.

    2003-09-02

    Alloys of transition metal suicides that contain one or more alloying elements are fabricated by a two-stage process involving mechanical activation as the first stage and densification and field-activated reaction as the second stage. Mechanical activation, preferably performed by high-energy planetary milling, results in the incorporation of atoms of the alloying element(s) into the crystal lattice of the transition metal, while the densification and field-activated reaction, preferably performed by spark plasma sintering, result in the formation of the alloyed transition metal silicide. Among the many advantages of the process are its ability to accommodate materials that are incompatible in other alloying methods.

  19. Semiconductor-to-metal phase change in MoTe2 layers (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Davydov, Albert V.; Krylyuk, Sergiy; Kalish, Irina; Meshi, Louisa; Beams, Ryan; Kalanyan, Berc; Sharma, Deepak K.; Beck, Megan; Bergeron, Hadallia; Hersam, Mark C.

    2016-09-01

    Molybdenum ditelluride (MoTe2), which can exist in a semiconducting prismatic hexagonal (2H) or a metallic distorted octahedral (1T') phases, is one of the very few materials that exhibit metal-semiconductor transition. Temperature-driven 2H - 1T' phase transition in bulk MoTe2 occurs at high temperatures (above 900 °C) and it is usually accompanied by Te loss. The latter can exacerbate the control over reversibility of the phase transition. Here, we study effects of high-temperature annealing on phase transition in MoTe2 single crystals. First, MoTe2 were grown in sealed evacuated quartz ampoules from polycrystalline MoTe2 powder in an iodine-assisted chemical vapor transport process at 1000 °C. The 2H and 1T' phases were stabilized by controlling the cooling rate after the growth. In particular, slow cooling at 10 °C/h rate yielded the 2H phase whereas the 1T' phase was stabilized by ice-water quenching. Next, the phase conversion was achieved by annealing MoTe2 single crystals in vacuum-sealed ampoules at 1000 °C with or without additional poly-MoTe2 powder followed by fast or slow cooling. Similarly to the CVT growth, slow cooling and quenching consistently produced 2H and 1T' phases, respectively, regardless of the initial MoTe2 crystal structure. We will discuss structural and optical properties of the as-grown and phase-converted MoTe2 single crystals using TEM, SEM/EDS, XRD, XPS and Raman. Electrical characteristics of two-terminal devices made from metallic 1T' and bottom-gated FETs made from 2H exfoliated crystals will also be presented.

  20. ALLOYING-DRIVEN PHASE STABILITY IN GROUP-VB TRANSITION METALS UNDER COMPRESSION

    SciTech Connect

    Landa, A; Soderlind, P

    2011-04-11

    The change in phase stability of Group-VB (V, Nb, and Ta) transition metals due to pressure and alloying is explored by means of first-principles electronic-structure calculations. It is shown that under compression stabilization or destabilization of the ground-state body-centered cubic (bcc) phase of the metal is mainly dictated by the band-structure energy that correlates well with the position of the Kohn anomaly in the transverse acoustic phonon mode. The predicted position of the Kohn anomaly in V, Nb, and Ta is found to be in a good agreement with data from the inelastic x-ray or neutron scattering measurements. In the case of alloying the change in phase stability is defined by the interplay between the band-structure and Madelung energies. We show that band-structure effects determine phase stability when a particular Group-VB metal is alloyed with its nearest neighbors within the same d-transition series: the neighbor with less and more d electrons destabilize and stabilize the bcc phase, respectively. When V is alloyed with neighbors of a higher (4d- or 5d-) transition series, both electrostatic Madelung and band-structure energies stabilize the body-centered-cubic phase. The opposite effect (destabilization) happens when Nb or Ta is alloyed with neighbors of the 3d-transition series.

  1. Precipitation of Niobium Boride Phases at the Base Metal/Weld Metal Interface in Dissimilar Weld Joints

    NASA Astrophysics Data System (ADS)

    Výrostková, Anna; Kepič, Ján; Homolová, Viera; Falat, Ladislav

    2015-07-01

    In this work, the analysis of failure mechanism in the heat affected zone is described in dissimilar weld joints between advanced martensitic steel T92 and Ni-base weld metal. The joints were treated with two different post-weld heat treatments and tested. For the creep, tensile, and Charpy impact tests, the samples with interfacially located notch were used. Moreover long term aging at 625 °C was applied before the tensile and notch toughness tests. Decohesion fractures ran along carbides at the T92 BM/WM interfaces in case of the modified PWHT, whereas type IV cracking was the prevailing failure mechanism after the classical PWHT in the creep test. In the notch tensile and Charpy impact tests, with the notch at T92 base metal/weld metal interface, fractures ran along the interface with a hard phase on the fracture surface along with the ductile dimple and brittle quasi-cleavage fracture. The phase identified as niobium boride (either NbB and/or Nb3B2) was produced during welding at the end of the solidification process. It was found in the welds regardless of the post-weld heat treatment and long-term aging.

  2. Phase engineering of monolayer transition-metal dichalcogenide through coupled electron doping and lattice deformation

    SciTech Connect

    Ouyang, Bin; Lan, Guoqiang; Song, Jun; Guo, Yinsheng; Mi, Zetian

    2015-11-09

    First-principles calculations were performed to investigate the phase stability and transition within four monolayer transition-metal dichalcogenide (TMD) systems, i.e., MX{sub 2} (M = Mo or W and X = S or Se) under coupled electron doping and lattice deformation. With the lattice distortion and electron doping density treated as state variables, the energy surfaces of different phases were computed, and the diagrams of energetically preferred phases were constructed. These diagrams assess the competition between different phases and predict conditions of phase transitions for the TMDs considered. The interplay between lattice deformation and electron doping was identified as originating from the deformation induced band shifting and band bending. Based on our findings, a potential design strategy combining an efficient electrolytic gating and a lattice straining to achieve controllable phase engineering in TMD monolayers was demonstrated.

  3. Phase diagram of the ultrafast photoinduced insulator-metal transition in vanadium dioxide

    NASA Astrophysics Data System (ADS)

    Cocker, T. L.; Titova, L. V.; Fourmaux, S.; Holloway, G.; Bandulet, H.-C.; Brassard, D.; Kieffer, J.-C.; El Khakani, M. A.; Hegmann, F. A.

    2012-04-01

    We use time-resolved terahertz spectroscopy to probe the ultrafast dynamics of the insulator-metal phase transition induced by femtosecond laser pulses in a nanogranular vanadium dioxide (VO2) film. Based on the observed thresholds for characteristic transient terahertz dynamics, a phase diagram of critical pump fluence versus temperature for the insulator-metal phase transition in VO2 is established for the first time over a broad range of temperatures down to 17 K. We find that both Mott and Peierls mechanisms are present in the insulating state and that the photoinduced transition is nonthermal. We propose a critical-threshold model for the ultrafast photoinduced transition based on a critical density of electrons and a critical density of coherently excited phonons necessary for the structural transition to the metallic state. As a result, evidence is found at low temperatures for an intermediate metallic state wherein the Mott state is melted but the Peierls distortion remains intact, consistent with recent theoretical predictions. Finally, the observed terahertz conductivity dynamics above the photoinduced transition threshold reveal nucleation and growth of metallic nanodomains over picosecond time scales.

  4. Nonergodic metallic and insulating phases of Josephson junction chains.

    PubMed

    Pino, Manuel; Ioffe, Lev B; Altshuler, Boris L

    2016-01-19

    Strictly speaking, the laws of the conventional statistical physics, based on the equipartition postulate [Gibbs J W (1902) Elementary Principles in Statistical Mechanics, developed with especial reference to the rational foundation of thermodynamics] and ergodicity hypothesis [Boltzmann L (1964) Lectures on Gas Theory], apply only in the presence of a heat bath. Until recently this restriction was believed to be not important for real physical systems because a weak coupling to the bath was assumed to be sufficient. However, this belief was not examined seriously until recently when the progress in both quantum gases and solid-state coherent quantum devices allowed one to study the systems with dramatically reduced coupling to the bath. To describe such systems properly one should revisit the very foundations of statistical mechanics. We examine this general problem for the case of the Josephson junction chain that can be implemented in the laboratory and show that it displays a novel high-temperature nonergodic phase with finite resistance. With further increase of the temperature the system undergoes a transition to the fully localized state characterized by infinite resistance and exponentially long relaxation.

  5. Nonergodic metallic and insulating phases of Josephson junction chains

    PubMed Central

    Pino, Manuel; Ioffe, Lev B.; Altshuler, Boris L.

    2016-01-01

    Strictly speaking, the laws of the conventional statistical physics, based on the equipartition postulate [Gibbs J W (1902) Elementary Principles in Statistical Mechanics, developed with especial reference to the rational foundation of thermodynamics] and ergodicity hypothesis [Boltzmann L (1964) Lectures on Gas Theory], apply only in the presence of a heat bath. Until recently this restriction was believed to be not important for real physical systems because a weak coupling to the bath was assumed to be sufficient. However, this belief was not examined seriously until recently when the progress in both quantum gases and solid-state coherent quantum devices allowed one to study the systems with dramatically reduced coupling to the bath. To describe such systems properly one should revisit the very foundations of statistical mechanics. We examine this general problem for the case of the Josephson junction chain that can be implemented in the laboratory and show that it displays a novel high-temperature nonergodic phase with finite resistance. With further increase of the temperature the system undergoes a transition to the fully localized state characterized by infinite resistance and exponentially long relaxation. PMID:26719416

  6. Anticancer Activity of Metal Complexes: Involvement of Redox Processes

    PubMed Central

    Jungwirth, Ute; Kowol, Christian R.; Keppler, Bernhard K.; Hartinger, Christian G.; Berger, Walter; Heffeter, Petra

    2012-01-01

    Cells require tight regulation of the intracellular redox balance and consequently of reactive oxygen species for proper redox signaling and maintenance of metal (e.g., of iron and copper) homeostasis. In several diseases, including cancer, this balance is disturbed. Therefore, anticancer drugs targeting the redox systems, for example, glutathione and thioredoxin, have entered focus of interest. Anticancer metal complexes (platinum, gold, arsenic, ruthenium, rhodium, copper, vanadium, cobalt, manganese, gadolinium, and molybdenum) have been shown to strongly interact with or even disturb cellular redox homeostasis. In this context, especially the hypothesis of “activation by reduction” as well as the “hard and soft acids and bases” theory with respect to coordination of metal ions to cellular ligands represent important concepts to understand the molecular modes of action of anticancer metal drugs. The aim of this review is to highlight specific interactions of metal-based anticancer drugs with the cellular redox homeostasis and to explain this behavior by considering chemical properties of the respective anticancer metal complexes currently either in (pre)clinical development or in daily clinical routine in oncology. PMID:21275772

  7. Activated Carbon Textile via Chemistry of Metal Extraction for Supercapacitors.

    PubMed

    Lam, Do Van; Jo, Kyungmin; Kim, Chang-Hyun; Kim, Jae-Hyun; Lee, Hak-Joo; Lee, Seung-Mo

    2016-12-27

    Carbothermic reduction in the chemistry of metal extraction (MO(s) + C(s) → M(s) + CO(g)) using carbon as a sacrificial agent has been used to smelt metals from diverse oxide ores since ancient times. Here, we paid attention to another aspect of the carbothermic reduction to prepare an activated carbon textile for high-rate-performance supercapacitors. On the basis of thermodynamic reducibility of metal oxides reported by Ellingham, we employed not carbon, but metal oxide as a sacrificial agent in order to prepare an activated carbon textile. We conformally coated ZnO on a bare cotton textile using atomic layer deposition, followed by pyrolysis at high temperature (C(s) + ZnO(s) → C'(s) + Zn(g) + CO(g)). We figured out that it leads to concurrent carbonization and activation in a chemical as well as mechanical way. Particularly, the combined effects of mechanical buckling and fracture that occurred between ZnO and cotton turned out to play an important role in carbonizing and activating the cotton textile, thereby significantly increasing surface area (nearly 10 times) compared with the cotton textile prepared without ZnO. The carbon textiles prepared by carbothermic reduction showed impressive combination properties of high power and energy densities (over 20-fold increase) together with high cyclic stability.

  8. Generation of copper rich metallic phases from waste printed circuit boards.

    PubMed

    Cayumil, R; Khanna, R; Ikram-Ul-Haq, M; Rajarao, R; Hill, A; Sahajwalla, V

    2014-10-01

    The rapid consumption and obsolescence of electronics have resulted in e-waste being one of the fastest growing waste streams worldwide. Printed circuit boards (PCBs) are among the most complex e-waste, containing significant quantities of hazardous and toxic materials leading to high levels of pollution if landfilled or processed inappropriately. However, PCBs are also an important resource of metals including copper, tin, lead and precious metals; their recycling is appealing especially as the concentration of these metals in PCBs is considerably higher than in their ores. This article is focused on a novel approach to recover copper rich phases from waste PCBs. Crushed PCBs were heat treated at 1150°C under argon gas flowing at 1L/min into a horizontal tube furnace. Samples were placed into an alumina crucible and positioned in the cold zone of the furnace for 5 min to avoid thermal shock, and then pushed into the hot zone, with specimens exposed to high temperatures for 10 and 20 min. After treatment, residues were pulled back to the cold zone and kept there for 5 min to avoid thermal cracking and re-oxidation. This process resulted in the generation of a metallic phase in the form of droplets and a carbonaceous residue. The metallic phase was formed of copper-rich red droplets and tin-rich white droplets along with the presence of several precious metals. The carbonaceous residue was found to consist of slag and ∼30% carbon. The process conditions led to the segregation of hazardous lead and tin clusters in the metallic phase. The heat treatment temperature was chosen to be above the melting point of copper; molten copper helped to concentrate metallic constituents and their separation from the carbonaceous residue and the slag. Inert atmosphere prevented the re-oxidation of metals and the loss of carbon in the gaseous fraction. Recycling e-waste is expected to lead to enhanced metal recovery, conserving natural resources and providing an environmentally

  9. An active metallic nanomatryushka with two similar super-resonances

    NASA Astrophysics Data System (ADS)

    Wu, D. J.; Cheng, Y.; Wu, X. W.; Liu, X. J.

    2014-07-01

    The optical properties of a simple metallic nanomatryushka (nanosphere-in-a-nanoshell) with gain have been investigated theoretically. The spaser (surface plasmon amplification by stimulated emission of radiation) phenomena can be observed at two critical wavelengths in the active metallic nanomatryushkas. With increasing the gain coefficient of the middle layer, a similar super surface plasmon (SP) resonance is first found at the ω-+|1 mode of the active nanoparticles and then breaks down. With further increasing the gain coefficient, another similar super-resonance occurs at the ω--|1 mode. The near-field enhancements in the active nanomatryushkas also have been greatly amplified at the critical wavelengths for ω-+|1 and ω--|1 modes. It is further found that the amplifications of SPs in the active Ag-SiO2-Au nanoshell are strongest in four kinds of nanoshells and hence the largest near fields. The giant near-field enhancement can greatly enhance the Raman excitation and emission.

  10. Aqueous phase sensing of cyanide ions using a hydrolytically stable metal-organic framework.

    PubMed

    Karmakar, Avishek; Joarder, Biplab; Mallick, Abhik; Samanta, Partha; Desai, Aamod V; Basu, Sudipta; Ghosh, Sujit K

    2017-01-19

    A pure aqueous phase recognition and corresponding detoxification of highly toxic cyanide ions has been achieved by a fluorescent metal-organic framework (MOF). The cyanide detoxification has been shown to be effective even in in vitro studies and the MOF could be recycled to show the same efficiency of detoxification.

  11. Why do disk galaxies present a common gas-phase metallicity gradient?

    NASA Astrophysics Data System (ADS)

    Chang, R.; Zhang, Shuhui; Shen, Shiyin; Yin, Jun; Hou, Jinliang

    2017-03-01

    CALIFA data show that isolated disk galaxies present a common gas-phase metallicity gradient, with a characteristic slope of -0.1dex/re between 0.3 and 2 disk effective radius re (Sanchez et al. 2014). Here we construct a simple model to investigate which processes regulate the formation and evolution.

  12. Laser opto-acoustic study of phase transitions in metals confined by transparent dielectric

    NASA Astrophysics Data System (ADS)

    Ivochkin, A. Yu.; Kaptilniy, A. G.; Karabutov, A. A.; Ksenofontov, D. M.

    2012-07-01

    First-order phase transitions in metal induced by nanosecond laser pulse are studied here. The metal surface is irradiated through a layer of transparent dielectric—an optical glass. Such confinement considerably increases the efficiency of pressure generation at the metal surface. This technique allows to obtain near-critical states of metals—with temperatures ˜104 K and pressures ˜104 atm with table-top equipment. At the same time the glass prevents the ablation plume formation—so the surface temperature can be measured using thermal radiation data. An experimental setup for simultaneous measurements of pressure, temperature and reflectivity was assembled based on the elaborated method of experimental research. The processes of melting of lead and boiling of mercury were studied. The onset of the phase transition process led to a considerable tightening of the pressure pulse. A substantial drop of surface reflectivity due to increase of temperature and decrease of density was observed.

  13. Spectral descriptors for bulk metallic glasses based on the thermodynamics of competing crystalline phases

    PubMed Central

    Perim, Eric; Lee, Dongwoo; Liu, Yanhui; Toher, Cormac; Gong, Pan; Li, Yanglin; Simmons, W. Neal; Levy, Ohad; Vlassak, Joost J.; Schroers, Jan; Curtarolo, Stefano

    2016-01-01

    Metallic glasses attract considerable interest due to their unique combination of superb properties and processability. Predicting their formation from known alloy parameters remains the major hindrance to the discovery of new systems. Here, we propose a descriptor based on the heuristics that structural and energetic ‘confusion' obstructs crystalline growth, and demonstrate its validity by experiments on two well-known glass-forming alloy systems. We then develop a robust model for predicting glass formation ability based on the geometrical and energetic features of crystalline phases calculated ab initio in the AFLOW framework. Our findings indicate that the formation of metallic glass phases could be much more common than currently thought, with more than 17% of binary alloy systems potential glass formers. Our approach pinpoints favourable compositions and demonstrates that smart descriptors, based solely on alloy properties available in online repositories, offer the sought-after key for accelerated discovery of metallic glasses. PMID:27480126

  14. Polarization conversion based on plasmonic phase control by an ultra-thin metallic nano-strips

    NASA Astrophysics Data System (ADS)

    Wei, Helei; Hu, Dejiao; Deng, Yunsheng; Wu, Xuannan; Xiao, Xiao; Hou, Yidong; Wang, Yunjiao; Shi, Ruiying; Wang, Deqiang; Du, Jinglei

    2016-12-01

    Ultra-thin metallic nano-strips (thinner than skin depth) can lead to anomalous reflection for a transverse magnetic (TM) incidence of some wave-lengths, due to the phase modulation of localized surface plasmon resonance. Based on the principle above, we proposed a method of polarization modulation using ultra-thin metallic nano-strips. When irradiating nano-strips vertically by light with a given polarized angle, we can utilize the phase difference of the TM transmission and transverse electric (TE) transmission near anomalous reflection region to modulate transmission polarization. We have designed and fabricated the ultra-thin metallic nano-strips with the function of quarter-wave plate, the attained transmission Stokes parameter S3 is 0.95. The nano-strips is easy to design and fabricate, also compatible with other optics devices, hence has the potential applications in integrated optics field.

  15. REVIEWS OF TOPICAL PROBLEMS: Properties of high pressure phases in metal-hydrogen systems

    NASA Astrophysics Data System (ADS)

    Ponyatovskiĭ, E. G.; Antonov, Vladimir E.; Belash, I. T.

    1982-08-01

    The development of high-pressure technology has in recent years permitted obtaining extensive new information on the properties of hydrides of group VI-VIII transition metals. In this review, the experimental procedures for compressing macroscopic quantities of hydrogen to record high pressures, phase transitions, and structures of new high-pressure phases in Me-H systems are briefly described. Special attention is devoted to the magnetic properties of solid solutions of hydrogen in 3d metals and their alloys, whose study has yielded definite conclusions concerning the effect of hydrogen on the band structure and exchange interaction in these materials. The role of structural instabilities in the formation of superconducting properties of hydrogen solutions in 4d metal alloys based on palladium is examined.

  16. Homochiral metal-organic framework used as a stationary phase for high-performance liquid chromatography.

    PubMed

    Kong, Jiao; Zhang, Mei; Duan, Ai-Hong; Zhang, Jun-Hui; Yang, Rui; Yuan, Li-Ming

    2015-02-01

    Metal-organic frameworks are promising porous materials. Chiral metal-organic frameworks have attracted considerable attention in controlling enantioselectivity. In this study, a homochiral metal-organic framework [Co(2) (D-cam)(2) (TMDPy)] (D-cam = D-camphorates, TMDPy = 4,4'-trimethylenedipyridine) with a non-interpenetrating primitive cubic net has been used as a chiral stationary phase in high-performance liquid chromatography. It has allowed the successful separation of six positional isomers and six chiral compounds. The good selectivity and baseline separation, or at least 60% valley separation, confirmed its excellent molecular recognition characteristics. The relative standard deviations for the retention time of run-to-run and column-to-column were less than 1.8 and 3.1%, respectively. These results demonstrate that [Co(2) (D-cam)(2) (TMDPy)] may represent a promising chiral stationary phase for use in high-performance liquid chromatography.

  17. New insights into hard phases of CoCrMo metal-on-metal hip replacements.

    PubMed

    Liao, Y; Pourzal, R; Stemmer, P; Wimmer, M A; Jacobs, J J; Fischer, A; Marks, L D

    2012-08-01

    The microstructural and mechanical properties of the hard phases in CoCrMo prosthetic alloys in both cast and wrought conditions were examined using transmission electron microscopy and nanoindentation. Besides the known carbides of M(23)C(6)-type (M=Cr, Mo, Co) and M(6)C-type which are formed by either eutectic solidification or precipitation, a new mixed-phase hard constituent has been found in the cast alloys, which is composed of ∼100 nm fine grains. The nanosized grains were identified to be mostly of M(23)C(6) type using nano-beam precession electron diffraction, and the chemical composition varied from grain to grain being either Cr- or Co-rich. In contrast, the carbides within the wrought alloy having the same M(23)C(6) structure were homogeneous, which can be attributed to the repeated heating and deformation steps. Nanoindentation measurements showed that the hardness of the hard phase mixture in the cast specimen was ∼15.7 GPa, while the M(23)C(6) carbides in the wrought alloy were twice as hard (∼30.7 GPa). The origin of the nanostructured hard phase mixture was found to be related to slow cooling during casting. Mixed hard phases were produced at a cooling rate of 0.2 °C/s, whereas single phase carbides were formed at a cooling rate of 50 °C/s. This is consistent with sluggish kinetics and rationalizes different and partly conflicting microstructural results in the literature, and could be a source of variations in the performance of prosthetic devices in-vivo.

  18. High-internal-phase emulsions stabilized by metal-organic frameworks and derivation of ultralight metal-organic aerogels

    PubMed Central

    Zhang, Bingxing; Zhang, Jianling; Liu, Chengcheng; Peng, Li; Sang, Xinxin; Han, Buxing; Ma, Xue; Luo, Tian; Tan, Xiuniang; Yang, Guanying

    2016-01-01

    To design high-internal-phase emulsion (HIPE) systems is of great interest from the viewpoints of both fundamental researches and practical applications. Here we demonstrate for the first time the utilization of metal-organic framework (MOF) for HIPE formation. By stirring the mixture of water, oil and MOF at room temperature, the HIPE stabilized by the assembly of MOF nanocrystals at oil-water interface could be formed. The MOF-stabilized HIPE provides a novel route to produce highly porous metal-organic aerogel (MOA) monolith. After removing the liquids from the MOF-stabilized HIPE, the ultralight MOA with density as low as 0.01 g·cm−3 was obtained. The HIPE approach for MOA formation has unique advantages and is versatile in producing different kinds of ultralight MOAs with tunable porosities and structures. PMID:26892258

  19. Competing dynamic phases of active polymer networks

    NASA Astrophysics Data System (ADS)

    Freedman, Simon; Banerjee, Shiladitya; Dinner, Aaron R.

    Recent experiments on in-vitro reconstituted assemblies of F-actin, myosin-II motors, and cross-linking proteins show that tuning local network properties can changes the fundamental biomechanical behavior of the system. For example, by varying cross-linker density and actin bundle rigidity, one can switch between contractile networks useful for reshaping cells, polarity sorted networks ideal for directed molecular transport, and frustrated networks with robust structural properties. To efficiently investigate the dynamic phases of actomyosin networks, we developed a coarse grained non-equilibrium molecular dynamics simulation of model semiflexible filaments, molecular motors, and cross-linkers with phenomenologically defined interactions. The simulation's accuracy was verified by benchmarking the mechanical properties of its individual components and collective behavior against experimental results at the molecular and network scales. By adjusting the model's parameters, we can reproduce the qualitative phases observed in experiment and predict the protein characteristics where phase crossovers could occur in collective network dynamics. Our model provides a framework for understanding cells' multiple uses of actomyosin networks and their applicability in materials research. Supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship (NDSEG) Program.

  20. Phase measurements of erythrocytes affected by metal ions with quantitative interferometric microscopy

    NASA Astrophysics Data System (ADS)

    Wang, Shouyu; Yan, Keding; Shan, Yanke; Xu, Mingfei; Liu, Fei; Xue, Liang

    2015-12-01

    Erythrocyte morphology is an important factor in disease diagnosis, however, traditional setups as microscopes and cytometers cannot provide enough quantitative information of cellular morphology for in-depth statistics and analysis. In order to capture variations of erythrocytes affected by metal ions, quantitative interferometric microscopy (QIM) is applied to monitor their morphology changes. Combined with phase retrieval and cell recognition, erythrocyte phase images, as well as phase area and volume, can be accurately and automatically obtained. The research proves that QIM is an effective tool in cellular observation and measurement.

  1. Hydrogen and Carbon Effects on Al2O3 Surface Phases and Metal Deposition

    NASA Astrophysics Data System (ADS)

    Wang, Xiao-Gang; Smith, John

    2005-03-01

    Effects of H and C impurities on α-Al2O3 (0001) surface stability and metal wetting behavior are determined from first principles[1]. The ab initio surface phase diagram for H and C on the alumina surface reveals six distinct surface phases. These different surface phases exhibit a variety of adhesion strengths with Cu and Co, and correspondingly different wetting behaviors. These results are consistent with the varied wetting characteristics observed experimentally. [1] Xiao-Gang Wang and John R. Smith, Phys. Rev. B70, Rapid communications, 081401 (2004).

  2. Phonons and phase stability in Ti-V approximants to gum metal

    NASA Astrophysics Data System (ADS)

    Hanlumyuang, Y.; Sankaran, R. P.; Sherburne, M. P.; Morris, J. W., Jr.; Chrzan, D. C.

    2012-04-01

    The stability of competing phases within body-centered-cubic Ti-V approximants to gum metal is considered from the perspective of phonon dispersion. Phonons are associated with the potential to form the ω and α'' phases. It is argued that alloys can be designed to be linearly stable with respect to the formation of both phases, even as the ideal shear strength approaches zero. The reduction in ideal strength is associated with softening of the phonons along Γ-N and is reflected in diffuse-scattering diffraction experiments.

  3. Consequences of abnormal CDK activity in S phase.

    PubMed

    Anda, Silje; Rothe, Christiane; Boye, Erik; Grallert, Beáta

    2016-01-01

    Cyclin Dependent Kinases (CDKs) are important regulators of DNA replication. In this work we have investigated the consequences of increasing or decreasing the CDK activity in S phase. To this end we identified S-phase regulators of the fission yeast CDK, Cdc2, and used appropriate mutants to modulate Cdc2 activity. In fission yeast Mik1 has been thought to be the main regulator of Cdc2 activity in S phase. However, we find that Wee1 has a major function in S phase and thus we used wee1 mutants to investigate the consequences of increased Cdc2 activity. These wee1 mutants display increased replication stress and, particularly in the absence of the S-phase checkpoint, accumulate DNA damage. Notably, more cells incorporate EdU in a wee1(-) strain as compared to wildtype, suggesting altered regulation of DNA replication. In addition, a higher number of cells contain chromatin-bound Cdc45, an indicator of active replication forks. In addition, we found that Cdc25 is required to activate Cdc2 in S phase and used a cdc25 mutant to explore a situation where Cdc2 activity is reduced. Interestingly, a cdc25 mutant has a higher tolerance for replication stress than wild-type cells, suggesting that reduced CDK activity in S phase confers resistance to at least some forms of replication stress.

  4. Basic Chad Arabic: The Active Phase.

    ERIC Educational Resources Information Center

    Absi, Samir Abu; Sinaud, Andre

    This third volume in the course on Chad Arabic emphasizes the active development of speaking skills in the target language. The active participation of the student requires imitation and induction of linguistic structures to a large extent. Some 45 units present grammatical material on gender, parts of speech, and verbs. Each unit contains a…

  5. Why do high-redshift galaxies show diverse gas-phase metallicity gradients?

    NASA Astrophysics Data System (ADS)

    Ma, Xiangcheng; Hopkins, Philip F.; Feldmann, Robert; Torrey, Paul; Faucher-Giguère, Claude-André; Kereš, Dušan

    2017-01-01

    Recent spatially resolved observations of galaxies at z ˜ 0.6-3 reveal that high-redshift galaxies show complex kinematics and a broad distribution of gas-phase metallicity gradients. To understand these results, we use a suite of high-resolution cosmological zoom-in simulations from the Feedback in Realistic Environments (FIRE) project, which include physically motivated models of the multi-phase ISM, star formation, and stellar feedback. Our simulations reproduce the observed diversity of kinematic properties and metallicity gradients, broadly consistent with observations at z ˜ 0-3. Strong negative metallicity gradients only appear in galaxies with a rotating disk, but not all rotationally supported galaxies have significant gradients. Strongly perturbed galaxies with little rotation always have flat gradients. The kinematic properties and metallicity gradient of a high-redshift galaxy can vary significantly on short time-scales, associated with starburst episodes. Feedback from a starburst can destroy the gas disk, drive strong outflows, and flatten a pre-existing negative metallicity gradient. The time variability of a single galaxy is statistically similar to the entire simulated sample, indicating that the observed metallicity gradients in high-redshift galaxies reflect the instantaneous state of the galaxy rather than the accretion and growth history on cosmological time-scales. We find weak dependence of metallicity gradient on stellar mass and specific star formation rate (sSFR). Low-mass galaxies and galaxies with high sSFR tend to have flat gradients, likely due to the fact that feedback is more efficient in these galaxies. We argue that it is important to resolve feedback on small scales in order to produce the diverse metallicity gradients observed.

  6. Phase transition and possible metallization in CeVO{sub 4} under pressure

    SciTech Connect

    Garg, Alka B.; Shanavas, K.V.; Wani, B.N.; Sharma, Surinder M.

    2013-07-15

    Phase stability of CeVO{sub 4} under pressure has been investigated using synchrotron based angle dispersive x-ray diffraction (ADXRD), electrical resistance and first principles calculations. The results indicate that the ambient zircon structure of the compound transforms to a low symmetry monoclinic monazite phase beyond 3.8 GPa with nearly 8.6% volume discontinuity. Beyond 11 GPa, the pattern could be fitted to a similar monazite structure which is about 12.7% denser and has a much larger monoclinic beta angle. On pressure release the first monoclinic phase is recovered. The electrical resistance data show a large drop in resistance with pressure indicating substantial narrowing down of the band gap. Electronic structure calculations support these observations and suggest possible pressure induced metallization in this material. - Pressure induced structural phase transition in CeVO{sub 4} as observed by x- ray diffraction (pressure vs. volume) and possible metallization in CeVO{sub 4} through electrical resistance and first principles electronic structure calculations. - Highlights: • Structural and electrical behavior of CeVO{sub 4} under pressure studied using x-ray diffraction and electrical resistance measurements and first principles calculations. • Two successive structural transitions confirmed by experiment and theory: zircon–monazite I–monazite II. • Band gap collapse and possible metallization is indicated by electrical resistance measurements and electronic structure calculations under pressure. • Novel observation of lower bulk modulus in the high pressure phase (both by experiment and calculations) explained through structural analysis.

  7. Nanoscale-phase-separated Pd-Rh boxes synthesized via metal migration: an archetype for studying lattice strain and composition effects in electrocatalysis.

    PubMed

    Sneed, Brian T; Brodsky, Casey N; Kuo, Chun-Hong; Lamontagne, Leo K; Jiang, Ying; Wang, Yong; Tao, Franklin Feng; Huang, Weixin; Tsung, Chia-Kuang

    2013-10-02

    Developing syntheses of more sophisticated nanostructures comprising late transition metals broadens the tools to rationally design suitable heterogeneous catalysts for chemical transformations. Herein, we report a synthesis of Pd-Rh nanoboxes by controlling the migration of metals in a core-shell nanoparticle. The Pd-Rh nanobox structure is a grid-like arrangement of two distinct metal phases, and the surfaces of these boxes are {100} dominant Pd and Rh. The catalytic behaviors of the particles were examined in electrochemistry to investigate strain effects arising from this structure. It was found that the trends in activity of model fuel cell reactions cannot be explained solely by the surface composition. The lattice strain emerging from the nanoscale separation of metal phases at the surface also plays an important role.

  8. High pressure phase-transformation induced texture evolution and strengthening in zirconium metal: Experiment and modeling

    DOE PAGES

    Yu, Xiaohui; Zhang, Ruifeng; Weldon, David; ...

    2015-07-28

    We studied the phase-transition induced texture changes and strengthening mechanism for zirconium metal under quasi-hydrostatic compression and uni-axial deformation under confined high pressure using the deformation-DIA (D-DIA) apparatus. It is shown that the experimentally obtained texture for ω-phase Zr can be qualitatively described by combining a subset of orientation variants previously proposed in two different models. The determined flow stress for the high-pressure ω-phase is 0.5–1.2 GPa, more than three times higher than that of the α-phase. Using first-principles calculations, we investigated the mechanical and electronic properties of the two Zr polymorphs. We find that the observed strengthening can bemore » attributed to the relatively strong directional bonding in the ω phase, which significantly increases its shear plastic resistance over the α-phase Zr. The present findings provide an alternate route for Zr metal strengthening by high-pressure phase transformation.« less

  9. High Pressure Phase-Transformation Induced Texture Evolution and Strengthening in Zirconium Metal: Experiment and Modeling

    PubMed Central

    Yu, Xiaohui; Zhang, Ruifeng; Weldon, David; Vogel, Sven C.; Zhang, Jianzhong; Brown, Donald W.; Wang, Yanbin; Reiche, Helmut M.; Wang, Shanmin; Du, Shiyu; Jin, Changqing; Zhao, Yusheng

    2015-01-01

    We studied the phase-transition induced texture changes and strengthening mechanism for zirconium metal under quasi-hydrostatic compression and uni-axial deformation under confined high pressure using the deformation-DIA (D-DIA) apparatus. It is shown that the experimentally obtained texture for ω-phase Zr can be qualitatively described by combining a subset of orientation variants previously proposed in two different models. The determined flow stress for the high-pressure ω-phase is 0.5–1.2 GPa, more than three times higher than that of the α-phase. Using first-principles calculations, we investigated the mechanical and electronic properties of the two Zr polymorphs. We find that the observed strengthening can be attributed to the relatively strong directional bonding in the ω phase, which significantly increases its shear plastic resistance over the α-phase Zr. The present findings provide an alternate route for Zr metal strengthening by high-pressure phase transformation. PMID:26218405

  10. High pressure phase-transformation induced texture evolution and strengthening in zirconium metal: Experiment and modeling

    SciTech Connect

    Yu, Xiaohui; Zhang, Ruifeng; Weldon, David; Vogel, Sven C.; Zhang, Jianzhong; Brown, Donald W.; Wang, Yanbin; Reiche, Helmut M.; Wang, Shanmin; Du, Shiyu; Jin, Changqing; Zhao, Yusheng

    2015-07-28

    We studied the phase-transition induced texture changes and strengthening mechanism for zirconium metal under quasi-hydrostatic compression and uni-axial deformation under confined high pressure using the deformation-DIA (D-DIA) apparatus. It is shown that the experimentally obtained texture for ω-phase Zr can be qualitatively described by combining a subset of orientation variants previously proposed in two different models. The determined flow stress for the high-pressure ω-phase is 0.5–1.2 GPa, more than three times higher than that of the α-phase. Using first-principles calculations, we investigated the mechanical and electronic properties of the two Zr polymorphs. We find that the observed strengthening can be attributed to the relatively strong directional bonding in the ω phase, which significantly increases its shear plastic resistance over the α-phase Zr. The present findings provide an alternate route for Zr metal strengthening by high-pressure phase transformation.

  11. Active Nematics Are Intrinsically Phase Separated

    NASA Astrophysics Data System (ADS)

    Mishra, Shradha; Ramaswamy, Sriram

    2006-09-01

    Two-dimensional nonequilibrium nematic steady states, as found in agitated granular-rod monolayers or films of orientable amoeboid cells, were predicted [Europhys. Lett. 62, 196 (2003)EULEEJ0295-507510.1209/epl/i2003-00346-7] to have giant number fluctuations, with the standard deviation proportional to the mean. We show numerically that the steady state of such systems is macroscopically phase separated, yet dominated by fluctuations, as in the Das-Barma model [Phys. Rev. Lett. 85, 1602 (2000)PRLTAO0031-900710.1103/PhysRevLett.85.1602]. We suggest experimental tests of our findings in granular and living-cell systems.

  12. Electronic Structure and Spin Configuration Trends of Single Transition Metal Impurity in Phase Change Material

    NASA Astrophysics Data System (ADS)

    Li, H.; Pei, J.; Shi, L. P.

    2016-10-01

    Fe doped phase change material GexSbyTez has shown experimentally the ability to alter its magnetic properties by phase change. This engineered spin degree of freedom into the phase change material offers the possibility of logic devices or spintronic devices where they may enable fast manipulation of ferromagnetism by a phase change mechanism. The electronic structures and spin configurations of isolated transition metal dopant in phase change material (iTM-PCM) is important to understand the interaction between localized metal d states and the unique delocalized host states of phase change material. Identifying an impurity center that has, in isolation, a nonvanishing magnetic moment is the first step to study the collective magnetic ordering, which originates from the interaction among close enough individual impurities. Theoretical description of iTM-PCM is challenging. In this work, we use a screened exchange hybrid functional to study the single 3d transition metal impurity in crystalline GeTe and GeSb2Te4. By curing the problem of local density functional (LDA) such as over-delocalization of the 3d states, we find that Fe on the Ge/Sb site has its majority d states fully occupied while its minority d states are empty, which is different from the previously predicted electronic configuration by LDA. From early transition metal Cr to heavier Ni, the majority 3d states are gradually populated until fully occupied and then the minority 3d states begin to be filled. Interpretive orbital interaction pictures are presented for understanding the local and total magnetic moments.

  13. Twelve Year Study of Underground Corrosion of Activated Metals

    SciTech Connect

    M. Kay Adler Flitton; Timothy S. Yoder

    2012-03-01

    The subsurface radioactive disposal facility located at the U.S. Department of Energy’s Idaho site contains neutron-activated metals from non-fuel nuclear-reactor-core components. A long-term corrosion study is being conducted to obtain site-specific corrosion rates to support efforts to more accurately estimate the transfer of activated elements in an arid vadose zone environment. The study uses non-radioactive metal coupons representing the prominent neutron-activated material buried at the disposal location, namely, two types of stainless steels, welded stainless steel, welded nickel-chromium steel alloy, zirconium alloy, beryllium, and aluminum. Additionally, carbon steel (the material used in cask disposal liners and other disposal containers) and duplex stainless steel (high-integrity containers) are also included in the study. This paper briefly describes the test program and presents the corrosion rate results through twelve years of underground exposure.

  14. Anticancer activity of Arkeshwara Rasa - A herbo-metallic preparation

    PubMed Central

    Nafiujjaman, Md; Nurunnabi, Md; Saha, Samir Kumar; Jahan, Rownak; Lee, Yong-kyu; Rahmatullah, Mohammed

    2015-01-01

    Introduction: Though metal based drugs have been prescribed in Ayurveda for centuries to treat various diseases, such as rheumatoid arthritis and cancer, toxicity of these drugs containing heavy metal is a great drawback for practical application. So, proper scientific validation of herbo-metallic drugs like Arkeshwara Rasa (AR) have become one of the focused research arena of new drugs against cancers. Aim: To investigate the in vitro anticancer effects of AR. Materials and Methods: Anticancer activity of AR was investigated on two human cancer cell lines, which represent two different tissues (pancreas and skin). Lactate dehydrogenase (LDH) assay for enzyme activity and trypan blue assay for cell morphology were performed for further confirmation. Results: AR showed potent activity against pancreatic cancer cells (MIA-PaCa-2). LDH activity confirmed that AR was active against pancreatic cancer cells. Finally, it was observed that AR exhibited significant effects on cancer cells due to synergistic effects of different compounds of AR. Conclusion: The study strongly suggests that AR has the potential to be an anticancer drug against pancreatic cancer. PMID:27313425

  15. Select metal adsorption by activated carbon made from peanut shells.

    PubMed

    Wilson, Kermit; Yang, Hong; Seo, Chung W; Marshall, Wayne E

    2006-12-01

    Agricultural by-products, such as peanut shells, contribute large quantities of lignocellulosic waste to the environment each growing season; but few, if any, value-added uses exist for their disposal. The objective of this study was to convert peanut shells to activated carbons for use in adsorption of select metal ions, namely, cadmium (Cd2+), copper (Cu2+), lead (Pb2+), nickel (Ni2+) and zinc (Zn2+). Milled peanut shells were pyrolyzed in an inert atmosphere of nitrogen gas, and then activated with steam at different activation times. Following pyrolysis and activation, the carbons underwent air oxidation. The prepared carbons were evaluated either for adsorption efficiency or adsorption capacity; and these parameters were compared to the same parameters obtained from three commercial carbons, namely, DARCO 12x20, NORIT C GRAN and MINOTAUR. One of the peanut shell-based carbons had metal ion adsorption efficiencies greater than two of the three commercial carbons but somewhat less than but close to Minotaur. This study demonstrates that peanut shells can serve as a source for activated carbons with metal ion-removing potential and may serve as a replacement for coal-based commercial carbons in applications that warrant their use.

  16. Open volume defects and magnetic phase transition in Fe60Al40 transition metal aluminide

    NASA Astrophysics Data System (ADS)

    Liedke, M. O.; Anwand, W.; Bali, R.; Cornelius, S.; Butterling, M.; Trinh, T. T.; Wagner, A.; Salamon, S.; Walecki, D.; Smekhova, A.; Wende, H.; Potzger, K.

    2015-04-01

    Magnetic phase transition in the Fe60Al40 transition metal aluminide from the ferromagnetic disordered A2-phase to the paramagnetic ordered B2-phase as a function of annealing up to 1000 °C has been investigated by means of magneto-optical and spectroscopy techniques, i.e., Kerr effect, positron annihilation, and Mössbauer spectroscopy. The positron annihilation spectroscopy has been performed in-situ sequentially after each annealing step at the Apparatus for In-situ Defect Analysis that is a unique tool combining positron annihilation spectroscopy with temperature treatment, material evaporation, ion irradiation, and sheet resistance measurement techniques. The overall goal was to investigate the importance of the open volume defects onto the magnetic phase transition. No evidence of variation in the vacancy concentration in matching the magnetic phase transition temperature range (400-600 °C) has been found, whereas higher temperatures showed an increase in the vacancy concentration.

  17. Association of soil organic matter with metal phases examined by selective dissolution approach: limitations and advantages

    NASA Astrophysics Data System (ADS)

    Wagai, R.; Mayer, L. M.

    2014-12-01

    Positive co-variation of organic matter (OM) with iron and aluminum phases has been known for decades in soil and, in case of OM-Fe, in marine sediments. More recent studies point to the metal control on the mean residence time of organic carbon in soils, suggesting that better understanding of the role of these metal phases and the nature of these organo-metal associations would help to improve the models of soil OM dynamics. We developed a selective dissolution approach to assess these associations (Wagai and Mayer, 2007; Wagai et al., 2013). By taking advantage of well-established extraction techniques that were targeted to dissolve specific metal and aluminosilicate phases in soil, we quantified the amounts of OM co-dissolved by the selective dissolution of these inorganic phases. The inherent limitations in this conceptually simple approach include the presence of C-based compounds (often as complexing agent for metal) in the extractants and the lack of selectivity when dissolving specific inorganic phases. The former was resolved by using nitrogen (N), instead of C, as a surrogate for OM because (i) soil N is mostly present as soil OM with relatively narrow C:N ratio, and (ii) the extractants are N free. We were able to partially overcome the lack of selectivity problem by comparing the co-dissolution of OM from a variety of extractants that use reductive, complexation, and acid/alkaline dissolutions. The potential advantages of our approach include the ability (i) to estimate the contribution of specific inorganic phases to OM stabilization, and (ii) to infer the possible modes of the organo-mineral associations that were extracted from field soils (e.g., adsorptive association vs. coprecipitation of organo-metallic complexes). In this presentation, we will further consider the advantages and limitations of this approach (e.g., methodological cautions), present some of the previous and new findings gained from this approach (including its application to

  18. Phase partitioning of trace metals in a contaminated estuary influenced by industrial effluent discharge.

    PubMed

    Wang, Wenhao; Wang, Wen-Xiong

    2016-07-01

    Severe trace metal pollution due to industrial effluents releases was found in Jiulong River Estuary, Southern China. In this study, water samples were collected during effluent release events to study the dynamic changes of environmental conditions and metal partitioning among dissolved, particulate and colloidal phases controlled by estuarine mixing. Intermittent effluent discharges during low tide caused decreasing pH and dissolved oxygen, and induced numerous suspended particulate materials and dissolved organic carbon to the estuary. Different behaviors of Cu, Zn, Ni, Cr and Pb in the dissolved fraction against the conservative index salinity indicated different sources, e.g., dissolved Ni from the intermittent effluent. Although total metal concentrations increased markedly following effluent discharges, Cu, Zn, Cr, Pb were predominated by the particulate fraction. Enhanced adsorption onto particulates in the mixing process resulted in elevated partitioning coefficient (Kd) values for Cu and Zn, and the particle concentration effect was not obvious under such anthropogenic impacts. Colloidal proportion of these metals (especially Cu and Zn) showed positive correlations with dissolved or colloidal organic carbon, suggesting the metal-organic complexation. However, the calculated colloidal partitioning coefficients were relatively constant, indicating the excess binding capacity. Overall, the intermittent effluent discharge altered the particulate/dissolved and colloidal/soluble phase partitioning process and may further influence the bioavailability and potential toxicity to aquatic organisms.

  19. H18 Carbon: A New Metallic Phase with sp2-sp3 Hybridized Bonding Network

    PubMed Central

    Zhao, Chun-Xiang; Niu, Chun-Yao; Qin, Zhi-Jie; Ren, Xiao Yan; Wang, Jian-Tao; Cho, Jun-Hyung; Jia, Yu

    2016-01-01

    Design and synthesis of three-dimensional metallic carbons are currently one of the hot issues in contemporary condensed matter physics because of their fascinating properties. Here, based on first-principles calculations, we discover a novel stable metallic carbon allotrope (termed H18 carbon) in () symmetry with a mixed sp2-sp3 hybridized bonding network. The dynamical stability of H18 carbon is verified by phonon mode analysis and molecular dynamics simulations, and its mechanical stability is analyzed by elastic constants, bulk modulus, and shear modulus. By simulating the x-ray diffraction patterns, we propose that H18 carbon would be one of the unidentified carbon phases observed in recent detonation experiments. The analysis of the band structure and density of states reveal that this new carbon phase has a metallic feature mainly due to the C atoms with sp2 hybridization. This novel 3D metallic carbon phase is anticipated to be useful for practical applications such as electronic and mechanical devices. PMID:26903234

  20. H18 Carbon: A New Metallic Phase with sp2-sp3 Hybridized Bonding Network.

    PubMed

    Zhao, Chun-Xiang; Niu, Chun-Yao; Qin, Zhi-Jie; Ren, Xiao Yan; Wang, Jian-Tao; Cho, Jun-Hyung; Jia, Yu

    2016-02-23

    Design and synthesis of three-dimensional metallic carbons are currently one of the hot issues in contemporary condensed matter physics because of their fascinating properties. Here, based on first-principles calculations, we discover a novel stable metallic carbon allotrope (termed H18 carbon) in () symmetry with a mixed sp(2)-sp(3) hybridized bonding network. The dynamical stability of H18 carbon is verified by phonon mode analysis and molecular dynamics simulations, and its mechanical stability is analyzed by elastic constants, bulk modulus, and shear modulus. By simulating the x-ray diffraction patterns, we propose that H18 carbon would be one of the unidentified carbon phases observed in recent detonation experiments. The analysis of the band structure and density of states reveal that this new carbon phase has a metallic feature mainly due to the C atoms with sp(2) hybridization. This novel 3D metallic carbon phase is anticipated to be useful for practical applications such as electronic and mechanical devices.

  1. Ligational behavior of Schiff bases towards transition metal ion and metalation effect on their antibacterial activity

    NASA Astrophysics Data System (ADS)

    Devi, Jai; Batra, Nisha; Malhotra, Rajesh

    2012-11-01

    New Schiff bases pyrazine-2-carboxylicacid (phenyl-pyridin-2-yl-methylene)-hydrazide (Hpch-bp) HL1 and pyrazine-2-carboxylicacid (pyridin-2-ylmethylene)-hydrazide (Hpch-pc) HL2 derived from condensation of pyrazine carboxylic hydrazide (Hpch) with 2-benzoyl pyridine (bp) or pyridine 2-carbaldehyde (pc) and their transition metal complexes of type ML(1-2)2 have been synthesized, where M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). Characterization of ligands and their metal complexes was carried out by elemental analysis, conductimetric studies, magnetic susceptibility, spectroscopic techniques (IR, UV-VIS, NMR, ESR, Mass) and thermogravimetric analysis. The physico-chemical studies revealed octahedral geometry or distorted octahedral geometry around metal ion. These azomethine Schiff base ligands acted as tridentate ? coordinating through carbonyl, azomethine and pyridine nitrogen present in the ligand. The thermodynamic and thermal properties of the complexes have been investigated and it was observed on the basis of these studies that thermal stability of complexes follows the order Mn < Zn < Cu < Co < Ni. The ligands and their complexes were tested for in vitro antibacterial activity at different concentrations against bacteria viz. Gram positive Bacillus subtilis, Micrococcus luteus and Gram negative Pseudomonas aeruginosa, Pseudomonas mendocina. A marked enhancement in biocidal activity of the ligands under similar experimental conditions was observed as a consequence of coordination with metal ions. The trend of growth inhibition in the complexes was found to be in the order: Cu > Mn > Ni > Co > Zn.

  2. Optical waveguide loss minimized into gallium nitride based structures grown by metal organic vapor phase epitaxy

    NASA Astrophysics Data System (ADS)

    Stolz, A.; Cho, E.; Dogheche, E.; Androussi, Y.; Troadec, D.; Pavlidis, D.; Decoster, D.

    2011-04-01

    The waveguide properties are reported for wide bandgap gallium nitride (GaN) structures grown by metal organic vapor phase epitaxy on sapphire using a AlN/GaN short period-superlattice (SPS) buffer layer system. A detailed optical characterization of GaN structures has been performed using the prism coupling technique in order to evaluate its properties and, in particular, the refractive index dispersion and the propagation loss. In order to identify the structural defects in the samples, we performed transmission electron microscopy analysis. The results suggest that AlN/GaN SPS plays a role in acting as a barrier to the propagation of threading dislocations in the active GaN epilayer; above this defective region, the dislocations density is remarkably reduced. The waveguide losses were reduced to a value around 0.65dB/cm at 1.55 μm, corresponding to the best value reported so far for a GaN-based waveguide.

  3. Automatic In-Syringe Dispersive Microsolid Phase Extraction Using Magnetic Metal-Organic Frameworks.

    PubMed

    Maya, Fernando; Palomino Cabello, Carlos; Estela, Jose Manuel; Cerdà, Víctor; Turnes Palomino, Gemma

    2015-08-04

    A novel automatic strategy for the use of micro- and nanomaterials as sorbents for dispersive microsolid phase extraction (D-μ-SPE) based on the lab-in-syringe concept is reported. Using the developed technique, the implementation of magnetic metal-organic framework (MOF) materials for automatic solid-phase extraction has been achieved for the first time. A hybrid material based on submicrometric MOF crystals containing Fe3O4 nanoparticles was prepared and retained in the surface of a miniature magnetic bar. The magnetic bar was placed inside the syringe of an automatic bidirectional syringe pump, enabling dispersion and subsequent magnetic retrieval of the MOF hybrid material by automatic activation/deactivation of magnetic stirring. Using malachite green (MG) as a model adsorption analyte, a limit of detection of 0.012 mg/L and a linear working range of 0.04-2 mg/L were obtained for a sample volume equal to the syringe volume (5 mL). MG preconcentration was linear up to a volume of 40 mL, obtaining an enrichment factor of 120. The analysis throughput is 18 h(-1), and up to 3000 extractions/g of material can be performed. Recoveries ranging between 95 and 107% were obtained for the analysis of MG in different types of water and trout fish samples. The developed automatic D-μ-SPE technique is a safe alternative for the use of small-sized materials for sample preparation and is readily implementable to other magnetic materials independent of their size and shape and can be easily hyphenated to the majority of detectors and separation techniques.

  4. Metal nanoparticles in liquid phase catalysis; from recent advances to future goals.

    PubMed

    Zahmakıran, Mehmet; Ozkar, Saim

    2011-09-01

    Metal nanoparticles have attracted much attention over the last decade owing to their unique properties, different to their bulk counterparts, which pave the way for their application in different fields from materials science and engineering to biomedical applications. Of particular interest, the use of metal nanoparticles in catalysis has brought superior efficiency in terms of activity, selectivity and lifetime to heterogeneous catalysis. This article reviews the recent developments in the synthesis routes and the catalytic performance of metal nanoparticles depending on the solvent used for various organic and inorganic transformations. Additionally, we also discuss the prevalent complications and their possible solutions plus future prospects in the field of nanocatalysis.

  5. A New Process for Hot Metal Production at Low Fuel Rate - Phase 1 Feasibility Study

    SciTech Connect

    Dr. Wei-Kao Lu

    2006-02-01

    The project is part of the continuing effort by the North American steel industry to develop a coal-based, cokeless process for hot metal production. The objective of Phase 1 is to determine the feasibility of designing and constructing a pilot scale facility with the capacity of 42,000 mtpy of direct reduced iron (DRI) with 95% metallization. The primary effort is performed by Bricmont, Inc., an international engineering firm, under the supervision of McMaster University. The study focused on the Paired Straight Hearth furnace concept developed previously by McMaster University, The American Iron and Steel Institute and the US Department of Energy.

  6. Magnetic Fluctuations in Metallic and Insulating Phases of V_2O_3

    NASA Astrophysics Data System (ADS)

    Bao, Wei

    1996-03-01

    V_2O3 is a canonical Mott system where strong correlations among electrons drive spectacular metal-insulator transitions. Metallic V_2O3 has served as a prototype of the Brinkman-Rice strongly correlated Fermi liquid. Research in Mott-Hubbard systems has largely focused on charge dynamics. Spin dynamics on both sides of the Mott transition are often described in terms of localized spin fluctuations on the grounds that electrons in the metallic state are nearly localized. Using magnetic neutron scattering, an incommensurate spin density wave, resulting from a Fermi surface instability, was discovered in the metallic state at low temperatures(W. Bao, C. Broholm, S. A. Carter, T. F. Rosenbaum, G. Aeppli, S. F. Trevino, P. Metcalf, J. M. Honig and J. Spalek, Phys. Rev. Lett. 71), 766 (1993).. Energetic spin fluctuations (hbar ω > 20 k T_N) with large spectral weight (int^18meV M^2(ω) > 4M_0^2) were observed throughout the metallic phases, reflecting the itinerant nature of magnetism in metallic V_2O3 even on the verge of the Mott transition. Spin fluctuations in the paramagnetic insulating phase were found to be related to those of the metallic state rather than to the antiferromagnetic order of insulating V_2O3 at low temperatures. Spin correlation in the paramagnetic insulator are limited to nearest neighbors even in the immediate vicinity of T_N. This result cannot be understood in terms of a conventional spin hamiltonian and points to the importance of orbital fluctuations in V_2O_3.

  7. Anaerobic bioleaching of metals from waste activated sludge.

    PubMed

    Meulepas, Roel J W; Gonzalez-Gil, Graciela; Teshager, Fitfety Melese; Witharana, Ayoma; Saikaly, Pascal E; Lens, Piet N L

    2015-05-01

    Heavy metal contamination of anaerobically digested waste activated sludge hampers its reuse as fertilizer or soil conditioner. Conventional methods to leach metals require aeration or the addition of leaching agents. This paper investigates whether metals can be leached from waste activated sludge during the first, acidifying stage of two-stage anaerobic digestion without the supply of leaching agents. These leaching experiments were done with waste activated sludge from the Hoek van Holland municipal wastewater treatment plant (The Netherlands), which contained 342 μg g(-1) of copper, 487 μg g(-1) of lead, 793 μg g(-1) of zinc, 27 μg g(-1) of nickel and 2.3 μg g(-1) of cadmium. During the anaerobic acidification of 3 gdry weight L(-1) waste activated sludge, 80-85% of the copper, 66-69% of the lead, 87% of the zinc, 94-99% of the nickel and 73-83% of the cadmium were leached. The first stage of two-stage anaerobic digestion can thus be optimized as an anaerobic bioleaching process and produce a treated sludge (i.e., digestate) that meets the land-use standards in The Netherlands for copper, zinc, nickel and cadmium, but not for lead.

  8. Hidden amorphous phase and reentrant supercooled liquid in Pd-Ni-P metallic glasses.

    PubMed

    Lan, S; Ren, Y; Wei, X Y; Wang, B; Gilbert, E P; Shibayama, T; Watanabe, S; Ohnuma, M; Wang, X-L

    2017-03-17

    An anomaly in differential scanning calorimetry has been reported in a number of metallic glass materials in which a broad exothermal peak was observed between the glass and crystallization temperatures. The mystery surrounding this calorimetric anomaly is epitomized by four decades long studies of Pd-Ni-P metallic glasses, arguably the best glass-forming alloys. Here we show, using a suite of in situ experimental techniques, that Pd-Ni-P alloys have a hidden amorphous phase in the supercooled liquid region. The anomalous exothermal peak is the consequence of a polyamorphous phase transition between two supercooled liquids, involving a change in the packing of atomic clusters over medium-range length scales as large as 18 Å. With further temperature increase, the alloy reenters the supercooled liquid phase, which forms the room-temperature glass phase on quenching. The outcome of this study raises a possibility to manipulate the structure and hence the stability of metallic glasses through heat treatment.

  9. Hidden amorphous phase and reentrant supercooled liquid in Pd-Ni-P metallic glasses

    PubMed Central

    Lan, S.; Ren, Y.; Wei, X. Y.; Wang, B.; Gilbert, E. P.; Shibayama, T.; Watanabe, S.; Ohnuma, M.; Wang, X. -L.

    2017-01-01

    An anomaly in differential scanning calorimetry has been reported in a number of metallic glass materials in which a broad exothermal peak was observed between the glass and crystallization temperatures. The mystery surrounding this calorimetric anomaly is epitomized by four decades long studies of Pd-Ni-P metallic glasses, arguably the best glass-forming alloys. Here we show, using a suite of in situ experimental techniques, that Pd-Ni-P alloys have a hidden amorphous phase in the supercooled liquid region. The anomalous exothermal peak is the consequence of a polyamorphous phase transition between two supercooled liquids, involving a change in the packing of atomic clusters over medium-range length scales as large as 18 Å. With further temperature increase, the alloy reenters the supercooled liquid phase, which forms the room-temperature glass phase on quenching. The outcome of this study raises a possibility to manipulate the structure and hence the stability of metallic glasses through heat treatment. PMID:28303882

  10. A Transition to Metallic Hydrogen: Evidence of the Plasma Phase Transition

    NASA Astrophysics Data System (ADS)

    Silvera, Isaac; Zaghoo, Mohamed; Salamat, Ashkan

    The insulator-metal transition in hydrogen is one of the most outstanding problems in condensed matter physics. The high-pressure metallic phase is now predicted to be liquid atomic from T =0 K to very high temperatures. We have conducted measurements of optical properties of hot dense hydrogen in the region of 1.1-1.7 Mbar and up to 2200 K in a diamond anvil cell using pulsed laser heating of the sample. We present evidence in two forms: a plateau in the heating curves (average laser power vs temperature) characteristic of a first-order phase transition with latent heat, and changes in transmittance and reflectance characteristic of a metal for temperatures above the plateau temperature. For thick films the reflectance saturates at ~0.5. The phase line of this transition has a negative slope in agreement with theories of the so-called plasma phase transition. The NSF, Grant DMR-1308641, the DOE Stockpile Stewardship Academic Alliance Program, Grant DE-FG52-10NA29656, and NASA Earth and Space Science Fellowship Program, Award NNX14AP17H supported this research.

  11. A theoretical study of the omega-phase transformation in metals

    NASA Astrophysics Data System (ADS)

    Sanati, Mahdi

    I have studied the formation of o-phase from electronic and mesoscopic (domain wall) points of view. To study the formation of domain walls, I have extended the Landau model of Cook for the o-phase transition by including a spatial gradient (Ginzburg) term of the scalar order parameter. In general, the Landau free energy is an asymmetric double-well potential. From the variational derivative of the total free energy I obtained a static equilibrium condition. By solving this equation for different physical parameters and boundary conditions, I obtained different quasi-one-dimensional soliton-like solutions. These solutions correspond to three different types of domain walls between the o-phase and the beta-matrix. These results are used to model the formation of the o-phase in bcc Ti. Canonical band model and first principles calculations confirmed the instability of the bcc-phase of group III and IV transition metals with respect to the o-phase transformation. I showed that the d-electron density is the controlling parameter for this type of the transformation. Also the possibility of formation of the o-phase for rare earth metals is discussed. First-principles full-potential linear muffin-tin orbital method (FPLMTO) calculations are performed for o-type displacement of the atoms to study the formation of the o-phase in TiAl and Ti 3Al2Nb alloys. The results of my calculations showed an instability in ordered B2 TiAl structure with respect to the o-phase when one third of the Al atoms are replaced by Nb atoms. These phenomena are explained, first by symmetry arguments; then a pair potential model is used to illustrate this instability based on interactions between different pair of atoms derived from the electronic structure. In addition, importance of the atomic arrangements on the structural stability of the Ti3Al2 Nb system is discussed.

  12. Defect-Stabilized Phases in Extensile Active Nematics

    NASA Astrophysics Data System (ADS)

    Redner, Gabriel; Decamp, Stephen; Dogic, Zvonimir; Hagan, Michael

    2015-03-01

    Active nematics are liquid crystals which are driven out of equilibrium by energy-dissipating active stresses. The equilibrium nematic state is unstable in these materials, leading to beautiful and surprising behaviors including the spontaneous generation of topological defect pairs which stream through the system and later annihilate, yielding a complex, seemingly chaotic dynamical steady-state. In this talk, I will describe the emergence of order from this chaos in the form of previously unknown broken-symmetry phases in which the topological defects themselves undergo orientational ordering. We have identified these defect-ordered phases in two realizations of an active nematic: first, a suspension of extensile bundles of microtubules and molecular motor proteins, and second, a computational model of extending hard rods. I will describe the defect-stabilized phases that manifest in these systems, our current understanding of their origins, and discuss whether such phases may be a general feature of extensile active nematics.

  13. Active directional switching of surface plasmon polaritons using a phase transition material

    NASA Astrophysics Data System (ADS)

    Kim, Sun-Je; Yun, Hansik; Park, Kyungsoo; Hong, Jongwoo; Yun, Jeong-Geun; Lee, Kyookeun; Kim, Joonsoo; Jeong, Sun Jae; Mun, Sang-Eun; Sung, Jangwoon; Lee, Yong Wook; Lee, Byoungho

    2017-03-01

    Active switching of near-field directivity, which is an essential functionality for compact integrated photonics and small optoelectronic elements, has been challenging due to small modulation depth and complicated fabrication methods for devices including active optical materials. Here, we theoretically and experimentally realize a nanoscale active directional switching of surface plasmon polaritons (SPPs) using a phase transition material for the first time. The SPP switching device with noticeable distinction is demonstrated based on the phase transition of vanadium dioxide (VO2) at the telecom wavelength. As the insulator-to-metal phase transition (IMT) of VO2 induces the large change of VO2 permittivity at telecom wavelengths, the plasmonic response of a nanoantenna made of VO2 can be largely tuned by external thermal stimuli. The VO2-insulator-metal (VIM) nanoantenna and its periodic array, the VIM metagrating, are suggested as optical switches. The directional power distinction ratio is designed to change from 8.13:1 to 1:10.56 by the IMT and it is experimentally verified that the ratio changes from 3.725:1 to 1:3.132 as the VIM metagratings are heated up to 90 °C. With an electro-thermally controllable configuration and an optimized resonant design, we expect potential applications of the active switching mechanism for integrable active plasmonic elements and reconfigurable imaging.

  14. Active directional switching of surface plasmon polaritons using a phase transition material

    PubMed Central

    Kim, Sun-Je; Yun, Hansik; Park, Kyungsoo; Hong, Jongwoo; Yun, Jeong-Geun; Lee, Kyookeun; Kim, Joonsoo; Jeong, Sun Jae; Mun, Sang-Eun; Sung, Jangwoon; Lee, Yong Wook; Lee, Byoungho

    2017-01-01

    Active switching of near-field directivity, which is an essential functionality for compact integrated photonics and small optoelectronic elements, has been challenging due to small modulation depth and complicated fabrication methods for devices including active optical materials. Here, we theoretically and experimentally realize a nanoscale active directional switching of surface plasmon polaritons (SPPs) using a phase transition material for the first time. The SPP switching device with noticeable distinction is demonstrated based on the phase transition of vanadium dioxide (VO2) at the telecom wavelength. As the insulator-to-metal phase transition (IMT) of VO2 induces the large change of VO2 permittivity at telecom wavelengths, the plasmonic response of a nanoantenna made of VO2 can be largely tuned by external thermal stimuli. The VO2-insulator-metal (VIM) nanoantenna and its periodic array, the VIM metagrating, are suggested as optical switches. The directional power distinction ratio is designed to change from 8.13:1 to 1:10.56 by the IMT and it is experimentally verified that the ratio changes from 3.725:1 to 1:3.132 as the VIM metagratings are heated up to 90 °C. With an electro-thermally controllable configuration and an optimized resonant design, we expect potential applications of the active switching mechanism for integrable active plasmonic elements and reconfigurable imaging. PMID:28262702

  15. Active directional switching of surface plasmon polaritons using a phase transition material.

    PubMed

    Kim, Sun-Je; Yun, Hansik; Park, Kyungsoo; Hong, Jongwoo; Yun, Jeong-Geun; Lee, Kyookeun; Kim, Joonsoo; Jeong, Sun Jae; Mun, Sang-Eun; Sung, Jangwoon; Lee, Yong Wook; Lee, Byoungho

    2017-03-06

    Active switching of near-field directivity, which is an essential functionality for compact integrated photonics and small optoelectronic elements, has been challenging due to small modulation depth and complicated fabrication methods for devices including active optical materials. Here, we theoretically and experimentally realize a nanoscale active directional switching of surface plasmon polaritons (SPPs) using a phase transition material for the first time. The SPP switching device with noticeable distinction is demonstrated based on the phase transition of vanadium dioxide (VO2) at the telecom wavelength. As the insulator-to-metal phase transition (IMT) of VO2 induces the large change of VO2 permittivity at telecom wavelengths, the plasmonic response of a nanoantenna made of VO2 can be largely tuned by external thermal stimuli. The VO2-insulator-metal (VIM) nanoantenna and its periodic array, the VIM metagrating, are suggested as optical switches. The directional power distinction ratio is designed to change from 8.13:1 to 1:10.56 by the IMT and it is experimentally verified that the ratio changes from 3.725:1 to 1:3.132 as the VIM metagratings are heated up to 90 °C. With an electro-thermally controllable configuration and an optimized resonant design, we expect potential applications of the active switching mechanism for integrable active plasmonic elements and reconfigurable imaging.

  16. Hydrogen-Induced Phase Transformations: a Base for a New Sphere of the Science of Metals (an Analytical Review)

    NASA Astrophysics Data System (ADS)

    Goltsov, V. A.

    2017-03-01

    Data on the phase transformations induced in metals by hydrogen are generalized and analyzed. It is suggested to classify hydrogen-induced phase transformations on the basis of allowance for the temperature dependence of the parameters of diffusion of substitutional and interstitial (hydrogen) atoms like in the classical science of metals. A pioneer classification of hydrogen-induced phase transformations by this method is developed.

  17. Liquid-phase extraction coupled with metal-organic frameworks-based dispersive solid phase extraction of herbicides in peanuts.

    PubMed

    Li, Na; Wang, Zhibing; Zhang, Liyuan; Nian, Li; Lei, Lei; Yang, Xiao; Zhang, Hanqi; Yu, Aimin

    2014-10-01

    Liquid-phase extraction coupled with metal-organic frameworks-based dispersive solid phase extraction was developed and applied to the extraction of pesticides in high fatty matrices. The herbicides were ultrasonically extracted from peanut using ethyl acetate as extraction solvent. The separation of the analytes from a large amount of co-extractive fat was achieved by dispersive solid-phase extraction using MIL-101(Cr) as sorbent. In this step, the analytes were adsorbed on MIL-101(Cr) and the fat remained in bulk. The herbicides were separated and determined by high-performance liquid chromatography. The experimental parameters, including type and volume of extraction solvent, ultrasonication time, volume of hexane and eluting solvent, amount of MIL-101(Cr) and dispersive solid phase extraction time, were optimized. The limits of detection for herbicides range from 0.98 to 1.9 μg/kg. The recoveries of the herbicides are in the range of 89.5-102.7% and relative standard deviations are equal or lower than 7.0%. The proposed method is simple, effective and suitable for treatment of the samples containing high content of fat.

  18. Role of sediment resuspension in the remobilization of particulate-phase metals from coastal sediments

    USGS Publications Warehouse

    Kalnejais, Linda H.; Martin, William R.; Signell, Richard P.; Bothner, Michael H.

    2007-01-01

    The release of particulate-phase trace metals due to sediment resuspension has been investigated by combining erosion chamber experiments that apply a range of shear stresses typically encountered in coastal environments with a shear stress record simulated by a hydrodynamic model. Two sites with contrasting sediment chemistry were investigated. Sediment particles enriched in silver, copper, and lead, 4−50 times greater than the bulk surface-sediment content, were the first particles to be eroded. As the shear-stress level was increased in the chamber, the total mass eroded increased, but the enrichment of these trace metals fell, approaching the bulk-sediment content. From the temporal distribution of shear stress generated by the hydrodynamic model for a site in Boston Harbor, resuspension fluxes were estimated. The erosion threshold of this site is exceeded during spring tides, releasing the particles enriched in trace metals into the water column. Due to the higher trace metal content and the regularity of resuspension, low-energy resuspension events (up to a shear stress of 0.2 N/m2) contribute up to 60% of the resuspension metal flux in an average year. The estimated annual quantity of copper and lead resuspended into the water column is higher than estimates of the total riverine flux for these metals. These results indicate that sediment resuspension is a very important mechanism for releasing metals into the water column and provide new insight into the chemical and physical processes controlling the long-term fate of trace metals in contaminated sediments.

  19. Phase equilibrium modeling for high temperature metallization on GaAs solar cells

    NASA Technical Reports Server (NTRS)

    Chung, M. A.; Davison, J. E.; Smith, S. R.

    1991-01-01

    Recent trends in performance specifications and functional requirements have brought about the need for high temperature metallization technology to be developed for survivable DOD space systems and to enhance solar cell reliability. The temperature constitution phase diagrams of selected binary and ternary systems were reviewed to determine the temperature and type of phase transformation present in the alloy systems. Of paramount interest are the liquid-solid and solid-solid transformations. Data are being utilized to aid in the selection of electrical contact materials to gallium arsenide solar cells. Published data on the phase diagrams for binary systems is readily available. However, information for ternary systems is limited. A computer model is being developed which will enable the phase equilibrium predictions for ternary systems where experimental data is lacking.

  20. Striped nanoscale phase separation at the metal-insulator transition of heteroepitaxial nickelates.

    PubMed

    Mattoni, G; Zubko, P; Maccherozzi, F; van der Torren, A J H; Boltje, D B; Hadjimichael, M; Manca, N; Catalano, S; Gibert, M; Liu, Y; Aarts, J; Triscone, J-M; Dhesi, S S; Caviglia, A D

    2016-11-02

    Nucleation processes of mixed-phase states are an intrinsic characteristic of first-order phase transitions, typically related to local symmetry breaking. Direct observation of emerging mixed-phase regions in materials showing a first-order metal-insulator transition (MIT) offers unique opportunities to uncover their driving mechanism. Using photoemission electron microscopy, we image the nanoscale formation and growth of insulating domains across the temperature-driven MIT in NdNiO3 epitaxial thin films. Heteroepitaxy is found to strongly determine the nanoscale nature of the phase transition, inducing preferential formation of striped domains along the terraces of atomically flat stepped surfaces. We show that the distribution of transition temperatures is a local property, set by surface morphology and stable across multiple temperature cycles. Our data provide new insights into the MIT of heteroepitaxial nickelates and point to a rich, nanoscale phenomenology in this strongly correlated material.

  1. Striped nanoscale phase separation at the metal-insulator transition of heteroepitaxial nickelates

    NASA Astrophysics Data System (ADS)

    Mattoni, G.; Zubko, P.; Maccherozzi, F.; van der Torren, A. J. H.; Boltje, D. B.; Hadjimichael, M.; Manca, N.; Catalano, S.; Gibert, M.; Liu, Y.; Aarts, J.; Triscone, J.-M.; Dhesi, S. S.; Caviglia, A. D.

    2016-11-01

    Nucleation processes of mixed-phase states are an intrinsic characteristic of first-order phase transitions, typically related to local symmetry breaking. Direct observation of emerging mixed-phase regions in materials showing a first-order metal-insulator transition (MIT) offers unique opportunities to uncover their driving mechanism. Using photoemission electron microscopy, we image the nanoscale formation and growth of insulating domains across the temperature-driven MIT in NdNiO3 epitaxial thin films. Heteroepitaxy is found to strongly determine the nanoscale nature of the phase transition, inducing preferential formation of striped domains along the terraces of atomically flat stepped surfaces. We show that the distribution of transition temperatures is a local property, set by surface morphology and stable across multiple temperature cycles. Our data provide new insights into the MIT of heteroepitaxial nickelates and point to a rich, nanoscale phenomenology in this strongly correlated material.

  2. Dynamical Piezoelectric and Magnetopiezoelectric Effects in Polar Metals from Berry Phases and Orbital Moments

    NASA Astrophysics Data System (ADS)

    Varjas, Dániel; Grushin, Adolfo G.; Ilan, Roni; Moore, Joel E.

    2016-12-01

    The polarization of a material and its response to applied electric and magnetic fields are key solid-state properties with a long history in insulators, although a satisfactory theory required new concepts such as Berry-phase gauge fields. In metals, quantities such as static polarization and the magnetoelectric θ term cease to be well defined. In polar metals, there can be analogous dynamical current responses, which we study in a common theoretical framework. We find that current responses to dynamical strain in polar metals depend on both the first and second Chern forms, related to polarization and magnetoelectricity in insulators as well as the orbital magnetization on the Fermi surface. We provide realistic estimates that predict that the latter contribution will dominate, and we investigate the feasibility of experimental detection of this effect.

  3. Phase transition and metallization of FeO at high pressures and temperatures

    SciTech Connect

    Fischer, Rebecca A.; Campbell, Andrew J.; Lord, Oliver T.; Shofner, Gregory A.; Dera, Przemyslaw; Prakapenka, Vitali B.

    2012-05-10

    Wuestite, Fe{sub 1-x}O, is an important component in the mineralogy of Earth's lower mantle and may also be a component of the core. Therefore its high pressure-temperature behavior, including its electronic structure, is essential to understanding the nature and evolution of Earth's deep interior. We performed X-ray diffraction and radiometric measurements on wuestite in a laser-heated diamond anvil cell, finding an insulator-metal transition at high pressures and temperatures. Our data show a negative slope for this apparently isostructural phase boundary, which is characterized by a volume decrease and emissivity increase. The metallic phase of FeO is stable at conditions of the lower mantle and core, which has implications for the high P-T character of Fe-O bonds, magnetic field propagation, and lower mantle conductivity.

  4. Systematic thermodynamics of Magneli-phase and other transition metal oxides.

    PubMed

    Glasser, Leslie

    2009-11-02

    Both the molar enthalpies of formation and the absolute entropies of eight transition metal oxides are found to correlate very strongly with their formula unit volumes at room temperature. The metals are Ti, V, Cr, Nb, Mo, Ce, Pr, and Tb. In particular, the thermodynamic values of additive entities (such as TiO(2) in Ti(n)O(2n-1)) in Magneli phases (that is, recombination phases based on rebuilding after shear) are very close to those of the entity as a pure compound. Thus, reliable values of these thermodynamic properties can readily be predicted for unmeasured or even unsynthesized examples, and literature values can be checked. These assertions are checked against published results for which incomplete data is available. The contributions of the disordered regions which form between the added entities is tentatively estimated.

  5. CMOS-compatible hybrid plasmonic modulator based on vanadium dioxide insulator-metal phase transition.

    PubMed

    Kim, Jin Tae

    2014-07-01

    To extend the application of an emerging plasmonic material, vanadium dioxide (VO₂), in silicon photonics technology, we propose a complementary metal-oxide-semiconductor (CMOS)-compatible hybrid plasmonic modulator using an VO₂ insulator-metal phase transition. The optical device is based on a directional coupler that consists of a Si waveguide and a Si-SiO₂-VO₂-SiO₂-Si hybrid plasmonic waveguide. By electrically triggering the phase of VO₂ with a driving voltage of 2 V, the propagation loss of the hybrid plasmonic waveguide is switched, and hence the output optical power is modulated. The on/off extinction ratio is larger than 3.0 dB on the entire C-band.

  6. Continuum Theory of Phase Separation Kinetics for Active Brownian Particles

    NASA Astrophysics Data System (ADS)

    Stenhammar, Joakim; Tiribocchi, Adriano; Allen, Rosalind J.; Marenduzzo, Davide; Cates, Michael E.

    2013-10-01

    Active Brownian particles (ABPs), when subject to purely repulsive interactions, are known to undergo activity-induced phase separation broadly resembling an equilibrium (attraction-induced) gas-liquid coexistence. Here we present an accurate continuum theory for the dynamics of phase-separating ABPs, derived by direct coarse graining, capturing leading-order density gradient terms alongside an effective bulk free energy. Such gradient terms do not obey detailed balance; yet we find coarsening dynamics closely resembling that of equilibrium phase separation. Our continuum theory is numerically compared to large-scale direct simulations of ABPs and accurately accounts for domain growth kinetics, domain topologies, and coexistence densities.

  7. Experimental comparison of chiral metal-organic framework used as stationary phase in chromatography.

    PubMed

    Xie, Sheng-Ming; Zhang, Mei; Fei, Zhi-Xin; Yuan, Li-Ming

    2014-10-10

    Chiral metal-organic frameworks (MOFs) are a new class of multifunctional material, which possess diverse structures and unusual properties such as high surface area, uniform and permanent cavities, as well as good chemical and thermal stability. Their chiral functionality makes them attractive as novel enantioselective adsorbents and stationary phases in separation science. In this paper, the experimental comparison of a chiral MOF [In₃O(obb)₃(HCO₂)(H₂O)] solvent used as a stationary phase was investigated in gas chromatography (GC), high-performance liquid chromatography (HPLC) and capillary electrochromatography (CEC). The potential relationship between the structure and components of chiral MOFs with their chiral recognition ability and selectivity are presented.

  8. Nano-optical investigations of the metal-insulator phase behavior of individual VO(2) microcrystals.

    PubMed

    Jones, Andrew C; Berweger, Samuel; Wei, Jiang; Cobden, David; Raschke, Markus B

    2010-05-12

    Despite the relatively simple stoichiometry and structure of VO(2), many questions regarding the nature of its famous metal-insulator transition (MIT) remain unresolved. This is in part due to the prevailing use of polycrystalline film samples and the limited spatial resolution in most studies, hindering access to and control of the complex phase behavior and its inevitable spatial inhomogeneities. Here, we investigate the MIT and associated nanodomain formation in individual VO(2) microcrystals subject to substrate stress. We employ symmetry-selective polarization Raman spectroscopy to identify crystals that are strain-stabilized in either the monoclinic M1 or M2 insulating phase at room-temperature. Raman measurements are further used to characterize the phase dependence on temperature, identifying the appearance of the M2 phase during the MIT. The associated formation and spatial evolution of rutile (R) metallic domains is studied with nanometer-scale spatial resolution using infrared scattering-scanning near-field optical microscopy (s-SNOM). We deduce that even for small crystals of VO(2), the MIT is influenced by the competition between the R, M1, and M2 crystal phases with their different lattice constants subjected to the external substrate-induced stress. The results have important implications for the interpretation of the investigations of conventional polycrystalline thin films where the mutual interaction of constituent crystallites may affect the nature of the MIT in VO(2).

  9. Structural phase stability in group IV metals under static high pressure

    SciTech Connect

    Velisavljevic, Nenad; Chesnut, Garry N; Dattelbaum, Dana M; Vohra, Yogesh K; Stemshorn, Andrew

    2009-01-01

    In group IV metals (Ti, Zr, and Hf) room temperature compression leads to a martensitic transformation from a ductile {alpha} to a brittle {omega} phase. {alpha} {yields} {omega} phase boundary decreases to lower pressure at high temperature and can limit the use of group IV metals in industrial applications. There is a large discrepancy in the transition pressure reported in literature, with some of the variation attributed to experimental conditions (i.e. hydrostatic vs. non-hydrostatic). Shear deformation in non-hydrostatic experiments drives {alpha} {yields} {omega} transition and decreases transition pressure. Impurities can also aid or suppress {alpha} {yields} {omega} transition. By performing x-ray diffraction experiments on samples in a diamond anvil cell we show that interstitial impurities, such as C, N, and O can obstruct {alpha} {yields} {omega} transition and stabilize {alpha} phase to higher pressure. We also show that reduction in grain size can also influence {alpha} {yields} {omega} phase boundary and help stabilize {alpha} phase to higher pressure under non-hydrostatic conditions.

  10. Metal Ions, Not Metal-Catalyzed Oxidative Stress, Cause Clay Leachate Antibacterial Activity

    PubMed Central

    Otto, Caitlin C.; Koehl, Jennifer L.; Solanky, Dipesh; Haydel, Shelley E.

    2014-01-01

    Aqueous leachates prepared from natural antibacterial clays, arbitrarily designated CB-L, release metal ions into suspension, have a low pH (3.4–5), generate reactive oxygen species (ROS) and H2O2, and have a high oxidation-reduction potential. To isolate the role of pH in the antibacterial activity of CB clay mixtures, we exposed three different strains of Escherichia coli O157:H7 to 10% clay suspensions. The clay suspension completely killed acid-sensitive and acid-tolerant E. coli O157:H7 strains, whereas incubation in a low-pH buffer resulted in a minimal decrease in viability, demonstrating that low pH alone does not mediate antibacterial activity. The prevailing hypothesis is that metal ions participate in redox cycling and produce ROS, leading to oxidative damage to macromolecules and resulting in cellular death. However, E. coli cells showed no increase in DNA or protein oxidative lesions and a slight increase in lipid peroxidation following exposure to the antibacterial leachate. Further, supplementation with numerous ROS scavengers eliminated lipid peroxidation, but did not rescue the cells from CB-L-mediated killing. In contrast, supplementing CB-L with EDTA, a broad-spectrum metal chelator, reduced killing. Finally, CB-L was equally lethal to cells in an anoxic environment as compared to the aerobic environment. Thus, ROS were not required for lethal activity and did not contribute to toxicity of CB-L. We conclude that clay-mediated killing was not due to oxidative damage, but rather, was due to toxicity associated directly with released metal ions. PMID:25502790

  11. SEQUESTERING AGENTS FOR ACTIVE CAPS - REMEDIATION OF METALS AND ORGANICS

    SciTech Connect

    Knox, A; Michael Paller, M; Danny D. Reible, D; Xingmao Ma, X; Ioana G. Petrisor, I

    2007-05-10

    This research evaluated organoclays, zeolites, phosphates, and a biopolymer as sequestering agents for inorganic and organic contaminants. Batch experiments were conducted to identify amendments and mixtures of amendments for metal and organic contaminants removal and retention. Contaminant removal was evaluated by calculating partitioning coefficients. Metal retention was evaluated by desorption studies in which residue from the removal studies was extracted with 1 M MgCl{sub 2} solution. The results indicated that phosphate amendments, some organoclays, and the biopolymer, chitosan, were very effective sequestering agents for metals in fresh and salt water. Organoclays were very effective sorbents for phenanthrene, pyrene, and benzo(a)pyrene. Partitioning coefficients for the organoclays were 3000-3500 ml g{sup -1} for benzo(a)pyrene, 400-450 ml g{sup -1} for pyrene, and 50-70 ml g{sup -1} for phenanthrene. Remediation of sites with a mixture of contaminants is more difficult than sites with a single contaminant because metals and organic contaminants have different fate and transport mechanisms in sediment and water. Mixtures of amendments (e.g., organoclay and rock phosphate) have high potential for remediating both organic and inorganic contaminants under a broad range of environmental conditions, and have promise as components in active caps for sediment remediation.

  12. Activation of Autophagy by Metals in Chlamydomonas reinhardtii.

    PubMed

    Pérez-Martín, Marta; Blaby-Haas, Crysten E; Pérez-Pérez, María Esther; Andrés-Garrido, Ascensión; Blaby, Ian K; Merchant, Sabeeha S; Crespo, José L

    2015-09-01

    Autophagy is an intracellular self-degradation pathway by which eukaryotic cells recycle their own material in response to specific stress conditions. Exposure to high concentrations of metals causes cell damage, although the effect of metal stress on autophagy has not been explored in photosynthetic organisms. In this study, we investigated the effect of metal excess on autophagy in the model unicellular green alga Chlamydomonas reinhardtii. We show in cells treated with nickel an upregulation of ATG8 that is independent of CRR1, a global regulator of copper signaling in Chlamydomonas. A similar effect on ATG8 was observed with copper and cobalt but not with cadmium or mercury ions. Transcriptome sequencing data revealed an increase in the abundance of the protein degradation machinery, including that responsible for autophagy, and a substantial overlap of that increased abundance with the hydrogen peroxide response in cells treated with nickel ions. Thus, our results indicate that metal stress triggers autophagy in Chlamydomonas and suggest that excess nickel may cause oxidative damage, which in turn activates degradative pathways, including autophagy, to clear impaired components and recover cellular homeostasis.

  13. A ferritin from Dendrorhynchus zhejiangensis with heavy metals detoxification activity.

    PubMed

    Li, Chenghua; Li, Zhen; Li, Ye; Zhou, Jun; Zhang, Chundan; Su, Xiurong; Li, Taiwu

    2012-01-01

    Ferritin, an iron homeostasis protein, has important functions in transition and storage of toxic metal ions. In this study, the full-length cDNA of ferritin was isolated from Dendrorhynchus zhejiangensis by cDNA library and RACE approaches. The higher similarity and conserved motifs for ferritin were also identified in worm counterparts, indicating that it belonged to a new member of ferritin family. The temporal expression of worm ferritin in haemocytes was analyzed by RT-PCR, and revealed the ferritin could be induced by Cd(2+), Pb(2+) and Fe(2+). The heavy metal binding activity of recombinant ferritin was further elucidated by atomic force microscopy (AFM). It was observed that the ferritin protein could form a chain of beads with different size against three metals exposure, and the largest one with 35~40 nm in height was identified in the Cd(2+) challenge group. Our results indicated that worm ferritin was a promising candidate for heavy metals detoxification.

  14. A Ferritin from Dendrorhynchus zhejiangensis with Heavy Metals Detoxification Activity

    PubMed Central

    Li, Chenghua; Li, Zhen; Li, Ye; Zhou, Jun; Zhang, Chundan; Su, Xiurong; Li, Taiwu

    2012-01-01

    Ferritin, an iron homeostasis protein, has important functions in transition and storage of toxic metal ions. In this study, the full-length cDNA of ferritin was isolated from Dendrorhynchus zhejiangensis by cDNA library and RACE approaches. The higher similarity and conserved motifs for ferritin were also identified in worm counterparts, indicating that it belonged to a new member of ferritin family. The temporal expression of worm ferritin in haemocytes was analyzed by RT-PCR, and revealed the ferritin could be induced by Cd2+, Pb2+ and Fe2+. The heavy metal binding activity of recombinant ferritin was further elucidated by atomic force microscopy (AFM). It was observed that the ferritin protein could form a chain of beads with different size against three metals exposure, and the largest one with 35∼40 nm in height was identified in the Cd2+ challenge group. Our results indicated that worm ferritin was a promising candidate for heavy metals detoxification. PMID:23284696

  15. Gas-Phase Reactions of Doubly Charged Lanthanide Cations with Alkanes and Alkenes. Trends in Metal(2+) Reactivity

    SciTech Connect

    Gibson, John K.; Marcalo, Joaquim; Santos, Marta; Pires de Matos, Antonio; Haire, Richard G.

    2008-12-08

    The gas-phase reactivity of doubly-charged lanthanide cations, Ln2+ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), with alkanes (methane, ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) was studied by Fourier transform ion cyclotron resonance mass spectrometry. The reaction products consisted of different combinations of doubly-charged organometallic ions?adducts or species formed via metal-ion-induced hydrogen, dihydrogen, alkyl, or alkane eliminations from the hydrocarbons?and singly-charged ions that resulted from electron, hydride, or methide transfers from the hydrocarbons to the metal ions. The only lanthanide cations capable of activating the hydrocarbons to form doubly-charged organometallic ions were La2+, Ce2+, Gd2+, and Tb2+, which have ground-state or low-lying d1 electronic configurations. Lu2+, with an accessible d1 electronic configuration but a rather high electron affinity, reacted only through transfer channels. The remaining Ln2+ reacted via transfer channels or adduct formation. The different accessibilities of d1 electronic configurations and the range of electron affinities of the Ln2+ cations allowed for a detailed analysis of the trends for metal(2+) reactivity and the conditions for occurrence of bond activation, adduct formation, and electron, hydride, and methide transfers.

  16. On the melting temperatures of low-temperature phases of polymorphic metals

    NASA Technical Reports Server (NTRS)

    Ohsaka, K.; Trinh, E. H.

    1992-01-01

    An improved analytical formula for determining the melting temperatures of the low-temperature phases of polymorphic metals is proposed which uses the specific heat differences at the equilibrium transition temperatures. The formula is solved by an iterative method, with no more than one iteration necessary to converge. The results obtained using the formula proposed here are generally in good agreement with the analytical solution.

  17. Surface modes in "photonic cholesteric liquid crystal-phase plate-metal" structure.

    PubMed

    Vetrov, S Ya; Pyatnov, M V; Timofeev, I V

    2014-05-01

    The light transmission spectrum has been calculated for a "cholesteric liquid crystal-phase plate-metal" structure. It is shown that the system can have an isolated waveguide surface mode with characteristics efficiently controllable by external fields acting on the cholesteric. The degree of localization of surface modes and the transmission coefficients have been found to differ considerably for the light of different polarizations.

  18. ACTIVATION OF HAGEMAN FACTOR IN SOLID AND FLUID PHASES

    PubMed Central

    Cochrane, C. G.; Revak, S. D.; Wuepper, K. D.

    1973-01-01

    The activation of Hageman factor in solid and fluid phase has been analyzed. Activation of highly purified Hageman factor occurred after it interacted with and became bound to a negatively charged surface. Activation was observed in the absence of enzymes that are inhibitable with diisopropylfluorophosphate, phenyl methyl sulfonyl fluoride and ε-amino-n-caproic acid. The binding of [125I]Hageman factor to the negatively charged surface was markedly inhibited by plasma or purified plasma proteins. Activation of Hageman factor in solution (fluid phase) was obtained with kallikrein, plasmin, and Factor XI (plasma thromboplastin antecedent). Kallikrein was greater than 10 times more active in its ability to activate Hageman factor than plasmin and Factor XI. The data offer a plausible explanation for the finding that highly purified kallikrein promotes clotting of normal plasma. In addition, the combined results of this and previously reported data from this laboratory indicate that the reciprocal activation of Hageman factor by kallikrein in fluid phase is essential for normal rate of activation of the intrinsic-clotting, kinin-forming, and fibrinolytic systems. Activation of Hageman factor was associated with three different structural changes in the molecule: (a) Purified Hageman factor, activated on negatively charged surfaces retained its native mol wt of 80–90,000. Presumably a conformational change accompanied activation. (b) In fluid phase, activation with kallikrein and plasmin did not result in cleavage of large fragments of rabbit Hageman factor, although the activation required hydrolytic capacity of the enzymes. (c) Activation of human Hageman factor with kallikrein or plasmin was associated with cleavage of the molecule to 52,000, 40,000, and 28,000 mol wt fragments. Activation of rabbit Hageman factor with trypsin resulted in cleavage of the molecule into three fragments, each of 30,000 mol wt as noted previously. This major cleavage occurred

  19. DNA nuclease activity of Rev-coupled transition metal chelates.

    PubMed

    Joyner, Jeff C; Keuper, Kevin D; Cowan, J A

    2012-06-07

    Artificial nucleases containing Rev-coupled metal chelates based on combinations of the transition metals Fe(2+), Co(2+), Ni(2+), and Cu(2+) and the chelators DOTA, DTPA, EDTA, NTA, tripeptide GGH, and tetrapeptide KGHK have been tested for DNA nuclease activity. Originally designed to target reactive transition metal chelates (M-chelates) to the HIV-1 Rev response element mRNA, attachment to the arginine-rich Rev peptide also increases DNA-binding affinity for the attached M-chelates. Apparent K(D) values ranging from 1.7 to 3.6 µM base pairs for binding of supercoiled pUC19 plasmid DNA by Ni-chelate-Rev complexes were observed, as a result of electrostatic attraction between the positively-charged Rev peptide and negatively-charged DNA. Attachment of M-chelates to the Rev peptide resulted in enhancements of DNA nuclease activity ranging from 1-fold (no enhancement) to at least 13-fold (for Cu-DTPA-Rev), for the rate of DNA nicking, with second order rate constants for conversion of DNA(supercoiled) to DNA(nicked) up to 6 × 10(6) M(-1) min(-1), and for conversion of DNA(nicked) to DNA(linear) up to 1 × 10(5) M(-1) min(-1). Freifelder-Trumbo analysis and the ratios of linearization and nicking rate constants (k(lin)/k(nick)) revealed concerted mechanisms for nicking and subsequent linearization of plasmid DNA for all of the Rev-coupled M-chelates, consistent with higher DNA residency times for the Rev-coupled M-chelates. Observed rates for Rev-coupled M-chelates were less skewed by differing DNA-binding affinities than for M-chelates lacking Rev, as a result of the narrow range of DNA-binding affinities observed, and therefore relationships between DNA nuclease activity and other catalyst properties, such as coordination unsaturation, the ability to consume ascorbic acid and generate diffusible radicals, and the identity of the metal center, are now clearly illustrated in light of the similar DNA-binding affinities of all M-chelate-Rev complexes. This work

  20. Copper toxicity to bioluminescent Nitrosomonas europaea in soil is explained by the free metal ion activity in pore water.

    PubMed

    Ore, S; Mertens, J; Brandt, K K; Smolders, E

    2010-12-01

    The terrestrial biotic ligand model (BLM) for metal toxicity in soil postulates that metal toxicity depends on the free metal ion activity in solution and on ions competing for metal sorption to the biotic ligand. Unequivocal evidence for the BLM assumptions is most difficult to obtain for native soil microorganisms because the abiotic and biotic compartments cannot be experimentally separated. Here, we report copper (Cu) toxicity to a bioluminescent Nitrosomonas europaea reporter strain that was used in a solid phase-contact assay and in corresponding soil extracts and artificial soil solutions. The Cu(2+) ion activities that halve bioluminescence (EC50) in artificial solutions ranged 10(-5) to 10(-7) M and increased with increasing activities of H(+), Ca(2+) and Mg(2+) according to the BLM concept. The solution based Cu(2+) EC50 values of N. europaea in six contaminated soils ranged 2 × 10(-6) to 2 × 10(-9) M and these thresholds for both solid phase or soil extract based assays were well predicted by the ion competition model fitted to artificial solution data. In addition, solution based Cu(2+) EC50 of the solid phase-contact assay were never smaller than corresponding values in soil extracts suggesting no additional solid phase toxic route. By restricting the analysis to the same added species, we show that the Cu(2+) in solution represents the toxic species to this bacterium.

  1. Correlation between the spin Hall angle and the structural phases of early 5d transition metals

    SciTech Connect

    Liu, Jun; Ohkubo, Tadakatsu; Mitani, Seiji; Hono, Kazuhiro; Hayashi, Masamitsu

    2015-12-07

    We have studied the relationship between the structure and the spin Hall angle of the early 5d transition metals in X/CoFeB/MgO (X = Hf, Ta, W, and Re) heterostructures. Spin Hall magnetoresistance (SMR) is used to characterize the spin Hall angle of the heavy metals. Transmission electron microscopy images show that all underlayers are amorphous-like when their thicknesses are small, however, crystalline phases emerge as the thickness is increased for certain elements. We find that the heavy metal layer thickness dependence of the SMR reflects these changes in structure. The largest spin Hall angle |θ{sub SH}| of Hf, Ta, W, and Re (∼0.11, 0.10, 0.23, and 0.07, respectively) is found when the dominant phase is amorphous-like. We find that the amorphous-like phase not only possesses large resistivity but also exhibits sizeable spin Hall conductivity, which both contribute to the emergence of the large spin Hall angle.

  2. Middeck Active Control Experiment (MACE), phase A

    NASA Technical Reports Server (NTRS)

    Crawley, Edward F.; Deluis, Javier; Miller, David W.

    1989-01-01

    A rationale to determine which structural experiments are sufficient to verify the design of structures employing Controlled Structures Technology was derived. A survey of proposed NASA missions was undertaken to identify candidate test articles for use in the Middeck Active Control Experiment (MACE). The survey revealed that potential test articles could be classified into one of three roles: development, demonstration, and qualification, depending on the maturity of the technology and the mission the structure must fulfill. A set of criteria was derived that allowed determination of which role a potential test article must fulfill. A review of the capabilities and limitations of the STS middeck was conducted. A reference design for the MACE test article was presented. Computing requirements for running typical closed-loop controllers was determined, and various computer configurations were studied. The various components required to manufacture the structure were identified. A management plan was established for the remainder of the program experiment development, flight and ground systems development, and integration to the carrier. Procedures for configuration control, fiscal control, and safety, reliabilty, and quality assurance were developed.

  3. Gas-phase Oxygen Abundances and Radial Metallicity Gradients in the Two nearby Spiral Galaxies NGC 7793 and NGC 4945

    NASA Astrophysics Data System (ADS)

    Stanghellini, Letizia; Magrini, Laura; Casasola, Viviana

    2015-10-01

    Gas-phase abundances in H ii regions of two spiral galaxies, NGC 7793 and NGC 4945, have been studied to determine their radial metallicity gradients. We used the strong-line method to derive oxygen abundances from spectra acquired with GMOS-S, the multi-object spectrograph on the 8 m Gemini South telescope. We found that NGC 7793 has a well-defined gas-phase radial oxygen gradient of -0.321 ± 0.112 dex {R}25-1 (or -0.054 ± 0.019 dex kpc-1) in the galactocentric range 0.17 < RG/R25 < 0.82, not dissimilar from gradients calculated with direct abundance methods in galaxies of similar mass and morphology. We also determined a shallow radial oxygen gradient in NGC 4945, -0.253 ± 0.149 dex {R}25-1 (or -0.019 ± 0.011 dex kpc-1) for 0.04 < RG/R25 < 0.51, where the larger relative uncertainty derives mostly from the larger inclination of this galaxy. NGC 7793 and NGC 4945 have been selected for this study because they are similar, in mass and morphology, to M33 and the Milky Way, respectively. Since at zeroth order we expect the radial metallicity gradients to depend on mass and galaxy type, we compared our galaxies in the framework of radial metallicity models best suited for M33 and the Galaxy. We found a good agreement between M33 and NGC 7793, pointing toward similar evolution for the two galaxies. We notice instead differences between NGC 4945 and the radial metallicity gradient model that best fits the Milky Way. We found that these differences are likely related to the presence of an active galactic nucleus combined with a bar in the central regions of NGC 4945, and to its interacting environment.

  4. Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts.

    PubMed

    Santos, Vera P; Wezendonk, Tim A; Jaén, Juan José Delgado; Dugulan, A Iulian; Nasalevich, Maxim A; Islam, Husn-Ubayda; Chojecki, Adam; Sartipi, Sina; Sun, Xiaohui; Hakeem, Abrar A; Koeken, Ard C J; Ruitenbeek, Matthijs; Davidian, Thomas; Meima, Garry R; Sankar, Gopinathan; Kapteijn, Freek; Makkee, Michiel; Gascon, Jorge

    2015-03-05

    Depletion of crude oil resources and environmental concerns have driven a worldwide research on alternative processes for the production of commodity chemicals. Fischer-Tropsch synthesis is a process for flexible production of key chemicals from synthesis gas originating from non-petroleum-based sources. Although the use of iron-based catalysts would be preferred over the widely used cobalt, manufacturing methods that prevent their fast deactivation because of sintering, carbon deposition and phase changes have proven challenging. Here we present a strategy to produce highly dispersed iron carbides embedded in a matrix of porous carbon. Very high iron loadings (>40 wt %) are achieved while maintaining an optimal dispersion of the active iron carbide phase when a metal organic framework is used as catalyst precursor. The unique iron spatial confinement and the absence of large iron particles in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation.

  5. Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts

    NASA Astrophysics Data System (ADS)

    Santos, Vera P.; Wezendonk, Tim A.; Jaén, Juan José Delgado; Dugulan, A. Iulian; Nasalevich, Maxim A.; Islam, Husn-Ubayda; Chojecki, Adam; Sartipi, Sina; Sun, Xiaohui; Hakeem, Abrar A.; Koeken, Ard C. J.; Ruitenbeek, Matthijs; Davidian, Thomas; Meima, Garry R.; Sankar, Gopinathan; Kapteijn, Freek; Makkee, Michiel; Gascon, Jorge

    2015-03-01

    Depletion of crude oil resources and environmental concerns have driven a worldwide research on alternative processes for the production of commodity chemicals. Fischer-Tropsch synthesis is a process for flexible production of key chemicals from synthesis gas originating from non-petroleum-based sources. Although the use of iron-based catalysts would be preferred over the widely used cobalt, manufacturing methods that prevent their fast deactivation because of sintering, carbon deposition and phase changes have proven challenging. Here we present a strategy to produce highly dispersed iron carbides embedded in a matrix of porous carbon. Very high iron loadings (>40 wt %) are achieved while maintaining an optimal dispersion of the active iron carbide phase when a metal organic framework is used as catalyst precursor. The unique iron spatial confinement and the absence of large iron particles in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation.

  6. Solid-liquid interface free energies of pure bcc metals and B2 phases

    SciTech Connect

    Wilson, S. R.; Gunawardana, K. G. S. H.; Mendelev, M. I.

    2015-04-07

    The solid-liquid interface (SLI) free energy was determined from molecular dynamics (MD) simulation for several body centered cubic (bcc) metals and B2 metallic compounds (space group: Pm3¯m ; prototype: CsCl). In order to include a bcc metal with a low melting temperature in our study, a semi-empirical potential was developed for Na. Two additional synthetic “Na” potentials were also developed to explore the effect of liquid structure and latent heat on the SLI free energy. The obtained MD data were compared with the empirical Turnbull, Laird, and Ewing relations. All three relations are found to predict the general trend observed in the MD data for bcc metals obtained within the present study. However, only the Laird and Ewing relations are able to predict the trend obtained within the sequence of “Na” potentials. The Laird relation provides the best prediction for our MD data and other MD data for bcc metals taken from the literature. Overall, the Laird relation also agrees well with our B2 data but requires a proportionality constant that is substantially different from the bcc case. It also fails to explain a considerable difference between the SLI free energies of some B2 phases which have nearly the same melting temperature. In contrast, this difference is satisfactorily described by the Ewing relation. Thus, the Ewing relation obtained from the bcc dataset also provides a reasonable description of the B2 data.

  7. Solid-liquid interface free energies of pure bcc metals and B2 phases.

    PubMed

    Wilson, S R; Gunawardana, K G S H; Mendelev, M I

    2015-04-07

    The solid-liquid interface (SLI) free energy was determined from molecular dynamics (MD) simulation for several body centered cubic (bcc) metals and B2 metallic compounds (space group: Pm3̄m; prototype: CsCl). In order to include a bcc metal with a low melting temperature in our study, a semi-empirical potential was developed for Na. Two additional synthetic "Na" potentials were also developed to explore the effect of liquid structure and latent heat on the SLI free energy. The obtained MD data were compared with the empirical Turnbull, Laird, and Ewing relations. All three relations are found to predict the general trend observed in the MD data for bcc metals obtained within the present study. However, only the Laird and Ewing relations are able to predict the trend obtained within the sequence of "Na" potentials. The Laird relation provides the best prediction for our MD data and other MD data for bcc metals taken from the literature. Overall, the Laird relation also agrees well with our B2 data but requires a proportionality constant that is substantially different from the bcc case. It also fails to explain a considerable difference between the SLI free energies of some B2 phases which have nearly the same melting temperature. In contrast, this difference is satisfactorily described by the Ewing relation. Moreover, the Ewing relation obtained from the bcc dataset also provides a reasonable description of the B2 data.

  8. Heavy-metal contamination and solid-phase fractionation in street dust.

    PubMed

    Merrikhpour, Hajar; Mahdavi, Shahriar

    2016-08-05

    Fourteen street-dust samples were collected from Hamedan, western Iran. Street-dust samples received different amounts of heavy-metal pollution. The samples were analyzed for total cadmium (Cd), copper (Cu), lead (Pb), nickel (Ni), and zinc (Zn), and binding forms of heavy metal were determined in five fractions. The results showed Cd was the only metal present appreciably, 25.21% and 25.92%, in the exchangeable and carbonates fractions, respectively, and Cu was the only metal predominantly associated, 31.77%, with organic fraction. Zn, 45.84%, was present mainly in the Fe-Mn oxide fraction, and the residual fraction was the most dominant solid phase pool of Ni and Pb, respectively, with 42.56% and 41.31%. The order of apparent mobility and potential metal bioavailability for these contaminated street-dust samples is Cd > Zn > Cu > Pb > Ni. The risk-assessment code results showed very high risk for Cd; medium risk for Cu, Pb, and Zn; and low risk for Ni.

  9. Solution-phase epitaxial growth of quasi-monocrystalline cuprous oxide on metal nanowires.

    PubMed

    Sciacca, Beniamino; Mann, Sander A; Tichelaar, Frans D; Zandbergen, Henny W; van Huis, Marijn A; Garnett, Erik C

    2014-10-08

    The epitaxial growth of monocrystalline semiconductors on metal nanostructures is interesting from both fundamental and applied perspectives. The realization of nanostructures with excellent interfaces and material properties that also have controlled optical resonances can be very challenging. Here we report the synthesis and characterization of metal-semiconductor core-shell nanowires. We demonstrate a solution-phase route to obtain stable core-shell metal-Cu2O nanowires with outstanding control over the resulting structure, in which the noble metal nanowire is used as the nucleation site for epitaxial growth of quasi-monocrystalline Cu2O shells at room temperature in aqueous solution. We use X-ray and electron diffraction, high-resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, photoluminescence spectroscopy, and absorption spectroscopy, as well as density functional theory calculations, to characterize the core-shell nanowires and verify their structure. Metal-semiconductor core-shell nanowires offer several potential advantages over thin film and traditional nanowire architectures as building blocks for photovoltaics, including efficient carrier collection in radial nanowire junctions and strong optical resonances that can be tuned to maximize absorption.

  10. Solid-liquid interface free energies of pure bcc metals and B2 phases

    DOE PAGES

    Wilson, S. R.; Gunawardana, K. G. S. H.; Mendelev, M. I.

    2015-04-07

    The solid-liquid interface (SLI) free energy was determined from molecular dynamics (MD) simulation for several body centered cubic (bcc) metals and B2 metallic compounds (space group: Pm3¯m ; prototype: CsCl). In order to include a bcc metal with a low melting temperature in our study, a semi-empirical potential was developed for Na. Two additional synthetic “Na” potentials were also developed to explore the effect of liquid structure and latent heat on the SLI free energy. The obtained MD data were compared with the empirical Turnbull, Laird, and Ewing relations. All three relations are found to predict the general trend observedmore » in the MD data for bcc metals obtained within the present study. However, only the Laird and Ewing relations are able to predict the trend obtained within the sequence of “Na” potentials. The Laird relation provides the best prediction for our MD data and other MD data for bcc metals taken from the literature. Overall, the Laird relation also agrees well with our B2 data but requires a proportionality constant that is substantially different from the bcc case. It also fails to explain a considerable difference between the SLI free energies of some B2 phases which have nearly the same melting temperature. In contrast, this difference is satisfactorily described by the Ewing relation. Thus, the Ewing relation obtained from the bcc dataset also provides a reasonable description of the B2 data.« less

  11. Development of High Performance CFRP/Metal Active Laminates

    NASA Astrophysics Data System (ADS)

    Asanuma, Hiroshi; Haga, Osamu; Imori, Masataka

    This paper describes development of high performance CFRP/metal active laminates mainly by investigating the kind and thickness of the metal. Various types of the laminates were made by hot-pressing of an aluminum, aluminum alloys, a stainless steel and a titanium for the metal layer as a high CTE material, a unidirectional CFRP prepreg as a low CTE/electric resistance heating material, a unidirectional KFRP prepreg as a low CTE/insulating material. The aluminum and its alloy type laminates have almost the same and the highest room temperature curvatures and they linearly change with increasing temperature up to their fabrication temperature. The curvature of the stainless steel type jumps from one to another around its fabrication temperature, whereas the titanium type causes a double curvature and its change becomes complicated. The output force of the stainless steel type attains the highest of the three under the same thickness. The aluminum type successfully increased its output force by increasing its thickness and using its alloys. The electric resistance of the CFRP layer can be used to monitor the temperature, that is, the curvature of the active laminate because the curvature is a function of temperature.

  12. Ligational behavior of Schiff bases towards transition metal ion and metalation effect on their antibacterial activity.

    PubMed

    Devi, Jai; Batra, Nisha; Malhotra, Rajesh

    2012-11-01

    New Schiff bases pyrazine-2-carboxylicacid (phenyl-pyridin-2-yl-methylene)-hydrazide (Hpch-bp) HL(1) and pyrazine-2-carboxylicacid (pyridin-2-ylmethylene)-hydrazide (Hpch-pc) HL(2) derived from condensation of pyrazine carboxylic hydrazide (Hpch) with 2-benzoyl pyridine (bp) or pyridine 2-carbaldehyde (pc) and their transition metal complexes of type ML((1-2)2) have been synthesized, where M=Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). Characterization of ligands and their metal complexes was carried out by elemental analysis, conductimetric studies, magnetic susceptibility, spectroscopic techniques (IR, UV-VIS, NMR, ESR, Mass) and thermogravimetric analysis. The physico-chemical studies revealed octahedral geometry or distorted octahedral geometry around metal ion. These azomethine Schiff base ligands acted as tridentate coordinating through carbonyl, azomethine and pyridine nitrogen present in the ligand. The thermodynamic and thermal properties of the complexes have been investigated and it was observed on the basis of these studies that thermal stability of complexes follows the order Mnactivity at different concentrations against bacteria viz. Gram positive Bacillus subtilis, Micrococcus luteus and Gram negative Pseudomonas aeruginosa, Pseudomonas mendocina. A marked enhancement in biocidal activity of the ligands under similar experimental conditions was observed as a consequence of coordination with metal ions. The trend of growth inhibition in the complexes was found to be in the order: Cu>Mn>Ni>Co>Zn.

  13. Phase response curves in the characterization of epileptiform activity

    NASA Astrophysics Data System (ADS)

    Perez Velazquez, J. L.; Galán, R. F.; Dominguez, L. Garcia; Leshchenko, Y.; Lo, S.; Belkas, J.; Erra, R. Guevara

    2007-12-01

    Coordinated cellular activity is a major characteristic of nervous system function. Coupled oscillator theory offers unique avenues to address cellular coordination phenomena. In this study, we focus on the characterization of the dynamics of epileptiform activity, based on some seizures that manifest themselves with very periodic rhythmic activity, termed absence seizures. Our approach consists in obtaining experimentally the phase response curves (PRCs) in the neocortex and thalamus, and incorporating these PRCs into a model of coupled oscillators. Phase preferences of the stationary states and their stability are determined, and these results from the model are compared with the experimental recordings, and interpreted in physiological terms.

  14. Metal concentration and antioxidant activity of edible mushrooms from Turkey.

    PubMed

    Sarikurkcu, Cengiz; Tepe, Bektas; Kocak, Mehmet Sefa; Uren, Mehmet Cemil

    2015-05-15

    This study presents information on the antioxidant activity and heavy metal concentrations of Polyporus sulphureus, Macrolepiota procera, Lycoperdon perlatum and Gomphus clavatus mushrooms collected from the province of Mugla in the South-Aegean Region of Turkey. Antioxidant activities of mushroom samples were evaluated by four complementary tests. All tests showed L. perlatum and G. clavatus to possess extremely high antioxidant potential. Antioxidant activity of the samples was strongly correlated with total phenolic-flavonoid content. In terms of heavy metal content, L. perlatum exceeded the legal limits for daily intake of Pb, Fe, Mn, Cr, Ni and Co contents (0.461, 738.00, 14.52, 1.27, 1.65, 0.417 mg/day, respectively) by a 60-kg consumer. Co contents of M. procera (0.026 mg/day) and P. sulphureus (0.030 mg/day) and Cd contents of G. clavatus (0.071 mg/day) were also above the legal limits. According to these results, L. perlatum should not be consumed, despite the potentially beneficial antioxidant activity. Additionally, M. procera and G. clavatus should not be consumed daily due to their high levels of Cd and Co.

  15. Immobilizing Highly Catalytically Active Pt Nanoparticles inside the Pores of Metal-Organic Framework: A Double Solvents Approach

    SciTech Connect

    Aijaz, Arshad; Karkamkar, Abhijeet J.; Choi, Young Joon; Tsumori, Nobuko; Ronnebro, Ewa; Autrey, Thomas; Shioyama, Hiroshi; Xu, Qiang

    2012-08-29

    Ultrafine Pt nanoparticles were successfully immobilized inside the pores of a metal-organic framework MIL-101 without deposition of Pt nanoparticles on the external surfaces of framework by using a 'double solvents' method. The resulting Pt@MIL-101 composites with different Pt loadings represent the first highly active MOF-immobilized metal nanocatalysts for catalytic reactions in all three phases: liquid-phase ammonia borane hydrolysis; solid-phase ammonia borane thermal dehy-drogenation and gas-phase CO oxidation. The observed excellent catalytic performances are at-tributed to the small Pt nanoparticles within the pores of MIL-101. 'We are thankful to AIST and METI for financial support. TA & AK are thankful for support from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. PNNL is operated by Battelle.'

  16. The Connection Between Local Icosahedral Order in Metallic Liquids and the Nucleation of Ordered Phases

    NASA Technical Reports Server (NTRS)

    Curreri, Peter A. (Technical Monitor); Kelton, K. F.; Gangopadhyay, A.; Lee, G. W.; Hyers, R. W.; Rathz, R. J.; Rogers, J.; Schenk, T.; Simonet, V.; Holland-Moritz, D.

    2003-01-01

    Over fifty years ago, David Turnbull showed that the temperature of many metallic liquids could be decreased far below their equilibrium melting temperature before crystallization occurred. To explain those surprising results, Charles Frank hypothesized that the local structures of undercooled metallic liquids are different from those of crystal phases, containing a significant degree of icosahedral order that is incompatible with extended periodicity. Such structural differences must create a barrier to the formation crystal phases, explaining the observed undercooling behavior. If true, the nucleation from the liquid of phases with extended icosahedral order should be easier. Icosahedral order is often favored in small clusters, as observed recently in liquid-like clusters of pure Pb on the (111) surface of Si, for example. However, it has never been shown that an increasing preference for icosahedral phase formation can be directly linked with the development of icosahedral order in the undercooled liquid. Owing to the combination of very recent advances in levitation techniques and the availability of synchrotron x-ray and high flux neutron facilities, this is shown here.

  17. The Connection Between Local Icosahedral Order in Metallic Liquids and the Nucleation of Ordered Phases

    NASA Technical Reports Server (NTRS)

    Kelton, K. F.; Gangopadhyay, A. K.; Lee, G. W.; Hyers, R. W.; Rathz, T. J.; Rogers, J. R.; Robinson, M. B.; Schenk, T.; Simonet, V.; Holland-Moritz, D.; Curreri, Peter A. (Technical Monitor)

    2002-01-01

    Over fifty years ago, David Turnbull showed that the temperature of many metallic liquids could be decreased far below their equilibrium melting temperature before crystallization occurred. To explain those surprising results, Charles Frank hypothesized that the local structures of undercooled metallic liquids are different from those of crystal phases, containing a significant degree of icosahedral order that is incompatible with extended periodicity. Such structural differences must create a barrier to the formation crystal phases, explaining the observed undercooling behavior. If true, the nucleation from the liquid of phases with extended icosahedral order should be easier. Icosahedral order is often favored in small clusters, as observed recently in liquid-like clusters of pure Pb on the (111) surface of Si(3), for example. However, it has never been shown that an increasing preference for icosahedral phase formation can be directly linked with the development of icosahedral order in the undercooled liquid. Owing to the combination of very recent advances in levitation techniques and the availability of synchrotron X-ray and high flux neutron facilities.

  18. The Connection Between Local Icosahedral Order in Metallic Liquids and the Nucleation Behavior of Ordered Phases

    NASA Technical Reports Server (NTRS)

    Kelton, K. F.; Gangopadhyay, A. K.; Lee, G. W.; Hyers, R. W.; Rathz, T. J.; Rogers, J. R.; Robinson, M. B.; Schenk, T.; Simonet, V.

    2003-01-01

    Over fifty years ago, David Turnbull showed that the temperature of many metallic liquids could be decreased far below their equilibrium melting temperature before crystallization occurred. To explain those surprising results, Charles Frank hypothesized that the local structures of undercooled metallic liquids are different from those of crystal phases, containing a significant degree of icosahedral order that is incompatible with extended periodicity. Such structural differences must create a barrier to the formation crystal phases, explaining the observed undercooling behavior. If true, the nucleation from the liquid of phases with extended icosahedral order should be easier. Icosahedral order is often favored in small clusters, as observed recently in liquid-like clusters of pure Pb on the (111) surface of Si[3], for example. However, it has never been shown that an increasing preference for icosahedral phase formation can be directly linked with the development of icosahedral order in the undercooled liquid. Owing to the combination of very recent advances in levitation techniques and the availability of synchrotron x-ray and high flux neutron facilities, this is shown here.

  19. Observation of Dirac-like semi-metallic phase in NdSb.

    PubMed

    Neupane, Madhab; Mofazzel Hosen, M; Belopolski, Ilya; Wakeham, Nicholas; Dimitri, Klauss; Dhakal, Nagendra; Zhu, Jian-Xin; Zahid Hasan, M; Bauer, Eric D; Ronning, Filip

    2016-06-15

    The search of new topological phases of matter is one of the new directions in condensed matter physics. Recent experimental realizations of Dirac semimetal phases pave the way to look for other exotic phases of matter in real materials. Here we present a systematic angle-resolved photoemission spectroscopy (ARPES) study of NdSb, a potential candidate for hosting a Dirac semi-metal phase. Our studies reveal two hole-like Fermi surface pockets present at the zone center ([Formula: see text]) point as well as two elliptical electron-pockets present in the zone corner (X) point of the Brillouin zone (BZ). Interestingly, Dirac-like linearly dispersive states are observed about the zone corner (X) point in NdSb. Our first-principles calculations agree with the experimentally observed bands at the [Formula: see text] point. Moreover, the Dirac-like state observed in NdSb may be a novel correlated state, not yet predicted in calculations. Our study opens a new direction to look for Dirac semi-metal states in other members of the rare earth monopnictide family.

  20. Observation of Dirac-like semi-metallic phase in NdSb

    NASA Astrophysics Data System (ADS)

    Neupane, Madhab; Mofazzel Hosen, M.; Belopolski, Ilya; Wakeham, Nicholas; Dimitri, Klauss; Dhakal, Nagendra; Zhu, Jian-Xin; Zahid Hasan, M.; Bauer, Eric D.; Ronning, Filip

    2016-06-01

    The search of new topological phases of matter is one of the new directions in condensed matter physics. Recent experimental realizations of Dirac semimetal phases pave the way to look for other exotic phases of matter in real materials. Here we present a systematic angle-resolved photoemission spectroscopy (ARPES) study of NdSb, a potential candidate for hosting a Dirac semi-metal phase. Our studies reveal two hole-like Fermi surface pockets present at the zone center (Γ ) point as well as two elliptical electron-pockets present in the zone corner (X) point of the Brillouin zone (BZ). Interestingly, Dirac-like linearly dispersive states are observed about the zone corner (X) point in NdSb. Our first-principles calculations agree with the experimentally observed bands at the Γ point. Moreover, the Dirac-like state observed in NdSb may be a novel correlated state, not yet predicted in calculations. Our study opens a new direction to look for Dirac semi-metal states in other members of the rare earth monopnictide family.

  1. Semi-active tuned mass dampers with phase control

    NASA Astrophysics Data System (ADS)

    Chung, Lap-Loi; Lai, Yong-An; Walter Yang, Chuang-Sheng; Lien, Kuan-Hua; Wu, Lai-Yun

    2013-07-01

    The present study aims at proposing an innovative phase control methodology for semi-active tuned mass dampers (SA-TMDs) that intend to minimize the off-tuned problems associated with passive tuned mass dampers (P-TMDs). The phase control algorithm is first developed, the essential of which is to apply the variable friction force to slow down the mass block at specific moments when the phase lag of the SA-TMD with respect to the structure is different from 90°, resulting in the SA-TMD back to the desired phase lag, i.e., -90° phase deviation, so that the SA-TMD has the maximum power flow to reduce the structural vibration. The feasibility of the application of the phase control in SA-TMDs is verified by performing numerical analyses of a simplified Taipei 101 structure model with a SA-TMD subjected to sinusoidal loads and design level wind loads. The numerical simulation results show that the SA-TMD implemented with phase control can enable the mass block to vibrate in a manner with a phase lag close to the -90° when the structure model is under sinusoidal excitations with frequencies different from the structural fundamental mode. The SA-TMD with phase control not only exhibits better performance than the optimal P-TMD in terms of suppressing the structural vibration, but also enhances its robustness, particularly when the SA-TMD is off-tuned to the structure.

  2. Synthesis and Characterization of Layered Double Hydroxides Containing Optically Active Transition Metal Ion

    NASA Astrophysics Data System (ADS)

    Tyagi, S. B.; Kharkwal, Aneeta; Nitu; Kharkwal, Mamta; Sharma, Raghunandan

    2017-01-01

    The acetate intercalated layered double hydroxides of Zn and Mn, have been synthesized by chimie douce method. The materials were characterized by XRD, TGA, CHN, IR, XPS, SEM-EDX and UV-visible spectroscopy. The photoluminescence properties was also studied. The optical properties of layered hydroxides are active transition metal ion dependent, particularly d1-10 system plays an important role. Simultaneously the role of host - guest orientation has been considered the basis of photoluminescence. Acetate ion can be exchanged with iodide and sulphate ions. The decomposed product resulted the pure phase Mn doped zinc oxide are also reported.

  3. Hydrogen Sulfide Induced Carbon Dioxide Activation by Metal-Free Dual Catalysis.

    PubMed

    Kumar, Manoj; Francisco, Joseph S

    2016-03-18

    The role of metal free dual catalysis in the hydrogen sulfide (H2S)-induced activation of carbon dioxide (CO2) and subsequent decomposition of resulting monothiolcarbonic acid in the gas phase has been explored. The results suggest that substituted amines and monocarboxylic type organic or inorganic acids via dual activation mechanisms promote both activation and decomposition reactions, implying that the judicious selection of a dual catalyst is crucial to the efficient C-S bond formation via CO2 activation. Considering that our results also suggest a new mechanism for the formation of carbonyl sulfide from CO2 and H2S, these new insights may help in better understanding the coupling between the carbon and sulfur cycles in the atmospheres of Earth and Venus.

  4. Microstructure and Performance of Kovar/Alumina Joints Made with Silver-Copper Base Active Metal Braze Alloys

    SciTech Connect

    STEPHENS, JOHN J.; VIANCO,PAUL T.; HLAVA,PAUL F.; WALKER,CHARLES A.

    1999-12-15

    Poor hermeticity performance was observed for Al{sub 2}O{sub 3}-Al{sub 2}O{sub 3} ceramic-ceramic joints having a Kovar{trademark} alloy interlayer. The active Ag-Cu-Ti filler metal was used to braze the substrates together. The Ti active element was scavenged from the filler metal by the formation of a (Fe, Ni, Co){sub x}Ti phase (x= 2-3) that prevented development of a continuous Ti{sub x}O{sub y} layer at the filler metal/Al{sub 2}O{sub 3} interface. Altering the process parameters did not circumvent the scavenging of Ti. Molybdenum barrier layers 1000, 2500, or 5000 {angstrom} thick on the Kovar{trademark} surfaces successfully allowed Ti{sub x}O{sub y} formation at the filler metal/Al{sub 2}O{sub 3} interface and hermetic joints. The problems with the Ag-Cu-Ti filler metal for Kovar{trademark}/Al{sub 2}O{sub 3} braze joints led to the evaluation of a Ag-Cu-Zr filler metal. The Zr (active element) in Ag-Cu-Zr filler metal was not susceptible to the scavenging problem.

  5. Surface phases of the transition-metal dichalcogenide IrT e2

    NASA Astrophysics Data System (ADS)

    Chen, Chen; Kim, Jisun; Yang, Yifan; Cao, Guixin; Jin, Rongying; Plummer, E. W.

    2017-03-01

    Transition-metal dichalcogenide IrT e2 has attracted attention because of its striped lattice, charge ordering, and superconductivity. We have investigated the surface structure of IrT e2 , using low-energy electron diffraction and scanning tunneling microscopy. A complex striped lattice modulation as a function of temperature is observed, which shows hysteresis between cooling and warming. While the bulk 5 × 1 and 8 × 1 phases appear at high temperatures, the surface ground state has the 6 × 1 phase, not seen in the bulk, and the surface transition temperatures are distinct from the bulk. The broken symmetry at the surface creates a quite different phase diagram, with the coexistence of several periodicities resembling devil's staircase behavior.

  6. Metal-Organic Framework Thin Films as Stationary Phases in Microfabricated Gas-Chromatography Columns.

    SciTech Connect

    Read, Douglas; Sillerud, Colin Halliday

    2016-01-01

    The overarching goal of this project is to integrate Sandia's microfabricated gas-chromatography ( GC) columns with a stationary phase material that is capable of retaining high-volatility chemicals and permanent gases. The successful integration of such a material with GCs would dramatically expand the repertoire of detectable compounds for Sandia's various microanalysis systems. One such promising class of candidate materials is metal-organic frameworks (MOFs). In this report we detail our methods for controlled deposition of HKUST-1 MOF stationary phases within GC columns. We demonstrate: the chromatographic separation of natural gas; a method for determining MOF film thickness from chromatography alone; and the first-reported GC x GC separation of natural gas -- in general -- let alone for two disparate MOF stationary phases. In addition we determine the fundamental thermodynamic constant for mass sorption, the partition coefficient, for HKUST-1 and several light hydrocarbons and select toxic industrial chemicals.

  7. Vapor phase hydrogenation of furfural over nickel mixed metal oxide catalysts derived from layered double hydroxides

    SciTech Connect

    Sulmonetti, Taylor P.; Pang, Simon H.; Claure, Micaela Taborga; Lee, Sungsik; Cullen, David A.; Agrawal, Pradeep K.; Jones, Christopher W.

    2016-05-01

    The hydrogenation of furfural is investigated over various reduced nickel mixed metal oxides derived from layered double hydroxides (LDHs) containing Ni-Mg-Al and Ni-Co-Al. Upon reduction, relatively large Ni(0) domains develop in the Ni-Mg-Al catalysts, whereas in the Ni-Co-Al catalysts smaller metal particles of Ni(0) and Co(0), potentially as alloys, are formed, as evidenced by XAS, XPS, STEM and EELS. All the reduced Ni catalysts display similar selectivities towards major hydrogenation products (furfuryl alcohol and tetrahydrofurfuryl alcohol), though the side products varied with the catalyst composition. The 1.1Ni-0.8Co-Al catalyst showed the greatest activity per titrated site when compared to the other catalysts, with promising activity compared to related catalysts in the literature. The use of base metal catalysts for hydrogenation of furanic compounds may be a promising alternative to the well-studied precious metal catalysts for making biomass-derived chemicals if catalyst selectivity can be improved in future work by alloying or tuning metal-oxide support interactions.

  8. Vapor phase hydrogenation of furfural over nickel mixed metal oxide catalysts derived from layered double hydroxides

    DOE PAGES

    Sulmonetti, Taylor P.; Pang, Simon H.; Claure, Micaela Taborga; ...

    2016-03-09

    The hydrogenation of furfural is investigated over various reduced nickel mixed metal oxides derived from layered double hydroxides (LDHs) containing Ni-Mg-Al and Ni-Co-Al. Upon reduction, relatively large Ni(0) domains develop in the Ni-Mg-Al catalysts, whereas in the Ni-Co-Al catalysts smaller metal particles of Ni(0) and Co(0), potentially as alloys, are formed, as evidenced by XAS, XPS, STEM and EELS. All the reduced Ni catalysts display similar selectivities towards major hydrogenation products (furfuryl alcohol and tetrahydrofurfuryl alcohol), though the side products varied with the catalyst composition. The 1.1Ni-0.8Co-Al catalyst showed the greatest activity per titrated site when compared to the othermore » catalysts, with promising activity compared to related catalysts in the literature. In conclusion, the use of base metal catalysts for hydrogenation of furanic compounds may be a promising alternative to the well-studied precious metal catalysts for making biomass-derived chemicals if catalyst selectivity can be improved in future work by alloying or tuning metal-oxide support interactions.« less

  9. Vapor phase hydrogenation of furfural over nickel mixed metal oxide catalysts derived from layered double hydroxides

    SciTech Connect

    Sulmonetti, Taylor P.; Pang, Simon H.; Claure, Micaela Taborga; Lee, Sungsik; Cullen, David A.; Agrawal, Pradeep K.; Jones, Christopher W.

    2016-03-09

    The hydrogenation of furfural is investigated over various reduced nickel mixed metal oxides derived from layered double hydroxides (LDHs) containing Ni-Mg-Al and Ni-Co-Al. Upon reduction, relatively large Ni(0) domains develop in the Ni-Mg-Al catalysts, whereas in the Ni-Co-Al catalysts smaller metal particles of Ni(0) and Co(0), potentially as alloys, are formed, as evidenced by XAS, XPS, STEM and EELS. All the reduced Ni catalysts display similar selectivities towards major hydrogenation products (furfuryl alcohol and tetrahydrofurfuryl alcohol), though the side products varied with the catalyst composition. The 1.1Ni-0.8Co-Al catalyst showed the greatest activity per titrated site when compared to the other catalysts, with promising activity compared to related catalysts in the literature. In conclusion, the use of base metal catalysts for hydrogenation of furanic compounds may be a promising alternative to the well-studied precious metal catalysts for making biomass-derived chemicals if catalyst selectivity can be improved in future work by alloying or tuning metal-oxide support interactions.

  10. Recovery Efficiency Test Project: Phase 1, Activity report

    SciTech Connect

    Overbey, W.K. Jr.; Wilkins, D.W.; Keltch, B.; Saradji, B.; Salamy, S.P.

    1988-04-01

    This report is the second volume of the Recovery Efficiency Test Phase I Report of Activities. Volume 1 covered selection, well planning, drilling, coring, logging and completion operations. This volume reports on well testing activities, reclamation activities on the drilling site and access roads, and the results of physical and mechanical properties tests on the oriented core material obtained from a horizontal section of the well. 3 refs., 21 figs., 10 tabs.

  11. Biofilms Versus Activated Sludge: Considerations in Metal and Metal Oxide Nanoparticle Removal from Wastewater.

    PubMed

    Walden, Connie; Zhang, Wen

    2016-08-16

    The increasing application of metal and metal oxide nanoparticles [Me(O)NPs] in consumer products has led to a growth in concentration of these nanoparticles in wastewater as emerging contaminants. This may pose a threat to ecological communities (e.g., biological nutrient removal units) within treatment plants and those subject to wastewater effluents. Here, the toxicity, fate, and process implications of Me(O)NPs within wastewater treatment, specifically during activated sludge processing and biofilm systems are reviewed and compared. Research showed activated sludge achieves high removal rate of Me(O)NPs by the formation of aggregates through adsorption. However, recent literature reveals evidence that inhibition is likely for nutrient removal capabilities such as nitrification. Biofilm systems were much less studied, but show potential to resist Me(O)NP inhibition and achieve removal through possible retention by sorption. Implicating factors during bacteria-Me(O)NP interactions such as aggregation, surface functionalization, and the presence of organics are summarized. At current modeled levels, neither activated sludge nor biofilm systems can achieve complete removal of Me(O)NPs, thus allowing for long-term environmental exposure of diverse biological communities to Me(O)NPs in streams receiving wastewater effluents. Future research directions are identified throughout in order to minimize the impact of these nanoparticles released.

  12. Development of processes for the production of solar grade silicon from halides and alkali metals, phase 1 and phase 2

    NASA Technical Reports Server (NTRS)

    Dickson, C. R.; Gould, R. K.; Felder, W.

    1981-01-01

    High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon are described. Product separation and collection processes were evaluated, measure heat release parameters for scaling purposes and effects of reactants and/or products on materials of reactor construction were determined, and preliminary engineering and economic analysis of a scaled up process were made. The feasibility of the basic process to make and collect silicon was demonstrated. The jet impaction/separation process was demonstrated to be a purification process. The rate at which gas phase species from silicon particle precursors, the time required for silane decomposition to produce particles, and the competing rate of growth of silicon seed particles injected into a decomposing silane environment were determined. The extent of silane decomposition as a function of residence time, temperature, and pressure was measured by infrared absorption spectroscopy. A simplistic model is presented to explain the growth of silicon in a decomposing silane enviroment.

  13. Origin of photogenerated carrier recombination at the metal-active layer interface in polymer solar cells.

    PubMed

    Kumar, Mukesh; Dubey, Ashish; Reza, Khan Mamun; Adhikari, Nirmal; Qiao, Qiquan; Bommisetty, Venkat

    2015-11-07

    The role of the metal-active layer interface in photogenerated recombination has been investigated using nanoscale current sensing atomic force microscopy (CS-AFM) and intensity modulated photocurrent spectroscopy (IMPS) in as-deposited, pre-annealed and post-annealed bulk heterojunction (BHJ) solar cells. Aluminum (Al) confined post-annealed BHJ solar cells exhibited a significantly improved device efficiency compared to pre-annealed BHJ solar cells having similar photocarrier harvesting ability in the active layer. The nanoscale topography and CS-AFM results indicate a uniform PCBM rich phase at the metal-active layer interface in the post-annealed cells, but PCBM segregation in the pre-annealed cells. These two different annealing processes showed different carrier dynamics revealed using IMPS under various light intensities. The IMPS results suggest reduced photo generated carrier recombination in uniform PCBM rich post-annealed BHJ solar cells. This study reveals the importance of the metal-bend interface in BHJ solar cells in order to obtain efficient charge carrier extraction for high efficiency.

  14. Topological Weyl superconductor to diffusive thermal Hall metal crossover in the B phase of UPt3

    NASA Astrophysics Data System (ADS)

    Goswami, Pallab; Nevidomskyy, Andriy H.

    2015-12-01

    The recent phase-sensitive measurements in the superconducting B phase of UPt3 provide strong evidence for the triplet, chiral kz(kx±i ky) 2 pairing symmetries, which endow the Cooper pairs with orbital angular momentum projections Lz=±2 along the c axis. In the absence of disorder such pairing can support both line and point nodes, and both types of nodal quasiparticles exhibit nontrivial topology in the momentum space. The point nodes, located at the intersections of the closed Fermi surfaces with the c axis, act as the double monopoles and the antimonopoles of the Berry curvature, and generalize the notion of Weyl quasiparticles. Consequently, the B phase should support an anomalous thermal Hall effect, the polar Kerr effect, in addition to the protected Fermi arcs on the (1 ,0 ,0 ) and the (0 ,1 ,0 ) surfaces. The line node at the Fermi surface equator acts as a vortex loop in the momentum space and gives rise to the zero-energy, dispersionless Andreev bound states on the (0 ,0 ,1 ) surface. At the transition from the B phase to the A phase, the time-reversal symmetry is restored, and only the line node survives inside the A phase. As both line and double-Weyl point nodes possess linearly vanishing density of states, we show that weak disorder acts as a marginally relevant perturbation. Consequently, an infinitesimal amount of disorder destroys the ballistic quasiparticle pole, while giving rise to a diffusive phase with a finite density of states at the zero energy. The resulting diffusive phase exhibits T -linear specific heat, and an anomalous thermal Hall effect. We predict that the low-temperature thermodynamic and transport properties display a crossover between a ballistic thermal Hall semimetal and a diffusive thermal Hall metal. By contrast, the diffusive phase obtained from a time-reversal-invariant pairing exhibits only the T -linear specific heat without any anomalous thermal Hall effect.

  15. Phase formation and mechanical properties of Cu-Zr-Ti bulk metallic glass composites

    NASA Astrophysics Data System (ADS)

    Kim, Byoung Jin; Yun, Young Su; Kim, Won Tae; Kim, Do Hyang

    2016-11-01

    The effect of the type of the crystalline phase and its volume fraction on the mechanical property of Cu50Zr50-xTix alloys (x = 0-10) bulk metallic glass composites has been investigated in this study. Up to 6 at% of Ti, B19' phase particles distributed in the glassy matrix, while at 8 and 10% of Ti, B2 phase particles are retained in the glass matrix due to suppression of the eutectoid transformation of B2 phase and by avoidance of martensitic transformation of B2 into B19'. The volume fraction of crystalline phase is strongly dependent on the cooling rate. The larger volume fraction of the crystalline phases results in the lower yield stress, the higher plastic strain, and the more pronounced work hardening behavior. At the crystalline volume fraction below 30%, the variation of the yield strength can be described by the rule of mixture model (ROM), while at the crystalline volume fraction higher than 50% by the load-bearing model (LBM). At the crystal fractions between 30 and 50%, there is a yield strength drop and a transition from the ROM to the LBM. This transition is due to the formation of the crystalline structural framework at higher crystal fraction.

  16. Thermodynamics of phase formation in the quantum critical metal Sr3Ru2O7

    PubMed Central

    Rost, A. W.; Grigera, S. A.; Bruin, J. A. N.; Perry, R. S.; Tian, D.; Raghu, S.; Kivelson, Steven Allan; Mackenzie, A. P.

    2011-01-01

    The behavior of matter near zero temperature continuous phase transitions, or “quantum critical points” is a central topic of study in condensed matter physics. In fermionic systems, fundamental questions remain unanswered: the nature of the quantum critical regime is unclear because of the apparent breakdown of the concept of the quasiparticle, a cornerstone of existing theories of strongly interacting metals. Even less is known experimentally about the formation of ordered phases from such a quantum critical “soup.” Here, we report a study of the specific heat across the phase diagram of the model system Sr3Ru2O7, which features an anomalous phase whose transport properties are consistent with those of an electronic nematic. We show that this phase, which exists at low temperatures in a narrow range of magnetic fields, forms directly from a quantum critical state, and contains more entropy than mean-field calculations predict. Our results suggest that this extra entropy is due to remnant degrees of freedom from the highly entropic state above Tc. The associated quantum critical point, which is “concealed” by the nematic phase, separates two Fermi liquids, neither of which has an identifiable spontaneously broken symmetry, but which likely differ in the topology of their Fermi surfaces. PMID:21933961

  17. Large Area Active Brazing of Multi-tile Ceramic-Metal Structures

    DTIC Science & Technology

    2012-05-01

    metal brazing . The active brazing alloys wet most materials (including ceramics and corrosion- resistant metals such as titanium alloys and stainless...bonding in ceramic-metal systems is active metal brazing . The active brazing alloys wet most materials (including ceramics and corrosion-resistant...an idea from the ‘50s by putting an “active” component, such as titanium, directly into a brazing alloy , typically a silver-copper eutectic, to

  18. Exploring Systematic Effects in the Relation Between Stellar Mass, Gas Phase Metallicity, and Star Formation Rate

    NASA Astrophysics Data System (ADS)

    Telford, O. Grace; Dalcanton, Julianne J.; Skillman, Evan D.; Conroy, Charlie

    2016-08-01

    There is evidence that the well-established mass-metallicity relation in galaxies is correlated with a third parameter: star formation rate (SFR). The strength of this correlation may be used to disentangle the relative importance of different physical processes (e.g., infall of pristine gas, metal-enriched outflows) in governing chemical evolution. However, all three parameters are susceptible to biases that might affect the observed strength of the relation between them. We analyze possible sources of systematic error, including sample bias, application of signal-to-noise ratio cuts on emission lines, choice of metallicity calibration, uncertainty in stellar mass determination, aperture effects, and dust. We present the first analysis of the relation between stellar mass, gas phase metallicity, and SFR using strong line abundance diagnostics from Dopita et al. for ˜130,000 star-forming galaxies in the Sloan Digital Sky Survey and provide a detailed comparison of these diagnostics in an appendix. Using these new abundance diagnostics yields a 30%-55% weaker anti-correlation between metallicity and SFR at fixed stellar mass than that reported by Mannucci et al. We find that, for all abundance diagnostics, the anti-correlation with SFR is stronger for the relatively few galaxies whose current SFRs are elevated above their past average SFRs. This is also true for the new abundance diagnostic of Dopita et al., which gives anti-correlation between Z and SFR only in the high specific star formation rate (sSFR) regime, in contrast to the recent results of Kashino et al. The poorly constrained strength of the relation between stellar mass, metallicity, and SFR must be carefully accounted for in theoretical studies of chemical evolution.

  19. Interaction of metallic clusters with biologically active curcumin molecules

    NASA Astrophysics Data System (ADS)

    Gupta, Sanjeev K.; He, Haiying; Liu, Chunhui; Dutta, Ranu; Pandey, Ravindra

    2015-09-01

    We have investigated the interaction of subnano metallic Gd and Au clusters with curcumin, an important biomolecule having pharmacological activity. Gd clusters show different site preference to curcumin and much stronger interaction strength, in support of the successful synthesis of highly stable curcumin-coated Gd nanoparticles as reported recently. It can be attributed to significant charge transfer from the Gd cluster to curcumin together with a relatively strong hybridization of the Gd df-orbitals with curcumin p-orbitals. These results suggest that Gd nanoparticles can effectively be used as delivery carriers for curcumin at the cellular level for therapy and medical imaging applications.

  20. Precipitation of sigma and chi phases in δ-ferrite of Type 316FR weld metals

    SciTech Connect

    Chun, Eun Joon; Baba, Hayato; Nishimoto, Kazutoshi; Saida, Kazuyoshi

    2013-12-15

    The decomposition behavior and kinetics of δ-ferrite are examined using aging treatments between 873 and 1073 K for Type 316FR stainless steel weld metals with different solidification modes (316FR AF, 316FR FA). The dominant precipitates are sigma, chi, and secondary austenite nucleated at δ-ferrite/austenite interfaces or in the interior of the ferrite grains. These precipitates consume all the ferrite during isothermal aging in both 316FR AF and FA weld metals. Differences in the precipitation behavior (precipitation initiation time and precipitation speed) between weld metals can be explained by i) the degree of Cr and Mo microsegregation within δ-ferrite or austenite near ferrite and ii) the nucleation sites induced due to the solidification mode (AF or FA), such as the ferrite amount. For both weld materials, a Johnson–Mehl-type equation can express the precipitation behavior of the sigma + chi phases and quantitatively predict the behavior at the service-exposure temperatures of a fast breed reactor. - Highlights: • Precipitation of σ and χ phase in Type 316FR welds (two solidification modes) • Different precipitation behaviors: precipitation initiation time and growth speed • Johnson-Mehl–type equation is the most applicable to the precipitation behaviors • Precipitation behaviors are predicted under service conditions of FBRs.

  1. Ultrathin phase-change coatings on metals for electrothermally tunable colors

    NASA Astrophysics Data System (ADS)

    Bakan, Gokhan; Ayas, Sencer; Saidzoda, Tohir; Celebi, Kemal; Dana, Aykutlu

    2016-08-01

    Metal surfaces coated with ultrathin lossy dielectrics enable color generation through strong interferences in the visible spectrum. Using a phase-change thin film as the coating layer offers tuning the generated color by crystallization or re-amorphization. Here, we study the optical response of surfaces consisting of thin (5-40 nm) phase-changing Ge2Sb2Te5 (GST) films on metal, primarily Al, layers. A color scale ranging from yellow to red to blue that is obtained using different thicknesses of as-deposited amorphous GST layers turns dim gray upon annealing-induced crystallization of the GST. Moreover, when a relatively thick (>100 nm) and lossless dielectric film is introduced between the GST and Al layers, optical cavity modes are observed, offering a rich color gamut at the expense of the angle independent optical response. Finally, a color pixel structure is proposed for ultrahigh resolution (pixel size: 5 × 5 μm2), non-volatile displays, where the metal layer acting like a mirror is used as a heater element. The electrothermal simulations of such a pixel structure suggest that crystallization and re-amorphization of the GST layer using electrical pulses are possible for electrothermal color tuning.

  2. Accumulation of fossil fuels and metallic minerals in active and ancient rift lakes

    USGS Publications Warehouse

    Robbins, E.I.

    1983-01-01

    A study of active and ancient rift systems around the world suggests that accumulations of fossil fuels and metallic minerals are related to the interactions of processes that form rift valleys with those that take place in and around rift lakes. The deposition of the precursors of petroleum, gas, oil shale, coal, phosphate, barite, Cu-Pb-Zn sulfides, and uranium begins with erosion of uplifted areas, and the consequent input of abundant nutrients and solute loads into swamps and tectonic lakes. Hot springs and volcanism add other nutrients and solutes. The resulting high biological productivity creates oxidized/reduced interfaces, and anoxic and H2S-rich bottom waters which preserves metal-bearing organic tissues and horizons. In the depositional phases, the fine-grained lake deposits are in contact with coarse-grained beach, delta, river, talus, and alluvial fan deposits. Earthquake-induced turbidites also are common coarse-grained deposits of rift lakes. Postdepositional processes in rifts include high heat flow and a resulting concentration of the organic and metallic components that were dispersed throughout the lakebeds. Postdepositional faulting brings organic- and metal-rich sourcebeds in contact with coarse-grained host and reservoir rocks. A suite of potentially economic deposits is therefore a characteristic of rift valleys. ?? 1983.

  3. CHEMICAL ACTIVATION OF MOLECULES BY METALS: EXPERIMENTAL STUDIES OF ELECTRON DISTRIBUTIONS AND BONDING

    SciTech Connect

    LICHTENBERGER, DENNIS L.

    2002-03-26

    This research program is directed at obtaining detailed experimental information on the electronic interactions between metals and organic molecules. These interactions provide low energy pathways for many important chemical and catalytic processes. A major feature of the program is the continued development and application of our special high-resolution valence photoelectron spectroscopy (UPS), and high-precision X-ray core photoelectron spectroscopy (XPS) instrumentation for study of organometallic molecules in the gas phase. The study involves a systematic approach towards understanding the interactions and activation of bound carbonyls, C-H bonds, methylenes, vinylidenes, acetylides, alkenes, alkynes, carbenes, carbynes, alkylidenes, alkylidynes, and others with various monometal, dimetal, and cluster metal species. Supporting ligands include -aryls, alkoxides, oxides, and phosphines. We are expanding our studies of both early and late transition metal species and electron-rich and electron-poor environments in order to more completely understand the electronic factors that serve to stabilize particular organic fragments and intermediates on metals. Additional new directions for this program are being taken in ultra-high vacuum surface UPS, XPS, scanning tunneling microscopy (STM) and atomic force microscopy (AFM) experiments on both physisorbed and chemisorbed organometallic thin films. The combination of these methods provides additional electronic structure information on surface-molecule and molecule-molecule interactions. A very important general result emerging from this program is the identification of a close relationship between the ionization energies of the species and the thermodynamics of the chemical and catalytic reactions of these systems.

  4. Pollution in the urban soils of Lianyungang, China, evaluated using a pollution index, mobility of heavy metals, and enzymatic activities.

    PubMed

    Li, Yu; Li, Hong-Guan; Liu, Fu-Cheng

    2017-01-01

    Soil samples from 16 urban sites in Lianyungang, China were collected and analyzed. A pollution index was used to assess the potential ecological risk of heavy metals and a sequential extraction procedure was used to evaluate the relative distribution of Cu, Zn, Pb, Cd, Cr, and As in exchangeable, carbonate, Fe/Mn oxide, organic/sulfide, and residual fractions. The mobility of heavy metals and urease (URE) activity, alkaline phosphatase (ALP) activity, and invertase (INV) activity of soils was determined. The results showed that the average concentrations of Cu, Zn, Pb, Cd, Cr, and As in Lianyungang soils were much higher than those in the coastal city soil background values of Jiangsu and China. Among the five studied regions (utilities, commercial, industrial, tourism, and roadside), the industrial region had the highest metal concentrations demonstrating that land use had a significant impact on the accumulation of heavy metals in Lianyungang soils. Compared to the other metals, Cd showed the highest ecological risk. According to chemical partitioning, Cu was associated with the organic/sulfides and Pb and Zn were mainly in the carbonate and the Fe/Mn oxide phase. The greatest amounts of Cd were found in exchangeable and carbonate fractions, while Cr and As were mainly in the residual fraction. Cd had the highest mobility of all metals, and the order of mobility (highest to lowest) of heavy metals in Lianyungang soils was Cd > Zn > Pb > Cu > As > Cr. Soil urease activity, alkaline phosphatase activity, and invertase activity varied considerably in different pollution degree sites. Soil enzyme activities had the lowest levels in roadside and industrial regions. Across all the soil data in the five regions, the total Cu, Zn, Pb, Cd, Cr, and As level was negatively correlated with urease activity, alkaline phosphatase activity, and invertase activity, but the relationship was not significant. In the industrial region, alkaline phosphatase activity had

  5. Improved description of metal oxide stability: Beyond the random phase approximation with renormalized kernels

    NASA Astrophysics Data System (ADS)

    Jauho, Thomas S.; Olsen, Thomas; Bligaard, Thomas; Thygesen, Kristian S.

    2015-09-01

    The renormalized adiabatic PBE (rAPBE) method has recently been shown to comprise a significant improvement over the random phase approximation (RPA) for total energy calculations of simple solids and molecules. Here we consider the formation energies of 19 group I and II metal oxides and a few transition-metal oxides. The mean absolute error relative to experiments is 0.21 eV and 0.38 eV per oxygen atom for rAPBE and RPA, respectively, and thus the rAPBE method greatly improves the description of metal-oxygen bonds across a wide range of oxides. The failure of the RPA can be partly attributed to the lack of error cancellation between the correlation energy of the oxide on the one hand and the bulk metal and oxygen molecule on the other hand, which are all separately predicted much too negative by the RPA. We ascribe the improved performance of the rAPBE to its significantly better description of absolute correlation energies which reduces the need for error cancellation. The rAPBE is just one out of an entire class of renormalized exchange-correlation kernels which should be further investigated.

  6. Transition metal activation and functionalization of carbon-hydrogen bonds

    SciTech Connect

    Jones, W.D.

    1992-06-01

    We are investigating the fundamental thermodynamic and kinetic factors that influence carbon-hydrogen bond activation at homogeneous transition metal centers and the conversion of hydrocarbons into functionalized products of potential use to the chemical industry. Advances have been made in both understanding the interactions of hydrocarbons with metals and in the functionalization of hydrocarbons. We have found that RhCl(PR{sub 3}){sub 2}(CNR) complexes can catalyze the insertion of isonitriles into the C-H bonds or arenes upon photolysis. The mechanism of these reactions was found to proceed by way of initial phosphine dissociation, followed by C-H activation and isonitrile insertion. We have also examined reactions of a series of arenes with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and begun to map out the kinetic and thermodynamic preferences for arene coordination. The effects of resonance, specifically the differences in the Hueckel energies of the bound vs free ligand, are now believed to fully control the C-H activation/{eta}{sup 2}-coordination equilibria. We have begun to examine the reactions of rhodium isonitrile pyrazolylborates for alkane and arene C-H bond activation. A new, labile, carbodiimide precursor has been developed for these studies. We have completed studies of the reactions of (C{sub 5}Me{sub 5})Rh(PMe{sub 3})H{sub 2} with D{sub 2} and PMe{sub 3} that indicate that both {eta}{sup 5} {yields} {eta}{sup 3} ring slippage and metal to ring hydride migration occur more facilely than thermal reductive elimination of H{sub 2}. We have examined the reactions of heterocycles with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and found that pyrrole and furan undergo C-H or N-H activation. Thiophene, however, undergoes C-S bond oxidative addition, and the mechanism of activation has been shown to proceed through sulfur coordination prior to C-S insertion.

  7. Correlation between structural heterogeneity and plastic deformation for phase separating FeCu metallic glasses

    PubMed Central

    Peng, Chuan-Xiao; Song, Kai-Kai; Wang, Li; Şopu, Daniel; Pauly, Simon; Eckert, Jürgen

    2016-01-01

    Unlike crystalline metals, the plastic deformation of metallic glasses (MGs) involves a competition between disordering and structural relaxation ordering, which is not well understood, yet. Molecular dynamics (MD) simulations were performed to investigate the evolutions of strain localizations, short-range order (SRO) as well as the free volume in the glass during compressive deformation of Fe50Cu50 MGs with different degrees of phase separation. Our findings indicate that the free volume in the phase separating MGs decreases while the shear strain localizations increase with increasing degree of phase separation. Cu-centered clusters show higher potential energies and Voronoi volumes, and bear larger local shear strains. On the other hand, Fe-centered pentagon-rich clusters in Cu-rich regions seem to play an important role to resist the shear transformation. The dilatation or annihilation of Voronoi volumes is due to the competition between ordering via structural relaxation and shear stress-induced deformation. The present study could provide a better understanding of the relationship between the structural inhomogeneity and the deformation of MGs. PMID:27681052

  8. Niobium doped TiO2: Intrinsic transparent metallic anatase versus highly resistive rutile phase

    NASA Astrophysics Data System (ADS)

    Zhang, S. X.; Kundaliya, D. C.; Yu, W.; Dhar, S.; Young, S. Y.; Salamanca-Riba, L. G.; Ogale, S. B.; Vispute, R. D.; Venkatesan, T.

    2007-07-01

    We report on the structural, electrical, and optical properties of 5% niobium doped TiO2 thin films grown on various substrates by pulsed laser deposition. The epitaxial anatase Nb:TiO2 film on LaAlO3 is shown to be an intrinsic transparent metal and its metallic property arises from Nb substitution into Ti site as evidenced by the Rutherford backscattering channeling result. In contrast, the rutile Nb:TiO2 thin films show insulating behaviors with 2-3 orders higher room temperature electrical resistivity and ˜30 times lower mobility. A blueshift in the optical absorption edge is observed in both phases, though of differing magnitude.

  9. Organic phase synthesis of noble metal-zinc chalcogenide core-shell nanostructures.

    PubMed

    Kumar, Prashant; Diab, Mahmud; Flomin, Kobi; Rukenstein, Pazit; Mokari, Taleb

    2016-10-15

    Multi-component nanostructures have been attracting tremendous attention due to their ability to form novel materials with unique chemical, optical and physical properties. Development of hybrid nanostructures that are composed of metal-semiconductor components using a simple approach is of interest. Herein, we report a robust and general organic phase synthesis of metal (Au or Ag)-Zinc chalcogenide (ZnS or ZnSe) core-shell nanostructures. This synthetic protocol also enabled the growth of more compositionally complex nanostructures of Au-ZnSxSe1-x alloys and Au-ZnS-ZnSe core-shell-shell. The optical and structural properties of these hybrid nanostructures are also presented.

  10. Computational studies of adsorption in metal organic frameworks and interaction of nanoparticles in condensed phases

    SciTech Connect

    Annapureddy, HVR; Motkuri, RK; Nguyen, PTM; Truong, TB; Thallapally, PK; McGrail, BP; Dang, LX

    2014-02-05

    In this review, we describe recent efforts to systematically study nano-structured metal organic frameworks (MOFs), also known as metal organic heat carriers, with particular emphasis on their application in heating and cooling processes. We used both molecular dynamics and grand canonical Monte Carlo simulation techniques to gain a molecular-level understanding of the adsorption mechanism of gases in these porous materials. We investigated the uptake of various gases such as refrigerants R12 and R143a. We also evaluated the effects of temperature and pressure on the uptake mechanism. Our computed results compared reasonably well with available measurements from experiments, thus validating our potential models and approaches. In addition, we investigated the structural, diffusive and adsorption properties of different hydrocarbons in Ni-2(dhtp). Finally, to elucidate the mechanism of nanoparticle dispersion in condensed phases, we studied the interactions among nanoparticles in various liquids, such as n-hexane, water and methanol.

  11. Matrix-assisted laser desorption mass spectrometry of gas-phase peptide-metal complexes

    NASA Astrophysics Data System (ADS)

    Hortal, Ana R.; Hurtado, Paola; Martínez-Haya, Bruno

    2008-12-01

    Cation attachment to a model peptide has been investigated in matrix-assisted laser desorption experiments. Angiotensin I (Asp-Arg-Val-Tyr-Ile-His-Pro-Phe-His-Leu) is chosen as a system for study, and Cu2+ and K+ salts are used as cationizing agents. Three fundamentally different types of samples are investigated: (1) a crystalline sample of Ang I, metal salt and MALDI matrix, prepared with the conventional dried droplet method; (2) a solvent-free fine powder mixture of the same three compounds, and (3) a solution of the angiotensin and the metal salt in an ionic liquid matrix (a molten organic salt that acts as a MALDI active solvent). Effective protonation and cationization of the peptide are achieved with the three methods. The transition metal systematically provides more efficient cationization than the alkali metal. At sufficiently high concentration of the salt, the attachment of up to four copper cations to the angiotensin is observed in the MALDI spectrum. In contrast, only one K+ cation is efficiently bound to the peptide. For a given salt concentration, the highest degree of cationization is obtained in the laser desorption from the ionic liquid matrix. This is attributed to the efficient transfer of free metal cations to the desorption plume, where the complexation takes place.

  12. A latchable thermally activated phase change actuator for microfluidic systems

    NASA Astrophysics Data System (ADS)

    Richter, Christiane; Sachsenheimer, Kai; Rapp, Bastian E.

    2016-03-01

    Complex microfluidic systems often require a high number of individually controllable active components like valves and pumps. In this paper we present the development and optimization of a latchable thermally controlled phase change actuator which uses a solid/liquid phase transition of a phase change medium and the displacement of the liquid phase change medium to change and stabilize the two states of the actuator. Because the phase change is triggered by heat produced with ohmic resistors the used control signal is an electrical signal. In contrast to pneumatically activated membrane valves this concept allows the individual control of several dozen actuators with only two external pressure lines. Within this paper we show the general working principle of the actuator and demonstrate its general function and the scalability of the concept at an example of four actuators. Additionally we present the complete results of our studies to optimize the response behavior of the actuator - the influence of the heating power as well as the used phase change medium on melting and solidifying times.

  13. Dynamic phases of active matter systems with quenched disorder

    NASA Astrophysics Data System (ADS)

    Sándor, Cs.; Libál, A.; Reichhardt, C.; Olson Reichhardt, C. J.

    2017-03-01

    Depinning and nonequilibrium transitions within sliding states in systems driven over quenched disorder arise across a wide spectrum of size scales ranging from atomic friction at the nanoscale, flux motion in type II superconductors at the mesoscale, colloidal motion in disordered media at the microscale, and plate tectonics at geological length scales. Here we show that active matter or self-propelled particles interacting with quenched disorder under an external drive represents a class of system that can also exhibit pinning-depinning phenomena, plastic flow phases, and nonequilibrium sliding transitions that are correlated with distinct morphologies and velocity-force curve signatures. When interactions with the substrate are strong, a homogeneous pinned liquid phase forms that depins plastically into a uniform disordered phase and then dynamically transitions first into a moving stripe coexisting with a pinned liquid and then into a moving phase-separated state at higher drives. We numerically map the resulting dynamical phase diagrams as a function of external drive, substrate interaction strength, and self-propulsion correlation length. These phases can be observed for active matter moving through random disorder. Our results indicate that intrinsically nonequilibrium systems can exhibit additional nonequilibrium transitions when subjected to an external drive.

  14. Phase-resolved pulse propagation through metallic photonic crystal slabs: plasmonic slow light.

    PubMed

    Schönhardt, Anja; Nau, Dietmar; Bauer, Christina; Christ, André; Gräbeldinger, Hedi; Giessen, Harald

    2017-03-28

    We characterized the electromagnetic field of ultra-short laser pulses after propagation through metallic photonic crystal structures featuring photonic and plasmonic resonances. The complete pulse information, i.e. the envelope and phase of the electromagnetic field, was measured using the technique of cross-correlation frequency resolved optical gating. In good agreement, measurements and scattering matrix simulations show a dispersive behaviour of the spectral phase at the position of the resonances. Asymmetric Fano-type resonances go along with asymmetric phase characteristics. Furthermore, the spectral phase is used to calculate the dispersion of the sample and possible applications in dispersion compensation are investigated. Group refractive indices of 700 and 70 and group delay dispersion values of 90 000 fs(2) and 5000 fs(2) are achieved in transverse electric and transverse magnetic polarization, respectively. The behaviour of extinction and spectral phase can be understood from an intuitive model using the complex transmission amplitude. An associated depiction in the complex plane is a useful approach in this context. This method promises to be valuable also in photonic crystal and filter design, for example, with regards to the symmetrization of the resonances.This article is part of the themed issue 'New horizons for nanophotonics'.

  15. Underground Corrosion of Activated Metals, 6-Year Exposure Analysis

    SciTech Connect

    M. K. Adler Flitton; T. S. Yoder

    2006-03-01

    The subsurface radioactive disposal site located at the Idaho National Laboratory contains neutronactivated metals from non-fuel nuclear-reactor-core components. A long-term underground corrosion test is being conducted to obtain site-specific corrosion rates to support efforts to more accurately estimate the transfer of activated elements in the surrounding arid vadose zone environment. The test uses nonradioactive metal coupons representing the prominent neutron-activated materials buried at the disposal location, namely, Type 304L stainless steel (UNS S30403), Type 316L stainless steel (S31603), nickel-chromium alloy (UNS NO7718), beryllium, aluminum 6061-T6 (A96061), and a zirconium alloy (UNS R60804). In addition, carbon steel (the material presently used in the cask disposal liners and other disposal containers) and a duplex stainless steel (UNS S32550) are also included in the test. This paper briefly describes the ongoing test and presents the results of corrosion analysis from coupons exposed underground for 1, 3, and 6 years.

  16. Nitrification and Heavy Metal Removal in the Activated Sludge Treatment Process.

    DTIC Science & Technology

    1976-08-01

    parameters to heavy metal removal in the activated sludge waste treatment process. The heavy metals studied were chromium and silver. Analyses...performed on the influent, mixed liquor, return sludge, and effluent included heavy metal concentration, pH, dissolved oxygen, temperature, suspended solids...related to heavy metal removal. Nitrification is only indirectly related. A theory for the mechanisms contributing to heavy metal removal is developed.

  17. First Principles Calculations of Transition Metal Binary Alloys: Phase Stability and Surface Effects

    NASA Astrophysics Data System (ADS)

    Aspera, Susan Meñez; Arevalo, Ryan Lacdao; Shimizu, Koji; Kishida, Ryo; Kojima, Kazuki; Linh, Nguyen Hoang; Nakanishi, Hiroshi; Kasai, Hideaki

    2017-03-01

    The phase stability and surface effects on binary transition metal nano-alloy systems were investigated using density functional theory-based first principles calculations. In this study, we evaluated the cohesive and alloying energies of six binary metal alloy bulk systems that sample each type of alloys according to miscibility, i.e., Au-Ag and Pd-Ag for the solid solution-type alloys (SS), Pd-Ir and Pd-Rh for the high-temperature solid solution-type alloys (HTSS), and Au-Ir and Ag-Rh for the phase-separation (PS)-type alloys. Our results and analysis show consistency with experimental observations on the type of materials in the bulk phase. Varying the lattice parameter was also shown to have an effect on the stability of the bulk mixed alloy system. It was observed, particularly for the PS- and HTSS-type materials, that mixing gains energy from the increasing lattice constant. We furthermore evaluated the surface effects, which is an important factor to consider for nanoparticle-sized alloys, through analysis of the (001) and (111) surface facets. We found that the stability of the surface depends on the optimization of atomic positions and segregation of atoms near/at the surface, particularly for the HTSS and the PS types of metal alloys. Furthermore, the increase in energy for mixing atoms at the interface of the atomic boundaries of PS- and HTSS-type materials is low enough to overcome by the gain in energy through entropy. These, therefore, are the main proponents for the possibility of mixing alloys near the surface.

  18. Phase diagram for assembly of biologically-active peptide amphiphiles.

    PubMed

    Tsonchev, Stefan; Niece, Krista L; Schatz, George C; Ratner, Mark A; Stupp, Samuel I

    2008-01-17

    We construct a phase diagram for self-assembling biologically active peptide amphiphiles. The structure and stability of the assemblies are studied as a function of pH and salinity of the solution. The general features of the phase diagram are predicted based on theoretical modeling of the self-assembly process, as well as experimental data, and further experiments are performed to verify and ascertain the boundary locations of the diagram. Depending on solution conditions, the amphiphiles can form cylindrical or spherical micelles, intermediate structures between these, or may not assemble at all. We also demonstrate that changing conditions may result in phase transitions among these structures. This type of phase diagram could be useful in the design of certain supramolecular nanostructures by providing information on the necessary conditions to form them.

  19. PHASE-FIELD SIMULATION OF IRRADIATED METALS: PART II: GAS BUBBLE KINETICS

    SciTech Connect

    Paul C Millett; Anter El-Azab

    2011-01-01

    We present a phase-field model for inert gas bubble formation and evolution in irradiated metals. The model evolves vacancy, self-interstitial, and fission gas atoms through a coupled set of Cahn-Hilliard and Allen-Cahn equations, capturing the processes of defect generation, recombination, annihilation at GB sinks, as well as intragranular and intergranular bubble nucleation and growth in polycrystalline microstructures. Illustrative results are presented that characterize bubble growth and shrinkage, as well as the bubble density, size and nucleation rate as a function of varying irradiation conditions. Finally, intergranular bubble characteristics such as shape, pinning energy on GB motion, and bubble density are investigated.

  20. Method for preparing surfaces of metal composites having a brittle phase for plating. [Patent application

    DOEpatents

    Coates, C.W.; Wilson, T.J.

    1982-05-19

    The present invention is directed to a method for preparing surfaces of two-phase metal composites having relatively brittle and malleable components for plating with corrosion-resistant material. In practice of the present invention, the surfaces of the composite are etched to remove a major portion or fraction of the brittle component. The etched surface is then peened with particulates for breaking the brittle component from the surfaces and for spreading or smearing the malleable component over the surfaces. The peened surface is then chemically cleaned of residual traces of the brittle component to which the corrosion-resistant material may be plated thereon in an adherent manner.

  1. Anomalous Metal Phase Emergent on the Verge of an Exciton Mott Transition

    NASA Astrophysics Data System (ADS)

    Sekiguchi, Fumiya; Mochizuki, Toshimitsu; Kim, Changsu; Akiyama, Hidefumi; Pfeiffer, Loren N.; West, Ken W.; Shimano, Ryo

    2017-02-01

    We investigate the exciton Mott transition (EMT) by using optical pump-terahertz probe spectroscopy on GaAs, with realizing the condition of Mott's gedanken experiment by the resonant excitation of 1 s excitons. We show that an anomalous metallic phase emerges on the verge of the EMT as manifested by a peculiar enhancement of the quasiparticle mass and scattering rate. From the temperature and density dependence, the observed anomaly is shown to originate from the electron-hole (e -h ) correlation which becomes prominent at low temperatures, possibly suggesting a precursor of e -h Cooper pairing.

  2. Semiconductor-to-metal phase transition in monolayer ZrS2: GGA+U study

    NASA Astrophysics Data System (ADS)

    Kumar, Ashok; He, Haiying; Pandey, Ravindra; Ahluwalia, P. K.; Tankeshwar, K.

    2015-06-01

    We report structural and electronic properties of ZrS2 monolayer within density functional theory (DFT) by inclusion of Hubbard on-site Coulomb and exchange interactions. The importance of on-site interactions for both ZrS2 bulk and monolayer has been highlighted that significantly improves the electronic band-gap. It is demonstrated that mechanical strain induces structural phase transition that results in semiconductor-to-metal transition in monolayer ZrS2. This phenomenon has important implications in technological applications such as flexible, low power and transparent electronic devices.

  3. TSCA Chemical Data Reporting Fact Sheet: Reporting Manufactured Chemical Substances from Metal Mining and Related Activities

    EPA Pesticide Factsheets

    This fact sheet provides guidance on the Chemical Data Reporting (CDR) rule requirements related to the reporting of mined metals, intermediates, and byproducts manufactured during metal mining and related activities.

  4. Pressure and phase equilibria in interacting active brownian spheres.

    PubMed

    Solon, Alexandre P; Stenhammar, Joakim; Wittkowski, Raphael; Kardar, Mehran; Kafri, Yariv; Cates, Michael E; Tailleur, Julien

    2015-05-15

    We derive a microscopic expression for the mechanical pressure P in a system of spherical active Brownian particles at density ρ. Our exact result relates P, defined as the force per unit area on a bounding wall, to bulk correlation functions evaluated far away from the wall. It shows that (i) P(ρ) is a state function, independent of the particle-wall interaction; (ii) interactions contribute two terms to P, one encoding the slow-down that drives motility-induced phase separation, and the other a direct contribution well known for passive systems; and (iii) P is equal in coexisting phases. We discuss the consequences of these results for the motility-induced phase separation of active Brownian particles and show that the densities at coexistence do not satisfy a Maxwell construction on P.

  5. Pressure-induced metallization and structural phase transition of the Mott-Hubbard insulator TiOBr

    NASA Astrophysics Data System (ADS)

    Kuntscher, C. A.; Frank, S.; Pashkin, A.; Hoffmann, H.; Schönleber, A.; van Smaalen, S.; Hanfland, M.; Glawion, S.; Klemm, M.; Sing, M.; Horn, S.; Claessen, R.

    2007-12-01

    We investigated the pressure-dependent optical response of the low-dimensional Mott-Hubbard insulator TiOBr by transmittance and reflectance measurements in the infrared and visible frequency range. A suppression of the transmittance above a critical pressure and a concomitant increase of the reflectance are observed, suggesting a pressure-induced metallization of TiOBr. The metallic phase of TiOBr at high pressure is confirmed by the presence of additional excitations extending down to the far-infrared range. The pressure-induced metallization coincides with a structural phase transition, according to the results of x-ray powder diffraction experiments under pressure.

  6. On the bad metallicity and phase diagrams of Fe1+δX (X =Te, Se, S, solid solutions): an electrical resistivity study

    NASA Astrophysics Data System (ADS)

    El Massalami, M.; Deguchi, K.; Machida, T.; Takeya, H.; Takano, Y.

    2014-12-01

    Based on a systematic analysis of the thermal evolution of the resistivities of Fe-based chalcogenides Fe1+δTe1-xXx (X = Se, S), it is inferred that their often observed nonmetallic resistivities are related to a presence of two resistive channels: one is a high- temperature thermally-activated process while the other is a low-temperature log-in-T process. On lowering temperature, there are often two metal-to-nonmetall crossover events: one from the high-T thermally-activated nonmetallic regime into a metal-like phase and the other from the log-in-T regime into a second metal-like phase. Based on these events, together with the magnetic and superconducting transitions, a phase diagram is constructed for each series. We discuss the origin of both processes as well as the associated crossover events. We also discuss how these resistive processes are being influenced by pressure, intercalation, disorder, doping, or sample condition and, in turn, how these modifications are shaping the associated phase diagrams.

  7. Impact of active phase chemical composition and dispersity on catalytic behavior in PROX reaction

    NASA Astrophysics Data System (ADS)

    Cherkezova-Zheleva, Z.; Paneva, D.; Todorova, S.; Kolev, H.; Shopska, M.; Yordanova, I.; Mitov, I.

    2014-04-01

    Iron and iron-platinum catalysts supported on activated carbon have been successfully synthesized by wet impregnation method and low-temperature treatment in inert atmosphere. The content of the supported phases corresponds to 10 wt % Fe and 0.5 wt % Pt. Four catalytic samples were synthesized: Sample A—activated carbon impregnated with Fe nitrate; Sample B—activated carbon impregnated with Pt salt; Sample C—activated carbon impregnated consequently with Fe and Pt salts; Sample D—activated carbon impregnated simultaneously with Fe and Pt salts. The as-prepared materials were characterized by Mössbauer spectroscopy, X-ray diffraction, infrared and X-ray photoelectron spectroscopy. The spectra show that the activated carbon support and the preparation procedure give rise to the synthesis of isolated metal Pt ions and ultradispersed Fe and Pt oxide species. Probably the presence of different functional groups of activated carbon gives rise to registered very high dispersion of loaded species on support. The catalytic tests were carried out in PROX reaction. A lower activity of bimetallic Pt-Fe samples was explained with the increase in surface oxygen species as a result of predomination of iron oxide on the support leading to the increase in selectivity to the H2 oxidation. Partial agglomeration of supported iron oxide phase was registered after catalytic tests.

  8. A novel hybrid metal-organic framework-polymeric monolith for solid-phase microextraction.

    PubMed

    Lin, Chen-Lan; Lirio, Stephen; Chen, Ya-Ting; Lin, Chia-Her; Huang, Hsi-Ya

    2014-03-17

    This study describes the fabrication of a novel hybrid metal-organic framework- organic polymer (MOF-polymer) for use as a stationary phase in fritless solid-phase microextraction (SPME) for validating analytical methods. The MOF-polymer was prepared by using ethylene dimethacrylate (EDMA), butyl methacrylate (BMA), and an imidazolium-based ionic liquid as porogenic solvent followed by microwave-assisted polymerization with the addition of 25 % MOF. This novel hybrid MOF-polymer was used to extract penicillin (penicillin G, penicillin V, oxacillin, cloxacillin, nafcillin, dicloxacillin) under different conditions. Quantitative analysis of the extracted penicillin samples using the MOF-organic polymer for SPME was conducted by using capillary electrochromatography (CEC) coupled with UV analysis. The penicillin recovery was 63-96.2 % with high reproducibility, sensitivity, and reusability. The extraction time with the proposed fabricated SPME was only 34 min.

  9. A molecular dynamics study of the phase transition in bcc metal nanoparticles.

    PubMed

    Shibuta, Yasushi; Suzuki, Toshio

    2008-10-14

    The phase transition between liquid and solid phases in body-centered cubic (bcc) metal nanoparticles of iron, chromium, molybdenum, and tungsten with size ranging from 2000 to 31,250 atoms was investigated using a molecular dynamics simulation. The nucleation from an undercooled liquid droplet was observed during cooling in all nanoparticles considered. It was found that a nucleus was generated near one side of the particle and solidification spread toward the other side the during nucleation process. On the other hand, the surface melting and subsequent inward melting of the solid core of the nanoparticles were observed during heating. The depression of the melting point was proportional to the inverse of the particle radius due to the Gibbs-Thomson effect. On the other hand, the depression of the nucleation temperature during cooling was not monotonic with respect to the particle radius since the nucleation from an undercooled liquid depends on the event probability of an embryo or a nucleus.

  10. Metal - Insulator Transition Driven by Vacancy Ordering in GeSbTe Phase Change Materials

    PubMed Central

    Bragaglia, Valeria; Arciprete, Fabrizio; Zhang, Wei; Mio, Antonio Massimiliano; Zallo, Eugenio; Perumal, Karthick; Giussani, Alessandro; Cecchi, Stefano; Boschker, Jos Emiel; Riechert, Henning; Privitera, Stefania; Rimini, Emanuele; Mazzarello, Riccardo; Calarco, Raffaella

    2016-01-01

    Phase Change Materials (PCMs) are unique compounds employed in non-volatile random access memory thanks to the rapid and reversible transformation between the amorphous and crystalline state that display large differences in electrical and optical properties. In addition to the amorphous-to-crystalline transition, experimental results on polycrystalline GeSbTe alloys (GST) films evidenced a Metal-Insulator Transition (MIT) attributed to disorder in the crystalline phase. Here we report on a fundamental advance in the fabrication of GST with out-of-plane stacking of ordered vacancy layers by means of three distinct methods: Molecular Beam Epitaxy, thermal annealing and application of femtosecond laser pulses. We assess the degree of vacancy ordering and explicitly correlate it with the MIT. We further tune the ordering in a controlled fashion attaining a large range of resistivity. Employing ordered GST might allow the realization of cells with larger programming windows. PMID:27033314

  11. Plasticity-improved Zr-Cu-Al bulk metallic glass matrix composites containing martensite phase

    SciTech Connect

    Sun, Y.F.; Wei, B.C.; Wang, Y.R.; Li, W.H.; Cheung, T.L.; Shek, C.H.

    2005-08-01

    Zr{sub 48.5}Cu{sub 46.5}Al{sub 5} bulk metallic glass matrix composites with diameters of 3 and 4 mm were produced through water-cooled copper mold casting. Micrometer-sized bcc based B2 structured CuZr phase containing martensite plate, together with some densely distributed nanocrystalline Zr{sub 2}Cu and plate-like Cu{sub 10}Zr{sub 7} compound, was found embedded in a glassy matrix. The microstructure formation strongly depends on the composition and cooling rate. Room temperature compression tests reveal significant strain hardening and plastic strains of 7.7% and 6.4% before failure are obtained for the 3-mm- and 4-mm-diam samples, respectively. The formation of the martensite phase is proposed to contribute to the strain hardening and plastic deformation of the materials.

  12. Selective reflection by deteriorated phase accumulation in Fabry-Perot cavity with aperiodic metallic nanomesh entry windows

    NASA Astrophysics Data System (ADS)

    Sun, Tianyi; Guo, Chuanfei; Kempa, Krzysztof; Ren, Zhifeng

    2014-03-01

    A Fabry-Perot reflection filter, consisting of semi-transparent metal and dielectric layers on opaque metals, is featured by selective absorption determined by the phase difference of waves from the two interfaces. In such systems, semi-transparency is usually realized by layers of reflective metals thinner than the penetration depth of the light. Here we present a filter cavity with entry windows not made of traditional thin layers, but of aperiodic metallic random nanomeshes thicker than the penetration depth, fabricated by grain boundary lithography. It is shown that due to the deteriorated phase caused by the interface between the random nanomesh and the dielectric layer, the width and location of the resonances can be tuned by metallic coverage. Further experiments show that this phenomenon can be used in designing aperiodic plasmonic metamaterial structures for visible and infrared applications.

  13. Anomalous large electrical capacitance of planar microstructures with vanadium dioxide films near the insulator-metal phase transition

    SciTech Connect

    Aliev, V. Sh. Bortnikov, S. G.; Badmaeva, I. A.

    2014-03-31

    The temperature dependence of electrical capacitance of planar microstructures with vanadium dioxide (VO{sub 2}) film near the insulator-metal phase transition has been investigated at the frequency of 1 MHz. Electrical capacitance measurements of the microstructures were performed by the technique based on the using of a two-terminal resistor-capacitor module simulating the VO{sub 2} layer behavior at the insulator-metal phase transition. At temperatures 325–342 K, the anomalous increase in microstructures capacitance was observed. Calculation of electric field in the microstructure showed that VO{sub 2} relative permittivity (ε) reaches ∼10{sup 8} at the percolation threshold. The high value of ε can be explained by the fractal nature of the interface between metal and insulator clusters formed near the insulator-metal phase transition.

  14. The carburization of transition metal molybdates (MxMoO₄, M= Cu, Ni or Co) and the generation of highly active metal/carbide catalysts for CO₂ hydrogenation

    SciTech Connect

    Rodriguez, Jose A.; Xu, Wenqian; Ramirez, Pedro J.; Stachiola, Dario; Brito, Joaquin L.

    2015-05-06

    A new approach has been tested for the preparation of metal/Mo₂C catalysts using mixed-metal oxide molybdates as precursors. Synchrotron-based in situ time-resolved X-ray diffraction was used to study the reduction and carburization processes of Cu₃(MoO₄)₂(OH)₂, a-NiMoO₄ and CoMoO₄•nH₂O by thermal treatment under mixtures of hydrogen and methane. In all cases, the final product was β-Mo₂C and a metal phase (Cu, Ni, or Co), but the transition sequence varied with the different metals, and it could be related to the reduction potential of the Cu²⁺, Ni²⁺ and Co²⁺ cations inside each molybdate. The synthesized Cu/Mo₂C, Ni/Mo₂C and Co/Mo₂C catalysts were highly active for the hydrogenation of CO₂. The metal/Mo₂C systems exhibited large variations in the selectivity towards methanol, methane and CnH₂n₊₂ (n > 2) hydrocarbons depending on the nature of the supported metal and its ability to cleave C-O bonds. Cu/Mo₂C displayed a high selectivity for CO and methanol production. Ni/Mo₂C and Co/Mo₂C were the most active catalysts for the activation and full decomposition of CO₂, showing high selectivity for the production of methane (Ni case) and CnH₂n₊₂ (n > 2) hydrocarbons (Co case).

  15. The carburization of transition metal molybdates (MxMoO₄, M= Cu, Ni or Co) and the generation of highly active metal/carbide catalysts for CO₂ hydrogenation

    DOE PAGES

    Rodriguez, Jose A.; Xu, Wenqian; Ramirez, Pedro J.; ...

    2015-05-06

    A new approach has been tested for the preparation of metal/Mo₂C catalysts using mixed-metal oxide molybdates as precursors. Synchrotron-based in situ time-resolved X-ray diffraction was used to study the reduction and carburization processes of Cu₃(MoO₄)₂(OH)₂, a-NiMoO₄ and CoMoO₄•nH₂O by thermal treatment under mixtures of hydrogen and methane. In all cases, the final product was β-Mo₂C and a metal phase (Cu, Ni, or Co), but the transition sequence varied with the different metals, and it could be related to the reduction potential of the Cu²⁺, Ni²⁺ and Co²⁺ cations inside each molybdate. The synthesized Cu/Mo₂C, Ni/Mo₂C and Co/Mo₂C catalysts were highlymore » active for the hydrogenation of CO₂. The metal/Mo₂C systems exhibited large variations in the selectivity towards methanol, methane and CnH₂n₊₂ (n > 2) hydrocarbons depending on the nature of the supported metal and its ability to cleave C-O bonds. Cu/Mo₂C displayed a high selectivity for CO and methanol production. Ni/Mo₂C and Co/Mo₂C were the most active catalysts for the activation and full decomposition of CO₂, showing high selectivity for the production of methane (Ni case) and CnH₂n₊₂ (n > 2) hydrocarbons (Co case).« less

  16. Noble metal catalyzed aqueous phase hydrogenation and hydrodeoxygenation of lignin-derived pyrolysis oil and related model compounds.

    PubMed

    Mu, Wei; Ben, Haoxi; Du, Xiaotang; Zhang, Xiaodan; Hu, Fan; Liu, Wei; Ragauskas, Arthur J; Deng, Yulin

    2014-12-01

    Aqueous phase hydrodeoxygenation of lignin pyrolysis oil and related model compounds were investigated using four noble metals supported on activated carbon. The hydrodeoxygenation of guaiacol has three major reaction pathways and the demethylation reaction, mainly catalyzed by Pd, Pt and Rh, produces catechol as the products. The presence of catechol and guaiacol in the reaction is responsible for the coke formation and the catalysts deactivation. As expected, there was a significant decrease in the specific surface area of Pd, Pt and Rh catalysts during the catalytic reaction because of the coke deposition. In contrast, no catechol was produced from guaiacol when Ru was used so a completely hydrogenation was accomplished. The lignin pyrolysis oil upgrading with Pt and Ru catalysts further validated the reaction mechanism deduced from model compounds. Fully hydrogenated bio-oil was produced with Ru catalyst.

  17. Unusual magnetic phases in the strong interaction limit of two-dimensional topological band insulators in transition metal oxides

    NASA Astrophysics Data System (ADS)

    Kargarian, Mehdi; Langari, Abdollah; Fiete, Gregory A.

    2013-03-01

    The expected phenomenology of non-interacting topological band insulators (TBI) is now largely theoretically understood. However, the fate of TBIs in the presence of interactions remains an active area of research with novel, interaction-driven topological states possible, as well as new exotic magnetic states. In this work we study the magnetic phases of an exchange Hamiltonian arising in the strong interaction limit of a Hubbard model on the honeycomb lattice whose non-interacting limit is a two-dimensional TBI recently proposed for the layered heavy transition metal oxide compound, (Li,Na)2IrO3. By a combination of analytical methods and exact diagonalization studies on finite size clusters, we map out the magnetic phase diagram of the model. We find that strong spin-orbit coupling can lead to a phase transition from an antiferromagnetic Neél state to a spiral or stripy ordered state. We also discuss the conditions under which a quantum spin liquid may appear in our model, and we compare our results with the different but related Kitaev-Heisenberg-J2-J3 model which has recently been studied in a similar context. We gratefully acknowledge financial support from ARO Grant No. W911NF-09-1-0527 and NSF Grant No. DMR-0955778

  18. Unusual magnetic phases in the strong interaction limit of two-dimensional topological band insulators in transition metal oxides

    NASA Astrophysics Data System (ADS)

    Kargarian, Mehdi; Langari, Abdollah; Fiete, Gregory A.

    2012-11-01

    The expected phenomenology of noninteracting topological band insulators (TBIs) is now largely theoretically understood. However, the fate of TBIs in the presence of interactions remains an active area of research with novel, interaction-driven topological states possible, as well as new exotic magnetic states. In this work we study the magnetic phases of an exchange Hamiltonian arising in the strong interaction limit of a Hubbard model on the honeycomb lattice whose noninteracting limit is a two-dimensional TBI recently proposed for the layered heavy transition metal oxide compound (Li,Na)2IrO3. By a combination of analytical methods and exact diagonalization studies on finite-size clusters, we map out the magnetic phase diagram of the model. We find that strong spin-orbit coupling can lead to a phase transition from an antiferromagnetic Neél state to a spiral or stripy ordered state. We also discuss the conditions under which a quantum spin liquid may appear in our model, and we compare our results with the different but related Kitaev-Heisenberg-J2-J3 model which has recently been studied in a similar context.

  19. Strain-induced topological phase transition at zigzag edges of monolayer transition-metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Li, Linhu; Castro, Eduardo V.; Sacramento, Pedro D.

    2016-11-01

    The effect of strain in zigzag ribbons of monolayer transition-metal dichalcogenides with induced superconductivity is studied using a minimal three-band tight-binding model. The unstrained system shows a topological phase with Majorana zero modes localized at the boundaries of the one-dimensional (1D) zigzag edges. By direct inspection of the spectrum and wave functions we examine the evolution of the topological phase as an in-plane, uniaxial deformation is imposed. It is found that strain shifts the energy of 1D edge states, thus causing a topological phase transition which eliminates the Majorana modes. For realistic parameter values, we show that the effect of strain can be changed from completely destructive—in which case a small built-in strain is enough to destroy the topological phase—to a situation where strain becomes an effective tuning parameter which can be used to manipulate Majorana zero modes. These two regimes are accessible by increasing the value of the applied Zeeman field within realistic values. We also study how strain effects are affected by the chemical potential, showing, in particular, how unwanted effects can be minimized. Finally, as a cross-check of the obtained results, we reveal the connection between 1D Majorana zero modes in the zigzag edge and the multiband Berry phase, which serves as a topological invariant of this system.

  20. Pontine respiratory activity involved in inspiratory/expiratory phase transition

    PubMed Central

    Mörschel, Michael; Dutschmann, Mathias

    2009-01-01

    Control of the timing of the inspiratory/expiratory (IE) phase transition is a hallmark of respiratory pattern formation. In principle, sensory feedback from pulmonary stretch receptors (Breuer–Hering reflex, BHR) is seen as the major controller for the IE phase transition, while pontine-based control of IE phase transition by both the pontine Kölliker–Fuse nucleus (KF) and parabrachial complex is seen as a secondary or backup mechanism. However, previous studies have shown that the BHR can habituate in vivo. Thus, habituation reduces sensory feedback, so the role of the pons, and specifically the KF, for IE phase transition may increase dramatically. Pontine-mediated control of the IE phase transition is not completely understood. In the present review, we discuss existing models for ponto-medullary interaction that may be involved in the control of inspiratory duration and IE transition. We also present intracellular recordings of pontine respiratory units derived from an in situ intra-arterially perfused brainstem preparation of rats. With the absence of lung inflation, this preparation generates a normal respiratory pattern and many of the recorded pontine units demonstrated phasic respiratory-related activity. The analysis of changes in membrane potentials of pontine respiratory neurons has allowed us to propose a number of pontine-medullary interactions not considered before. The involvement of these putative interactions in pontine-mediated control of IE phase transitions is discussed. PMID:19651653

  1. SOLID PHASE MICROEXTRACTION SAMPLING OF FIRE DEBRIS RESIDUES IN THE PRESENCE OF RADIONUCLIDE SURROGATE METALS

    SciTech Connect

    Duff, M; Keisha Martin, K; S Crump, S

    2007-03-23

    The Federal Bureau of Investigation (FBI) Laboratory currently does not have on site facilities for handling radioactive evidentiary materials and there are no established FBI methods or procedures for decontaminating highly radioactive fire debris (FD) evidence while maintaining evidentiary value. One experimental method for the isolation of FD residue from radionuclide metals involves using solid phase microextraction (SPME) fibers to remove the residues of interest. Due to their high affinity for organics, SPME fibers should have little affinity for most (radioactive) metals. The focus of this research was to develop an examination protocol that was applicable to safe work in facilities where high radiation doses are shielded from the workers (as in radioactive shielded cells or ''hot cells''). We also examined the affinity of stable radionuclide surrogate metals (Co, Ir, Re, Ni, Ba, Cs, Nb, Zr and Nd) for sorption by the SPME fibers. This was done under exposure conditions that favor the uptake of FD residues under conditions that will provide little contact between the SPME and the FD material (such as charred carpet or wood that contains commonly-used accelerants). Our results from mass spectrometric analyses indicate that SPME fibers show promise for use in the room temperature head space uptake of organic FD residue (namely, diesel fuel oil, kerosene, gasoline and paint thinner) with subsequent analysis by gas chromatography (GC) with mass spectrometric (MS) detection. No inorganic forms of ignitable fluids were included in this study.

  2. Computational studies of adsorption in metal organic frameworks and interaction of nanoparticles in condensed phases

    SciTech Connect

    Annapureddy, Harsha V.; Motkuri, Radha K.; Nguyen, Phuong T.; Truong, T. B.; Thallapally, Praveen K.; McGrail, B. Peter; Dang, Liem X.

    2014-01-08

    In this review, we describe recent efforts in which computer simulations were used to systematically study nano-structured metal organic frameworks, with particular emphasis on their application in heating and cooling processes. These materials also are known as metal organic heat carriers. We used both molecular dynamics and Grand Canonical Monte Carlo simulation techniques to gain a molecular-level understanding of the adsorption mechanism of gases in these porous materials. We investigated the uptake of various gases such as refrigerants R12 and R143a and also the elemental gases Xe and Rn by the metal organic framework (i.e., Ni2(dhtp)). We also evaluated the effects of temperature and pressure on the uptake mechanism. Our computed results compared reasonably well with available experimental measurements, thus validating our potential models and approaches. In addition, we also investigated the structural, diffusive, and adsorption properties of different hydrocarbons in Ni2(dhtp). To elucidate the mechanism of nanoparticle dispersion in condensed phases, we also studied the interactions among nanoparticles in various liquids, such as n-hexane, water and methanol. This work was performed at Pacific Northwest National Laboratory (PNNL) and was supported by the Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy (DOE). PNNL is operated by Battelle for the DOE. The authors also gratefully acknowledge support received from the National Energy Technology Laboratory of DOE's Office of Fossil Energy.

  3. Electrical conductivity of activated carbon-metal oxide nanocomposites under compression: a comparison study.

    PubMed

    Barroso-Bogeat, A; Alexandre-Franco, M; Fernández-González, C; Macías-García, A; Gómez-Serrano, V

    2014-12-07

    From a granular commercial activated carbon (AC) and six metal oxide (Al2O3, Fe2O3, SnO2, TiO2, WO3 and ZnO) precursors, two series of AC-metal oxide nanocomposites were prepared by wet impregnation, oven-drying at 120 °C, and subsequent heat treatment at 200 or 850 °C in an inert atmosphere. Here, the electrical conductivity of the resulting products was studied under moderate compression. The influence of the applied pressure, sample volume, mechanical work, and density of the hybrid materials was thoroughly investigated. The DC electrical conductivity of the compressed samples was measured at room temperature by the four-probe method. Compaction assays suggest that the mechanical properties of the nanocomposites are largely determined by the carbon matrix. Both the decrease in volume and the increase in density were relatively small and only significant at pressures lower than 100 kPa for AC and most nanocomposites. In contrast, the bulk electrical conductivity of the hybrid materials was strongly influenced by the intrinsic conductivity, mean crystallite size, content and chemical nature of the supported phases, which ultimately depend on the metal oxide precursor and heat treatment temperature. The supported nanoparticles may be considered to act as electrical switches either hindering or favouring the effective electron transport between the AC cores of neighbouring composite particles in contact under compression. Conductivity values as a rule were lower for the nanocomposites than for the raw AC, all of them falling in the range of semiconductor materials. With the increase in heat treatment temperature, the trend is toward the improvement of conductivity due to the increase in the crystallite size and, in some cases, to the formation of metals in the elemental state and even metal carbides. The patterns of variation of the electrical conductivity with pressure and mechanical work were slightly similar, thus suggesting the predominance of the pressure

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

    NASA Astrophysics Data System (ADS)

    Soni, Shubhangi; Kaurav, Netram; Jain, A.; Shah, S.; Choudhary, K. K.

    2015-06-01

    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.

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

    SciTech Connect

    Soni, Shubhangi; Kaurav, Netram Jain, A.; Shah, S.; Choudhary, K. K.

    2015-06-24

    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.

  6. Abnormal correlation between phase transformation and cooling rate for pure metals

    PubMed Central

    Han, J. J.; Wang, C. P.; Liu, X. J.; Wang, Y.; Liu, Z.-K.; Zhang, T.-Y.; Jiang, J. Z.

    2016-01-01

    This work aims to achieve deep insight into the phenomenon of phase transformation upon rapid cooling in metal systems and reveal the physical meaning of scatter in the time taken to reach crystallization. The total number of pure metals considered in this work accounts for 14. Taking pure copper as an example, the correlation between phase selection of crystal or glass and cooling rate was investigated using molecular dynamic simulations. The obtained results demonstrate that there exists a cooling rate region of 6.3 × 1011–16.6 × 1011 K/s, in which crystalline fractions largely fluctuate along with cooling rates. Glass transformation in this cooling rate region is determined by atomic structure fluctuation, which is controlled by thermodynamic factors. According to the feature of bond-orientation order at different cooling rates, we propose two mechanisms of glass formation: (i) kinetic retardation of atom rearrangement or structural relaxation at a high cooling rate; and (ii) competition of icosahedral order against crystal order near the critical cooling rate. PMID:26939584

  7. Modeling of microstructure evolution in direct metal laser sintering: A phase field approach

    NASA Astrophysics Data System (ADS)

    Nandy, Jyotirmoy; Sarangi, Hrushikesh; Sahoo, Seshadev

    2017-02-01

    Direct Metal Laser Sintering (DMLS) is a new technology in the field of additive manufacturing, which builds metal parts in a layer by layer fashion directly from the powder bed. The process occurs within a very short time period with rapid solidification rate. Slight variations in the process parameters may cause enormous change in the final build parts. The physical and mechanical properties of the final build parts are dependent on the solidification rate which directly affects the microstructure of the material. Thus, the evolving of microstructure plays a vital role in the process parameters optimization. Nowadays, the increase in computational power allows for direct simulations of microstructures during materials processing for specific manufacturing conditions. In this study, modeling of microstructure evolution of Al-Si-10Mg powder in DMLS process was carried out by using a phase field approach. A MATLAB code was developed to solve the set of phase field equations, where simulation parameters include temperature gradient, laser scan speed and laser power. The effects of temperature gradient on microstructure evolution were studied and found that with increase in temperature gradient, the dendritic tip grows at a faster rate.

  8. Polyamorphic phase transition of Yb-based metallic glass at high pressure

    NASA Astrophysics Data System (ADS)

    li, L.; Li, R.; Liu, H.; Chupas, P.

    2013-12-01

    A family of Yb-based bulk metallic glasses (BMG) has been fabricated based on strong liquid characteristic and excellent glass-forming ability. Using a diamond anvil cell with high-energy synchrotron X-ray, the total scattering of metallic glass Yb-Mg-Zn was studied at pressure up to 30GPa in a hydrostatic isopropanol pressure-medium. The local structure was investigated through direct Fourier transformation of the structure factor [S(Q)], pair distribution function (PDF) [G(r)] with background correction. Polyamorphic phase transition is achieved because smaller atoms are extruded into the clearance of the larger rare earth atoms and 4f electrons delocalized. Phase transition from a low-density state to a high-density state occurs, smaller atoms can be extruded is one of two reasons for the high compressibility of rare earth BMG. The second reason is the delocalization of 4f electrons, which can induce the volume collapse of rare earth atoms.

  9. Metal ion-mobilizing additives for comprehensive detection of femtomole amounts of phosphopeptides by reversed phase LC-MS.

    PubMed

    Seidler, Joerg; Zinn, Nico; Haaf, Erik; Boehm, Martin E; Winter, Dominic; Schlosser, Andreas; Lehmann, Wolf D

    2011-07-01

    It is hypothesized that metal ion-mediated adsorption of phosphorylated peptides on stationary phases of LC-columns is the major cause for their frequently observed poor detection efficiency in LC-MS. To study this phenomenon in more detail, sample solutions spiked with metal ion-mobilizing additives were analyzed by reversed phase μLC-ICP-MS or nanoLC-ESI-MS. Using μLC-ICP-MS, metal ions were analyzed directly as atomic ions. Using electrospray ionization, either metal ion chelates or phosphopeptide standard mixtures injected in subpicomole amounts were analyzed. Deferoxamine, imidazole, ascorbate, citrate, EDTA, and the tetrapeptide pSpSpSpS were tested as sample additives for the interlinked purposes of metal ion-mobilization and improvement of phosphopeptide recovery. Iron probably represents the major metal ion contamination of reversed phase columns. Based on the certified iron level in LC-grade solvents, a daily metal ion load of >10 pmol was estimated for typical nanoLC flow rates. In addition, phosphopeptide fractions from IMAC columns were identified as source for metal ion contamination of the LC column, as demonstrated for Ga(3+)-IMAC. The three metal ion-chelating additives, EDTA, citrate and pSpSpSpS, were found to perform best for improving the LC recovery of multiply phosphorylated peptides injected at subpicomole amounts. The benefits of metal ion-mobilizing LC (mimLC) characterized by metal ion complexing sample additives is demonstrated for three different instrumental setups comprising (a) a nanoUPLC-system with direct injection on the analytical column, (b) a nanoLC system with inclusion of a trapping column, and (c) the use of a HPLC-Chip system with integrated trapping and analytical column.

  10. Quantitative phase imaging technologies to assess neuronal activity (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Thouvenin, Olivier; Fink, Mathias; Boccara, Claude

    2016-03-01

    Active neurons tends to have a different dynamical behavior compared to resting ones. Non-exhaustively, vesicular transport towards the synapses is increased, since axonal growth becomes slower. Previous studies also reported small phase variations occurring simultaneously with the action potential. Such changes exhibit times scales ranging from milliseconds to several seconds on spatial scales smaller than the optical diffraction limit. Therefore, QPI systems are of particular interest to measure neuronal activity without labels. Here, we report the development of two new QPI systems that should enable the detection of such activity. Both systems can acquire full field phase images with a sub nanometer sensitivity at a few hundreds of frames per second. The first setup is a synchronous combination of Full Field Optical Coherence Tomography (FF-OCT) and Fluorescence wide field imaging. The latter modality enables the measurement of neurons electrical activity using calcium indicators. In cultures, FF-OCT exhibits similar features to Digital Holographic Microscopy (DHM), except from complex computational reconstruction. However, FF-OCT is of particular interest in order to measure phase variations in tissues. The second setup is based on a Quantitative Differential Interference Contrast setup mounted in an epi-illumination configuration with a spectrally incoherent illumination. Such a common path interferometer exhibits a very good mechanical stability, and thus enables the measurement of phase images during hours. Additionally, such setup can not only measure a height change, but also an optical index change for both polarization. Hence, one can measure simultaneously a phase change and a birefringence change.

  11. Reactions of metal ions and their clusters in the gas phase using laser ionization: Fourier transform mass spectrometry. Progress report, February 1, 1993--January 31, 1994

    SciTech Connect

    Freiser, B.S.

    1993-09-01

    This report focuses on progress in seven areas: (1) Gas-Phase Reactions of Fe(Benzyne){sup +} with Simple Alkyl Halides; (2) Photodissociation and Collision-Induced Dissociation of Molecular Ions From Methylphenol and Chloromethylphenol; (3) Isotopomer Differentiation Using Metal Ion Chemical Ionization Reagents; (4) Multiple Excitation Collisional Activation (MECA) in Fourier Transform Mass Spectrometry; (5) Chemistry of Fe{sup +}-Arene Ions with Halobenzenes; (6) Gas-Phase Photodissociaton Study of Ag(Benzene){sup +} and Ag(Toluene){sup +}; and (7) Reactivity of Ti{sup 2+} and V{sup 2+} with Small Alkanes.

  12. Metal-semiconductor phase transition of order arrays of VO2 nanocrystals

    NASA Astrophysics Data System (ADS)

    Lopez, Rene; Suh, Jae; Feldman, Leonard; Haglund, Richard

    2004-03-01

    The study of solid-state phase transitions at nanometer length scales provides new insights into the effects of material size on the mechanisms of structural transformations. Such research also opens the door to new applications, either because materials properties are modified as a function of particle size, or because the nanoparticles interact with a surrounding matrix material, or with each other. In this paper, we describe the formation of vanadium dioxide nanoparticles in silicon substrates by pulsed laser deposition of ion beam lithographically selected sites and thermal processing. We observe the collective behavior of 50 nm diameter VO2 oblate nanoparticles, 10 nm high, and ordered in square arrays with arbitrary lattice constant. The metal-semiconductor-transition of the VO2 precipitates shows different features in each lattice spacing substrate. The materials are characterized by electron microscopy, x-ray diffraction, Rutherford backscattering. The features of the phase transition are studied via infrared optical spectroscopy. Of particular interest are the enhanced scattering and the surface plasmon resonance when the particles reach the metallic state. This resonance amplifies the optical contrast in the range of near-infrared optical communication wavelengths and it is altered by the particle-particle coupling as in the case of noble metals. In addition the VO2 nanoparticles exhibit sharp transitions with up to 50 K of hysteresis, one of the largest values ever reported for this transition. The optical properties of the VO2 nanoarrays are correlated with the size of the precipitates and their inter-particle distance. Nonlinear and ultra fast optical measurements have shown that the transition is the fastest known solid-solid transformation. The VO2 nanoparticles show the same bulk property, transforming in times shorter than 150 fs. This makes them remarkable candidates for ultrafast optical and electronic switching applications.

  13. Transition Metals Catalyzed Element-Cyano Bonds Activations

    PubMed Central

    Wang, Rui; Falck, John R.

    2014-01-01

    Cyano group as a versatile functionalized intermediate has been explored for several decades, as it readily transfers to many useful functionalization groups such as amine, amide, acid, etc., which make it possess high popularization and use value in organic synthesis. Reactions involved with element-cyano bond cleavage can provide not only a new cyano group but also a freshly functionalized skeleton in one-pot, consequently making it of high importance. The highlights reviewed herein include H-CN, Si-CN, C-CN, B-CN, Sn-CN, Ge-CN, S-CN, Halo-CN, N-CN, and O-CN bonds cleavages and will summarize progress in such an important research area. This review article will focus on transition metal catalyzed reactions involving element-cyano bond activation. PMID:25558119

  14. Metal Fluxes from Porewaters and Labile Sediment Phases for Predicting Metal Exposure and Bioaccumulation in Benthic Invertebrates.

    PubMed

    Amato, Elvio D; Simpson, Stuart L; Belzunce-Segarra, Maria J; Jarolimek, Chad V; Jolley, Dianne F

    2015-12-15

    The use of diffusive gradients in thin films (DGT) for predicting metal bioavailability was investigated by exposing the bivalve Tellina deltoidalis to an identical series of metal-contaminated sediments deployed simultaneously in the field and laboratory. To understand the differences in metal exposure occurring between laboratory- and field-based bioassays, we investigated changes in metal fluxes to DGT probes in sediments and in metal concentrations and partitioning to porewaters and overlying waters. DGT-metal fluxes (Cu, Pb, and Zn) were lower in the overlying waters of most field bioassays compared to the laboratory, causing differences in Pb and Zn bioaccumulation between bivalves exposed to laboratory and field conditions. Overall, DGT-metal fluxes provided predictions of metal bioaccumulation similar to those obtained using dilute-acid extractable metal measurements. This study demonstrates that, irrespective of the physicochemical properties of the sediment and type of exposure (laboratory or field), sediments pose a significant risk of bioaccumulation by T. deltoidalis when the Cu, Pb, and Zn DGT flux exceeds 3.5, 1.3, and 156 μg/h/m(2), respectively. The results presented here support the use of the DGT technique for sediment quality assessment and the hypothesis that DGT-metal fluxes may potentially be useful surrogates for the lability of metals for all exposure routes.

  15. Inhibitory Activity Of Curcumin Derivatives Towards Metal-free And Metal-induced Amyloid-β Aggregation.

    PubMed

    Kochi, Akiko; Lee, Hyuck Jin; Vithanarachchi, Sashiprabha M; Padmini, Vediappen; Allen, Matthew J; Lim, Mi Hee

    2015-01-01

    When Alzheimer's disease (AD) progresses, several pathological features arise including accumulation of misfolded protein aggregates [e.g., amyloid-β (Aβ) plaques], metal ion dyshomeostasis, and oxidative stress. These characteristics are recently suggested to be interconnected through a potential factor, metal-associated Aβ (metal-Aβ) species. The role of metal-Aβ species in AD pathogenesis remains unclear, however. To elucidate the contribution of metal-Aβ species to AD pathology, as well as to develop small molecules as chemical tools and/or theranostic (therapeutic and diagnostic) agents for this disease, curcumin (Cur), a natural product from turmeric, and its derivatives have been studied towards both metal-free and metal-induced Aβ aggregation. Although Cur has indicated anti-amyloidogenic activities and antioxidant properties, its biological use has been hindered due to low solubility and stability in physiologically relevant conditions. Herein, we report the reactivity of Cur and its derivatives (Gd-Cur, a potential multimodal Aβ imaging agent; Cur-S, a water soluble derivative of Cur that has substitution at the phenolic hydroxyls) with metal-free Aβ and metal-Aβ species. Our results and observations indicate that Gd-Cur could modulate Cu(II)-triggered Aβ aggregation more noticeably over metal-free or Zn(II)-induced analogues; however, Cur-S was not observed to noticeably modulate Aβ aggregation with and without metal ions. Overall, our studies present information that could aid in optimizing the molecular scaffold of Cur for the development of chemical tools or theranostics for metal-Aβ species.

  16. Alkali metal cation binding affinities of cytosine in the gas phase: revisited.

    PubMed

    Yang, Bo; Rodgers, M T

    2014-08-14

    Binding of metal cations to the nucleobases can influence base pairing, base stacking and nucleobase tautomerism. Gas-phase condensation of dc discharge generated alkali metal cations and thermally vaporized cytosine (DC/FT) has been found to produce kinetically trapped excited tautomeric conformations of the M(+)(cytosine) complexes, which influences the threshold collision-induced dissociation (TCID) behavior. In order to elucidate the effects of the size of alkali metal cation on the strength of binding to the canonical form of cytosine, the binding affinities of Na(+) and K(+) to cytosine are re-examined here, and studies are extended to include Rb(+) and Cs(+) again using TCID techniques. The M(+)(cytosine) complexes are generated in an electrospray ionization source, which has been shown to produce ground-state tautomeric conformations of M(+)(cytosine). The energy-dependent cross sections are interpreted to yield bond dissociation energies (BDEs) using an analysis that includes consideration of unimolecular decay rates, the kinetic and internal energy distributions of the reactants, and multiple M(+)(cytosine)-Xe collisions. Revised BDEs for the Na(+)(cytosine) and K(+)(cytosine) complexes exceed those previously measured by 31.9 and 25.5 kJ mol(-1), respectively, consistent with the hypothesis proposed by Yang and Rodgers that excited tautomeric conformations are accessed when the complexes are generated by DC/FT ionization. Experimentally measured BDEs are compared to theoretical values calculated at the B3LYP and MP2(full) levels of theory using the 6-311+G(2d,2p)_HW* and def2-TZVPPD basis sets. The B3LYP/def2-TZVPPD level of theory is found to provide the best agreement with the measured BDEs, suggesting that this level of theory can be employed to provide reliable energetics for similar metal-ligand systems.

  17. Recovery of valuable metals from cathodic active material of spent lithium ion batteries: Leaching and kinetic aspects.

    PubMed

    Meshram, Pratima; Pandey, B D; Mankhand, T R

    2015-11-01

    This work is focussed on the processing of cathodic active material of spent lithium ion batteries (LIBs) to ensure resource recovery and minimize environmental degradation. The sulfuric acid leaching of metals was carried out for the recovery of all the valuable metals including nickel and manganese along with the frequently targeted metals like lithium and cobalt. The process parameters such as acid concentration, pulp density, time and temperature for the leaching of metals from the cathode powder containing 35.8% Co, 6.5% Li, 11.6% Mn and 10.06% Ni, were optimized. Results show the optimized leach recovery of 93.4% Li, 66.2% Co, 96.3% Ni and 50.2% Mn when the material was leached in 1M H2SO4 at 368 K and 50 g/L pulp density for 240 min. The need of a reductant for improved recovery of cobalt and manganese has been explained by the thermodynamic analysis (Eh-pH diagram) for these metals. Leaching of the valuable metals was found to follow the logarithmic rate law controlled by surface layer diffusion of the lixiviant reacting with the particles. The mode of leaching of the metals from the spent LIBs was further examined by chemical analysis of the samples at various stage of processing which was further corroborated by characterizing the untreated sample and the leach residues by XRD phase identification and the SEM-EDS studies.

  18. Crystal structure of the pressure-induced metallic phase of SiH4 from ab initio theory.

    PubMed

    Kim, D Y; Scheicher, R H; Lebègue, S; Prasongkit, J; Arnaud, B; Alouani, M; Ahuja, R

    2008-10-28

    Metallization of pure solid hydrogen is of great interest, not least because it could lead to high-temperature superconductivity, but it continues to be an elusive goal because of great experimental challenges. Hydrogen-rich materials, in particular, CH(4), SiH(4), and GeH(4), provide an opportunity to study related phenomena at experimentally achievable pressures, and they too are expected to be high-temperature superconductors. Recently, the emergence of a metallic phase has been observed in silane for pressures just above 60 GPa. However, some uncertainty exists about the crystal structure of the discovered metallic phase. Here, we show by way of elimination, that a single structure that possesses all of the required characteristics of the experimentally observed metallic phase of silane from a pool of plausible candidates can be identified. Our density functional theory and GW calculations show that a structure with space group P4/nbm is metallic at pressures >60 GPa. Based on phonon calculations, we furthermore demonstrate that the P4/nbm structure is dynamically stable at >43 GPa and becomes the ground state at 97 GPa when zero-point energy contributions are considered. These findings could lead the way for further theoretical analysis of metallic phases of hydrogen-rich materials and stimulate experimental studies.

  19. Active metal-matrix composites with embedded smart materials by ultrasonic additive manufacturing

    NASA Astrophysics Data System (ADS)

    Hahnlen, Ryan; Dapino, Marcelo J.

    2010-04-01

    This paper presents the development of active aluminum-matrix composites manufactured by Ultrasonic Additive Manufacturing (UAM), an emerging rapid prototyping process based on ultrasonic metal welding. Composites created through this process experience temperatures as low as 25 °C during fabrication, in contrast to current metal-matrix fabrication processes which require temperatures of 500 °C and above. UAM thus provides unprecedented opportunities to develop adaptive structures with seamlessly embedded smart materials and electronic components without degrading the properties that make these materials and components attractive. This research focuses on developing UAM composites with aluminum matrices and embedded shape memory NiTi, magnetostrictive Galfenol, and electroactive PVDF phases. The research on these composites will focus on: (i) electrical insulation between NiTi and Al phases for strain sensors, investigation and modeling of NiTi-Al composites as tunable stiffness materials and thermally invariant structures based on the shape memory effect; (ii) process development and composite testing for Galfenol-Al composites; and (iii) development of PVDF-Al composites for embedded sensing applications. We demonstrate a method to electrically insulate embedded materials from the UAM matrix, the ability create composites containing up to 22.3% NiTi, and their resulting dimensional stability and thermal actuation characteristics. Also demonstrated is Galfenol-Al composite magnetic actuation of up to 54 μ(see manuscript), and creation of a PVDF-Al composite sensor.

  20. A two-phase restricted equilibrium model for combustion of metalized solid propellants

    NASA Technical Reports Server (NTRS)

    Sabnis, J. S.; Dejong, F. J.; Gibeling, H. J.

    1992-01-01

    An Eulerian-Lagrangian two-phase approach was adopted to model the multi-phase reacting internal flow in a solid rocket with a metalized propellant. An Eulerian description was used to analyze the motion of the continuous phase which includes the gas as well as the small (micron-sized) particulates, while a Lagrangian description is used for the analysis of the discrete phase which consists of the larger particulates in the motor chamber. The particulates consist of Al and Al2O3 such that the particulate composition is 100 percent Al at injection from the propellant surface with Al2O3 fraction increasing due to combustion along the particle trajectory. An empirical model is used to compute the combustion rate for agglomerates while the continuous phase chemistry is treated using chemical equilibrium. The computer code was used to simulate the reacting flow in a solid rocket motor with an AP/HTPB/Al propellant. The computed results show the existence of an extended combustion zone in the chamber rather than a thin reaction region. The presence of the extended combustion zone results in the chamber flow field and chemical being far from isothermal (as would be predicted by a surface combustion assumption). The temperature in the chamber increases from about 2600 K at the propellant surface to about 3350 K in the core. Similarly the chemical composition and the density of the propellant gas also show spatially non-uniform distribution in the chamber. The analysis developed under the present effort provides a more sophisticated tool for solid rocket internal flow predictions than is presently available, and can be useful in studying apparent anomalies and improving the simple correlations currently in use. The code can be used in the analysis of combustion efficiency, thermal load in the internal insulation, plume radiation, etc.

  1. Rotating single cycle two-phase thermally activated heat pump

    SciTech Connect

    Fabris, G.

    1993-06-08

    A thermally activated heat pump is described which utilizes single working fluid which as a whole passes consecutively through all parts of the apparatus in a closed loop series; the working fluid in low temperature saturated liquid state at condensation is pumped to higher pressure with a pump; subsequently heat is added to the liquid of increased pressure, the liquid via the heating is brought to a high temperature saturated liquid state; the high temperature liquid passes and flashes subsequently in form of two-phase flow through a rotating two-phase flow turbine; in such a way the working fluid performs work on the two-phase turbine which in turn powers the liquid pump and a lower compressor; two-phase flow exiting the two-phase turbine separated by impinging tangentially on housing of the turbine; low temperature heat is added to the housing in such a way evaporating the separated liquid on the housing; in such a way the liquid is fully vaporized the vapor then enters a compressor, the compressor compresses the vapor to a higher condensation pressure and corresponding increased temperature, the vapor at the condensation pressure enters a condenser whereby heat is rejected and the vapor is fully condensed into state of saturated liquid, mid saturated liquid enters the pump and repeats the cycle.

  2. 77 FR 10544 - Agency Information Collection Activities: Comment Request for the Nonferrous Metals Surveys (30...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-02-22

    ... Geological Survey Agency Information Collection Activities: Comment Request for the Nonferrous Metals Surveys... requirements for the Nonferrous Metals Surveys. This collection consists of 30 forms. The revision includes... Metals Surveys. Type of Request: Revision of a currently approved collection. Affected Public:...

  3. 76 FR 9810 - Agency Information Collection Activities: Comment Request for the Ferrous Metals Surveys (17 Forms)

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-02-22

    ... Geological Survey Agency Information Collection Activities: Comment Request for the Ferrous Metals Surveys... to supply the USGS with domestic consumption data of 13 ores, concentrates, metals, and ferroalloys... OMB Control Number: 1028-0068. Form Number: Various (17 forms). Title: Ferrous Metals Surveys. Type...

  4. 76 FR 52686 - Agency Information Collection Activities: Comment Request for the Nonferrous Metals Surveys (30...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-08-23

    ... Geological Survey Agency Information Collection Activities: Comment Request for the Nonferrous Metals Surveys.... II. Data OMB Control Number: 1028-0053. Form Number: Various (30 forms). Title: Nonferrous Metals....S. nonfuel minerals producers of nonferrous and related metals. Respondent Obligation:...

  5. Phase Segregation of Passive Advective Particles in an Active Medium

    NASA Astrophysics Data System (ADS)

    Das, Amit; Polley, Anirban; Rao, Madan

    2016-02-01

    Localized contractile configurations or asters spontaneously appear and disappear as emergent structures in the collective stochastic dynamics of active polar actomyosin filaments. Passive particles which (un)bind to the active filaments get advected into the asters, forming transient clusters. We study the phase segregation of such passive advective scalars in a medium of dynamic asters, as a function of the aster density and the ratio of the rates of aster remodeling to particle diffusion. The dynamics of coarsening shows a violation of Porod behavior; the growing domains have diffuse interfaces and low interfacial tension. The phase-segregated steady state shows strong macroscopic fluctuations characterized by multiscaling and intermittency, signifying rapid reorganization of macroscopic structures. We expect these unique nonequilibrium features to manifest in the actin-dependent molecular clustering at the cell surface.

  6. Catalyst and method for aqueous phase reactions

    DOEpatents

    Elliott, Douglas C.; Hart, Todd R.

    1999-01-01

    The present invention is a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional metal deposited onto the support in a second dispersed phase. The additional metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase without substantially affecting the catalytic activity, thereby increasing the life time of the catalyst.

  7. Atomic structures of a liquid-phase bonded metal/nitride heterointerface

    PubMed Central

    Kumamoto, Akihito; Shibata, Naoya; Nayuki, Kei-ichiro; Tohei, Tetsuya; Terasaki, Nobuyuki; Nagatomo, Yoshiyuki; Nagase, Toshiyuki; Akiyama, Kazuhiro; Kuromitsu, Yoshirou; Ikuhara, Yuichi

    2016-01-01

    Liquid-phase bonding is a technologically important method to fabricate high-performance metal/ceramic heterostructures used for power electronic devices. However, the atomic-scale mechanisms of how these two dissimilar crystals specifically bond at the interfaces are still not well understood. Here we analyse the atomically-resolved structure of a liquid-phase bonded heterointerface between Al alloy and AlN single crystal using aberration corrected scanning transmission electron microscopy (STEM). In addition, energy-dispersive X-ray microanalysis, using dual silicon drift X-ray detectors in STEM, was performed to analyze the local chemistry of the interface. We find that a monolayer of MgO is spontaneously formed on the AlN substrate surface and that a polarity-inverted monolayer of AlN is grown on top of it. Thus, the Al alloy is bonded with the polarity-inverted AlN monolayer, creating a complex atomic-scale layered structure, facilitating the bonding between the two dissimilar crystals during liquid-phase bonding processes. Density-functional-theory calculations confirm that the bonding stability is strongly dependent on the polarity and stacking of AlN and MgO monolayers. Understanding the spontaneous formation of layered transition structures at the heterointerface will be key in fabricating very stable Al alloy/AlN heterointerface required for high reliability power electronic devices. PMID:26961157

  8. Preparation of nanocrystalline metal oxides and intermetallic phases by controlled thermolysis of organometallic coordination polymers

    NASA Astrophysics Data System (ADS)

    Rehbein, Marcus; Epple, Matthias; Fischer, R. Dieter

    2000-06-01

    Organometallic coordination polymers of the super-Prussian blue type [(Me 3Sn) nM(CN) 6] (Me=CH 3; n=3, 4; M=Fe, Co, Ru) were subjected to thermolysis in different atmospheres (air, argon, hydrogen/nitrogen). In air, oxides were found: Fe 2O 3/SnO 2 (crystalline and nanocrystalline), Co 2SnO 4 and RuO 2. In argon and in hydrogen, the intermetallic phases FeSn 2, CoSn 2, Ru 3Sn 7 and Fe 3SnC were obtained. A detailed mechanistic study was carried out using thermogravimetry (TG), X-ray diffraction (XRD), X-ray absorption spectroscopy (EXAFS) at Fe, Co, Ru and Sn K-edges, infrared spectroscopy (IR) and elemental analysis. Below 250°C, Me 3SnCN and (CN) 2 are released, whereas above 250°C oxidation or pyrolysis leads to the corresponding oxides or intermetallic phases. Polymeric cyanides containing at least two metals have turned out to be suitable precursors to prepare well-defined oxides and intermetallic phases at comparatively low temperature.

  9. Pressure-induced phase transitions in Pa metal from first-principles theory

    SciTech Connect

    Soederlind, P.; Eriksson, O.

    1997-11-01

    Protactinium metal is shown to undergo a phase transition to the {alpha}-U orthorhombic structure below 1 Mbar pressure. At higher pressures, the bct phase reenters in the phase diagram and at the highest pressures, an ideal hcp structure becomes stable. Hence, Pa undergoes a sequence of transitions; bct{r_arrow}{alpha}-U{r_arrow}bct{r_arrow}hcp, with the first transition taking place at 0.25 Mbar and the subsequent ones above 1 Mbar. The bct{r_arrow}{alpha}-U transition is triggered by the pressure-induced promotion of the spd valence states to 5f states. In this regard, Pa approaches uranium which at ambient conditions has one more 5f electron than Pa at similar conditions. At higher compression of Pa, the 5f band broadens and electrostatic interactions in combination with Born-Mayer repulsion become increasingly important and this drives Pa to gradually more close-packed structures. At ultrahigh pressures, the balance between electrostatic energy, Born-Mayer repulsion, and one-electron band energy stabilizes the hcp (ideal packing) structure. The electrostatic energy and Born-Mayer repulsion rule out open crystal structures under these conditions in Pa and between the close-packed structures, the hcp structure is shown to be stabilized by filling of the 5f band. {copyright} {ital 1997} {ital The American Physical Society}

  10. Thin-Film Phase Plates for Transmission Electron Microscopy Fabricated from Metallic Glasses.

    PubMed

    Dries, Manuel; Hettler, Simon; Schulze, Tina; Send, Winfried; Müller, Erich; Schneider, Reinhard; Gerthsen, Dagmar; Luo, Yuansu; Samwer, Konrad

    2016-10-01

    Thin-film phase plates (PPs) have become an interesting tool to enhance the contrast of weak-phase objects in transmission electron microscopy (TEM). The thin film usually consists of amorphous carbon, which suffers from quick degeneration under the intense electron-beam illumination. Recent investigations have focused on the search for alternative materials with an improved material stability. This work presents thin-film PPs fabricated from metallic glass alloys, which are characterized by a high electrical conductivity and an amorphous structure. Thin films of the zirconium-based alloy Zr65.0Al7.5Cu27.5 (ZAC) were fabricated and their phase-shifting properties were evaluated. The ZAC film was investigated by different TEM techniques, which reveal beneficial properties compared with amorphous carbon PPs. Particularly favorable is the small probability for inelastic plasmon scattering, which results from the combined effect of a moderate inelastic mean free path and a reduced film thickness due to a high mean inner potential. Small probability plasmon scattering improves contrast transfer at high spatial frequencies, which makes the ZAC alloy a promising material for PP fabrication.

  11. Atomic structures of a liquid-phase bonded metal/nitride heterointerface.

    PubMed

    Kumamoto, Akihito; Shibata, Naoya; Nayuki, Kei-Ichiro; Tohei, Tetsuya; Terasaki, Nobuyuki; Nagatomo, Yoshiyuki; Nagase, Toshiyuki; Akiyama, Kazuhiro; Kuromitsu, Yoshirou; Ikuhara, Yuichi

    2016-03-10

    Liquid-phase bonding is a technologically important method to fabricate high-performance metal/ceramic heterostructures used for power electronic devices. However, the atomic-scale mechanisms of how these two dissimilar crystals specifically bond at the interfaces are still not well understood. Here we analyse the atomically-resolved structure of a liquid-phase bonded heterointerface between Al alloy and AlN single crystal using aberration corrected scanning transmission electron microscopy (STEM). In addition, energy-dispersive X-ray microanalysis, using dual silicon drift X-ray detectors in STEM, was performed to analyze the local chemistry of the interface. We find that a monolayer of MgO is spontaneously formed on the AlN substrate surface and that a polarity-inverted monolayer of AlN is grown on top of it. Thus, the Al alloy is bonded with the polarity-inverted AlN monolayer, creating a complex atomic-scale layered structure, facilitating the bonding between the two dissimilar crystals during liquid-phase bonding processes. Density-functional-theory calculations confirm that the bonding stability is strongly dependent on the polarity and stacking of AlN and MgO monolayers. Understanding the spontaneous formation of layered transition structures at the heterointerface will be key in fabricating very stable Al alloy/AlN heterointerface required for high reliability power electronic devices.

  12. Atomic structures of a liquid-phase bonded metal/nitride heterointerface

    NASA Astrophysics Data System (ADS)

    Kumamoto, Akihito; Shibata, Naoya; Nayuki, Kei-Ichiro; Tohei, Tetsuya; Terasaki, Nobuyuki; Nagatomo, Yoshiyuki; Nagase, Toshiyuki; Akiyama, Kazuhiro; Kuromitsu, Yoshirou; Ikuhara, Yuichi

    2016-03-01

    Liquid-phase bonding is a technologically important method to fabricate high-performance metal/ceramic heterostructures used for power electronic devices. However, the atomic-scale mechanisms of how these two dissimilar crystals specifically bond at the interfaces are still not well understood. Here we analyse the atomically-resolved structure of a liquid-phase bonded heterointerface between Al alloy and AlN single crystal using aberration corrected scanning transmission electron microscopy (STEM). In addition, energy-dispersive X-ray microanalysis, using dual silicon drift X-ray detectors in STEM, was performed to analyze the local chemistry of the interface. We find that a monolayer of MgO is spontaneously formed on the AlN substrate surface and that a polarity-inverted monolayer of AlN is grown on top of it. Thus, the Al alloy is bonded with the polarity-inverted AlN monolayer, creating a complex atomic-scale layered structure, facilitating the bonding between the two dissimilar crystals during liquid-phase bonding processes. Density-functional-theory calculations confirm that the bonding stability is strongly dependent on the polarity and stacking of AlN and MgO monolayers. Understanding the spontaneous formation of layered transition structures at the heterointerface will be key in fabricating very stable Al alloy/AlN heterointerface required for high reliability power electronic devices.

  13. Pressure-induced phase transitions in Pa metal from first-principles theory

    NASA Astrophysics Data System (ADS)

    Söderlind, Per; Eriksson, Olle

    1997-11-01

    Protactinium metal is shown to undergo a phase transition to the α-U orthorhombic structure below 1 Mbar pressure. At higher pressures, the bct phase reenters in the phase diagram and at the highest pressures, an ideal hcp structure becomes stable. Hence, Pa undergoes a sequence of transitions; bct-->α-U-->bct-->hcp, with the first transition taking place at 0.25 Mbar and the subsequent ones above 1 Mbar. The bct-->α-U transition is triggered by the pressure-induced promotion of the spd valence states to 5f states. In this regard, Pa approaches uranium which at ambient conditions has one more 5f electron than Pa at similar conditions. At higher compression of Pa, the 5f band broadens and electrostatic interactions in combination with Born-Mayer repulsion become increasingly important and this drives Pa to gradually more close-packed structures. At ultrahigh pressures, the balance between electrostatic energy, Born-Mayer repulsion, and one-electron band energy stabilizes the hcp (ideal packing) structure. The electrostatic energy and Born-Mayer repulsion rule out open crystal structures under these conditions in Pa and between the close-packed structures, the hcp structure is shown to be stabilized by filling of the 5f band.

  14. Comparison of gamma-gamma Phase Coarsening Responses of Three Powder Metal Disk Superalloys

    NASA Technical Reports Server (NTRS)

    Gabb, T. P.; Gayda, J.; Johnson, D. F.; MacKay, R. A.; Rogers, R. B.; Sudbrack, C. K.; Garg, A.; Locci, I. E.; Semiatin, S. L.; Kang, E.

    2016-01-01

    The phase microstructures of several powder metal (PM) disk superalloys were quantitatively evaluated. Contents, chemistries, and lattice parameters of gamma and gamma strengthening phase were determined for conventionally heat treated Alloy 10, LSHR, and ME3 superalloys, after electrolytic phase extractions. Several of long term heat treatments were then performed, to allow quantification of the precipitation, content, and size distribution of gamma at a long time interval to approximate equilibrium conditions. Additional coarsening heat treatments were performed at multiple temperatures and shorter time intervals, to allow quantification of the precipitation, contents and size distributions of gamma at conditions diverging from equilibrium. Modest differences in gamma and gamma lattice parameters and their mismatch were observed among the alloys, which varied with heat treatment. Yet, gamma coarsening rates were very similar for all three alloys in the heat treatment conditions examined. Alloy 10 had higher gamma dissolution and formation temperatures than LSHR and ME3, but a lower lattice mismatch, which was slightly positive for all three alloys at room temperature. The gamma precipitates of Alloy 10 appeared to remain coherent at higher temperatures than for LSHR and ME3. Higher coarsening rates were observed for gamma precipitates residing along grain boundaries than for those within grains in all three alloys, during slow-moderate quenching from supersolvus solution heat treatments, and during aging at temperatures of 843 C and higher.

  15. Assessment of Trace Metals in Soil, Vegetation and Rodents in Relation to Metal Mining Activities in an Arid Environment.

    PubMed

    Méndez-Rodríguez, Lia C; Alvarez-Castañeda, Sergio Ticul

    2016-07-01

    Areas where abandoned metal-extraction mines are located contain large quantities of mineral wastes derived from environmentally unsafe mining practices. These wastes contain many pollutants, such as heavy metals, which could be released to the environment through weathering and leaching, hence becoming an important source of environmental metal pollution. This study evaluates differences in the levels of lead, iron, nickel, manganese, copper and cadmium in rodents sharing the same type of diet under different microhabitat use in arid areas with past mining activities. Samples of soil, roots, branches and seeds of Palo Adán (Fouquieria diguetii) and specimens of two rodent species (Chaetodipus arenarius and C. spinatus) were collected in areas with impact from past metal mining activities as well as from areas with no mining impact. Both rodent species mirrored nickel and iron levels in soil and seeds, as well as lead levels in soil; however, C. arenarius accumulated higher levels of manganese, copper and cadmium.

  16. Oxytocin discontinuation after the active phase of labor is established.

    PubMed

    Vlachos, Dimitrios-Efthymios G; Pergialiotis, Vasilios; Papantoniou, Nikolaos; Trompoukis, Stamoulis; Vlachos, Georgios D

    2015-08-01

    Despite the widespread usage of oxytocin, there is still no consensus on its mode of administration. The scope of the present meta-analysis was to assess the effect of oxytocin discontinuation after the active phase of labor is established on maternal fetal and neonatal outcomes. We searched Medline, Scopus, Popline, ClinicalTrials.gov and Google Scholar databases. Eight studies were finally retrieved, which involved 1232 parturient. We observed significantly decreased rates of cesarean sections among parturient that discontinued oxytocin (OR 0.51, 95% CI 0.35, 0.74) as well as decreased rates of uterine hyperstimulation (OR 0.33, 95% CI 0.19, 0.58). Similarly, cases of non-reassuring fetal heart rates were fewer among women that did not receive oxytocin after the establishment of the active phase of labor (OR 0.63, 95% CI 0.41, 0.97). Keeping in mind the aforementioned maternal and neonatal adverse effects that seem to result from infusion of oxytocin until delivery, future practice should aim towards its discontinuation after the establishment of the active phase of labor, as it does not seem to influence the total duration of labor. Future studies should aim towards specific populations of parturient in order to clarify whether different approaches are needed.

  17. Small Activity Differences Drive Phase Separation in Active-Passive Polymer Mixtures

    NASA Astrophysics Data System (ADS)

    Smrek, Jan; Kremer, Kurt

    2017-03-01

    Recent theoretical studies found that mixtures of active and passive colloidal particles phase separate but only at very high activity ratio. The high value poses serious obstacles for experimental exploration of this phenomenon. Here we show using simulations that when the active and passive particles are polymers, the critical activity ratio decreases with the polymer length. This not only facilitates the experiments but also has implications on the DNA organization in living cell nuclei. Entropy production can be used as an accurate indicator of this nonequilibrium phase transition.

  18. Method for the generation of variable density metal vapors which bypasses the liquidus phase

    DOEpatents

    Kunnmann, Walter; Larese, John Z.

    2001-01-01

    The present invention provides a method for producing a metal vapor that includes the steps of combining a metal and graphite in a vessel to form a mixture; heating the mixture to a first temperature in an argon gas atmosphere to form a metal carbide; maintaining the first temperature for a period of time; heating the metal carbide to a second temperature to form a metal vapor; withdrawing the metal vapor and the argon gas from the vessel; and separating the metal vapor from the argon gas. Metal vapors made using this method can be used to produce uniform powders of the metal oxide that have narrow size distribution and high purity.

  19. Activity and diffusion of metals in binary aluminum alloys

    SciTech Connect

    Jao, C. S.

    1980-12-01

    To determine the activity of zinc in Zn-Al alloys, the electromotive force (emf) of the cell: Zn/ZnCl/sub 2/-KC1 (eut)/Zn,Al was measured at temperatures between 569.5 K (296.5C) and 649.5 K (376.5C). The applicability of a two-suffix Margules equation was demonstrated, in good agreement with theoretical expectations. The diffusion coefficient of Zn in Al determined from a planar diffusion model for the experimental data was about 3 x 10/sup -10/ cm/sup 2//sec to 2 x 10/sup -9/ cm/sup 2//sec in the range of temperature studied. This is higher than that found in the literature. The most plausible reason appears to be the high alumina concentration in the working electrode because of partial oxidation. Oxidation of the alloying metals was the primary cause of poor alloying between calcium/or zinc and aluminum, thereby frustrating similar measurements at a Ca-Al/or Zn-Al alloy. The literature on the activity of calcium and zinc is aluminum is reviewed.

  20. Boosting catalytic activity of metal nanoparticles for 4-nitrophenol reduction: Modification of metal naoparticles with poly(diallyldimethylammonium chloride).

    PubMed

    You, Jyun-Guo; Shanmugam, Chandirasekar; Liu, Yao-Wen; Yu, Cheng-Ju; Tseng, Wei-Lung

    2017-02-15

    Most of the previously reported studies have focused on the change in the size, morphology, and composition of metal nanocatalysts for improving their catalytic activity. Herein, we report poly(diallyldimethylammonium chloride) [PDDA]-stabilized nanoparticles (NPs) of platinum (Pt) and palladium (Pd) as highly active and efficient catalysts for hydrogenation of 4-nitrophenol (4-NP) in the presence of NaBH4. PDDA-stabilized Pt and Pd NPs possessed similar particle size and same facet with citrate-capped Pt and Pd NPs, making this study to investigate the inter-relationship between catalytic activity and surface ligand without the consideration of the effects of particle size and facet. Compared to citrate-capped Pt and Pd NPs, PDDA-stabilized Pt and Pd NPs exhibited excellent pH and salt stability. PDDA could serve as an electron acceptor for metal NPs to produce the net positive charges on the metal surface, which provide strong electrostatic attraction with negatively charged nitrophenolate and borohydride ions. The activity parameter and rate constant of PDDA-stabilized metal NPs were higher than those of citrate-capped metal NPs. Compared to the previously reported Pd nanomaterials for the catalysis of NaBH4-mediated reduction of 4-NP, PDDA-stabilized Pd NPs exhibited the extremely high activity parameter (195s(-1)g(-1)) and provided excellent scalability and reusability.

  1. Metallic Fe phases in Apollo 16 fines - Their origin and characteristics as revealed by electron spin resonance studies

    NASA Technical Reports Server (NTRS)

    Tsay, F.-D.; Manatt, S. L.; Live, D. H.; Chan, S. I.

    1973-01-01

    The intense electron spin resonance (ESR) signals detected in the Apollo 16 fines from three sites (61141,4, Station 1; 64501,22, South Ray Crater; 67601,20, North Ray Crater) are found to be essentially similar in g-value, in lineshape asymmetry and in temperature dependence to those previously observed for the Apollo 11-15 fines. On the basis of these similarities, it is concluded that these ESR signals like those detected in the Apollo 11-15 fines are principally ferromagnetic in nature arising from metallic Fe phases having the body-centered cubic structure, and not from hematite, magnetite, or any other ferric oxides. It is shown that a quantitative correlation exists between the ESR linewidth observed for the Apollo 11-16 fines and their average Ni contents in the metallic Fe phases as determined by other means. A common source of meteoritic origin is indicated for the metallic Fe phases of these samples.

  2. Phased array ultrasonic testing of dissimilar metal welds using geometric based referencing delay law technique

    NASA Astrophysics Data System (ADS)

    Han, Taeyoung; Schubert, Frank; Hillmann, Susanne; Meyendorf, Norbert

    2015-03-01

    Phased array ultrasonic testing (PAUT) techniques are widely used for the non-destructive testing (NDT) of austenitic welds to find defects like cracks. However, the propagation of ultrasound waves through the austenitic material is intricate due to its inhomogeneous and anisotropic nature. Such a characteristic leads beam path distorted which causes the signal to be misinterpreted. By employing a reference block which is cutout from the mockup of which the structure is a dissimilar metal weld (DMW), a new method of PAUT named as Referencing Delay Law Technique (RDLT) is introduced. With the RDLT, full matrix capture (FMC) was used for data acquisition. To reconstruct the images, total focusing method (TFM) was used. After the focal laws were calculated, PAUT was then performed. As a result, the flaws are more precisely positioned with significantly increased signal-to-noise ratio (SNR).

  3. Method for preparing surfaces of metal composites having a brittle phase for plating

    DOEpatents

    Coates, Cameron W.; Wilson, Thomas J.

    1984-01-01

    The present invention is directed to a method for preparing surfaces of two-phase metal composites having relatively brittle and malleable components for plating with corrosion-resistant material. In practice of the present invention, the surfaces of the composites are etched to remove a major portion or fraction of the brittle component. The etched surface is then peened with particulates for breaking the brittle component from the surfaces and for spreading or smearing the malleable component over the surfaces. The peened surface is then chemically cleaned of residual traces of the brittle component so as to provide a surface of essentially the malleable component to which the corrosion-resistant material may be plated thereon in an adherent manner.

  4. Plasma sprayed coatings for containment of Cu-Mg-Si metallic phase change material

    DOE PAGES

    Withey, Elizabeth Ann; Kruizenga, Alan Michael; Andraka, Charles E.; ...

    2016-01-01

    In this study, the performance of Y2O3-stabilized ZrO2 (YSZ), Y2O3, and Al2O3 plasma sprayed coatings are investigated for their ability to prevent attack of Haynes 230 by a near-eutectic Cu-Mg-Si metallic phase change material (PCM) in a closed environment at 820 °C. Areas where coatings failed were identified with optical and scanning electron microscopy, while chemical interactions were clarified through elemental mapping using electron microprobe analysis. Despite its susceptibility to reduction by Mg, the Al2O3 coating performed well while the YSZ and Y2O3 coating showed clear areas of attack. These results are attributed to the evolution of gaseous Mg atmore » 820 °C leading to the formation of MgO and MgAl2O4.« less

  5. Emergence of a Metallic Quantum Solid Phase in a Rydberg-Dressed Fermi Gas.

    PubMed

    Li, Wei-Han; Hsieh, Tzu-Chi; Mou, Chung-Yu; Wang, Daw-Wei

    2016-07-15

    We examine possible low-temperature phases of a repulsively Rydberg-dressed Fermi gas in a three-dimensional free space. It is shown that the collective density excitations develop a roton minimum, which is softened at a wave vector smaller than the Fermi wave vector when the particle density is above a critical value. The mean field calculation shows that, unlike the insulating density wave states often observed in conventional condensed matters, a self-assembled metallic density wave state emerges at low temperatures. In particular, the density wave state supports a Fermi surface and a body-centered-cubic crystal order at the same time with the estimated critical temperature being about one tenth of the noninteracting Fermi energy. Our results suggest the emergence of a fermionic quantum solid that should be observable in the current experimental setup.

  6. Contact Forces between Single Metal Oxide Nanoparticles in Gas-Phase Applications and Processes

    PubMed Central

    2017-01-01

    In this work we present a comprehensive experimental study to determine the contact forces between individual metal oxide nanoparticles in the gas-phase using atomic force microscopy. In addition, we determined the amount of physisorbed water for each type of particle surface. By comparing our results with mathematical models of the interaction forces, we could demonstrate that classical continuum models of van der Waals and capillary forces alone cannot sufficiently describe the experimental findings. Rather, the discrete nature of the molecules has to be considered, which leads to ordering at the interface and the occurrence of solvation forces. We demonstrate that inclusion of solvation forces in the model leads to quantitative agreement with experimental data and that tuning of the molecular order by addition of isopropanol vapor allows us to control the interaction forces between the nanoparticles. PMID:28186771

  7. Phase Transformations and Metallization of Magnesium Oxide at High Pressure and Temperature

    NASA Astrophysics Data System (ADS)

    McWilliams, R. Stewart; Spaulding, Dylan K.; Eggert, Jon H.; Celliers, Peter M.; Hicks, Damien G.; Smith, Raymond F.; Collins, Gilbert W.; Jeanloz, Raymond

    2012-12-01

    Magnesium oxide (MgO) is representative of the rocky materials comprising the mantles of terrestrial planets, such that its properties at high temperatures and pressures reflect the nature of planetary interiors. Shock-compression experiments on MgO to pressures of 1.4 terapascals (TPa) reveal a sequence of two phase transformations: from B1 (sodium chloride) to B2 (cesium chloride) crystal structures above 0.36 TPa, and from electrically insulating solid to metallic liquid above 0.60 TPa. The transitions exhibit large latent heats that are likely to affect the structure and evolution of super-Earths. Together with data on other oxide liquids, we conclude that magmas deep inside terrestrial planets can be electrically conductive, enabling magnetic field-producing dynamo action within oxide-rich regions and blurring the distinction between planetary mantles and cores.

  8. In situ gas phase measurements during metal alkylamide atomic layer deposition.

    PubMed

    Maslar, J E; Kimes, W A; Sperling, B A

    2011-09-01

    Metal alkylamide compounds, such as tetrakis(ethylmethylamido) hafnium (TEMAH), represent a technologically important class of metalorganic precursors for the deposition of metal oxides and metal nitrides via atomic layer deposition (ALD) or chemical vapor deposition. The development of in situ diagnostics for processes involving these compounds could be beneficial in, e.g., developing deposition recipes and validating equipment-scale simulations. This report describes the performance of the combination of two techniques for the simultaneous, rapid measurement of the three major gas phase species during hafnium oxide thermal ALD using TEMAH and water: TEMAH, water, and methylethyl amine (MEA), the only major reaction by-product. For measurement of TEMAH and MEA, direct absorption methods based on a broadband infrared source with different mid-IR bandpass filters and utilizing amplitude modulation and synchronous detection were developed. For the measurement of water, wavelength modulation spectroscopy utilizing a near-IR distributed feedback diode laser was used. Despite the relatively simple reactor geometry employed here (a flow tube), differences were easily observed in the time-dependent species distributions in 300 mL/min of a helium carrier gas and in 1000 mL/min of a nitrogen carrier gas. The degree of TEMAH entrainment was lower in 300 mL/min of helium compared to that in 1000 mL/min of nitrogen. The capability to obtain detailed time-dependent species concentrations during ALD could potentially allow for the selection of carrier gas composition and flow rates that would minimize parasitic wall reactions. However, when nitrogen was employed at the higher flow rates, various flow effects were observed that, if detrimental to a deposition process, would effectively limit the upper range of useful flow rates.

  9. Asymmetric photoredox transition-metal catalysis activated by visible light

    NASA Astrophysics Data System (ADS)

    Huo, Haohua; Shen, Xiaodong; Wang, Chuanyong; Zhang, Lilu; Röse, Philipp; Chen, Liang-An; Harms, Klaus; Marsch, Michael; Hilt, Gerhard; Meggers, Eric

    2014-11-01

    Asymmetric catalysis is seen as one of the most economical strategies to satisfy the growing demand for enantiomerically pure small molecules in the fine chemical and pharmaceutical industries. And visible light has been recognized as an environmentally friendly and sustainable form of energy for triggering chemical transformations and catalytic chemical processes. For these reasons, visible-light-driven catalytic asymmetric chemistry is a subject of enormous current interest. Photoredox catalysis provides the opportunity to generate highly reactive radical ion intermediates with often unusual or unconventional reactivities under surprisingly mild reaction conditions. In such systems, photoactivated sensitizers initiate a single electron transfer from (or to) a closed-shell organic molecule to produce radical cations or radical anions whose reactivities are then exploited for interesting or unusual chemical transformations. However, the high reactivity of photoexcited substrates, intermediate radical ions or radicals, and the low activation barriers for follow-up reactions provide significant hurdles for the development of efficient catalytic photochemical processes that work under stereochemical control and provide chiral molecules in an asymmetric fashion. Here we report a highly efficient asymmetric catalyst that uses visible light for the necessary molecular activation, thereby combining asymmetric catalysis and photocatalysis. We show that a chiral iridium complex can serve as a sensitizer for photoredox catalysis and at the same time provide very effective asymmetric induction for the enantioselective alkylation of 2-acyl imidazoles. This new asymmetric photoredox catalyst, in which the metal centre simultaneously serves as the exclusive source of chirality, the catalytically active Lewis acid centre, and the photoredox centre, offers new opportunities for the `green' synthesis of non-racemic chiral molecules.

  10. Enhanced Antimicrobial Activity Of Antibiotics Mixed With Metal Nanoparticles

    NASA Astrophysics Data System (ADS)

    Kumar, Sandeep; Kumar, Neeraj; Bhanjana, Gaurav; Thakur, Rajesh; Dilbaghi, Neeraj

    2011-12-01

    Current producers of antimicrobial technology have a long lasting, environmentally safe, non-leaching, water soluble solution that will eventually replace all poisons and heavy metals. The transition metal ions inevitably exist as metal complexes in biological systems by interaction with the numerous molecules possessing groupings capable of complexation or chelation. Nanoparticles of metal oxides offer a wide variety of potential applications in medicine due to the unprecedented advances in nanobiotechnology research. the bacterial action of antibiotics like penicillin, erythryomycin, ampicillin, streptomycin, kanamycin etc. and that of a mixture of antibiotics and metal and metal oxide nanoparticles like zinc oxide, zirconium, silver and gold on microbes was examined by the agar-well-diffusion method, enumeration of colony-forming units (CFU) and turbidimetry.

  11. Interplay between Ferroelastic and Metal-Insulator Phase Transitions in Strained Quasi-2D VO[subscript 2] Nanoplatelets

    SciTech Connect

    Tselev, Alexander; Strelcov, Evgheni; Luk’yanchuk, Igor A.; Budai, John D.; Tischler, Jonathan Z.; Ivanov, Ilia N.; Jones, Keith; Proksch, Roger; Kalinin, Sergei V.; Kolmakov, Aandrei

    2010-07-06

    Formation of ferroelastic twin domains in vanadium dioxide (VO{sub 2}) nanosystems can strongly affect local strain distributions, and hence couple to the strain-controlled metal-insulator transition. Here we report polarized-light optical and scanning microwave microscopy studies of interrelated ferroelastic and metal-insulator transitions in single-crystalline VO{sub 2} quasi-two-dimensional (quasi-2D) nanoplatelets (NPls). In contrast to quasi-1D single-crystalline nanobeams, the 2D geometric frustration results in emergence of several possible families of ferroelastic domains in NPls, thus allowing systematic studies of strain-controlled transitions in the presence of geometrical frustration. We demonstrate the possibility of controlling the ferroelastic domain population by the strength of the NPl-substrate interaction, mechanical stress, and by the NPl lateral size. Ferroelastic domain species and domain walls are identified based on standard group-theoretical considerations. Using variable temperature microscopy, we imaged the development of domains of metallic and semiconducting phases during the metal-insulator phase transition and nontrivial strain-driven reentrant domain formation. A long-range reconstruction of ferroelastic structures accommodating metal-insulator domain formation has been observed. These studies illustrate that a complete picture of the phase transitions in single-crystalline and disordered VO{sub 2} structures can be drawn only if both ferroelastic and metal-insulator strain effects are taken into consideration and understood.

  12. Interplay between Ferroelastic and Metal-Insulator Phase Transitions in Strained Quasi-2D VO[subscript 2] Nanoplatelets

    SciTech Connect

    Tselev, Alexander; Strelcov, Evgheni; Luk’yanchuk, Igor A.; Budai, John D.; Tischler, Jonathan Z.; Ivanov, Ilia N.; Jones, Keith; Proksch, Roger; Kalinin, Sergei V.; Kolmakov, Andrei

    2011-08-09

    Formation of ferroelastic twin domains in vanadium dioxide (VO{sub 2}) nanosystems can strongly affect local strain distributions, and hence couple to the strain-controlled metal-insulator transition. Here we report polarized-light optical and scanning microwave microscopy studies of interrelated ferroelastic and metal-insulator transitions in single-crystalline VO{sub 2} quasi-two-dimensional (quasi-2D) nanoplatelets (NPls). In contrast to quasi-1D single-crystalline nanobeams, the 2D geometric frustration results in emergence of several possible families of ferroelastic domains in NPls, thus allowing systematic studies of strain-controlled transitions in the presence of geometrical frustration. We demonstrate the possibility of controlling the ferroelastic domain population by the strength of the NPl-substrate interaction, mechanical stress, and by the NPl lateral size. Ferroelastic domain species and domain walls are identified based on standard group-theoretical considerations. Using variable temperature microscopy, we imaged the development of domains of metallic and semiconducting phases during the metal-insulator phase transition and nontrivial strain-driven reentrant domain formation. A long-range reconstruction of ferroelastic structures accommodating metal-insulator domain formation has been observed. These studies illustrate that a complete picture of the phase transitions in single-crystalline and disordered VO{sub 2} structures can be drawn only if both ferroelastic and metal-insulator strain effects are taken into consideration and understood.

  13. Method of encapsulating a phase change material with a metal oxide

    DOEpatents

    Ram, Manoj Kumar; Jotshi, Chand K.; Stefanakos, Elias K.; Goswami, Dharendra Yogi

    2016-11-15

    Storage systems based on latent heat storage have high-energy storage density, which reduces the footprint of the system and the cost. However, phase change materials (PCMs), such as NaNO.sub.3, NaCl, KNO.sub.3, have very low thermal conductivities. To enhave the storage of PCMs, macroencapsulation of PCMs was performed using a metal oxide, such as SiO.sub.2 or a graphene-SiO.sub.2, over polyimide-coated or nickel-embedded, polyimide-coated pellets The macro encapsulation provides a self-supporting structure, enhances the heat transfer rate, and provides a cost effective and reliable solution for thermal energy storage for use in solar thermal power plants. NaNO.sub.3 was selected for thermal storage in a temperature range of 300.degree. C. to 500.degree. C. The PCM was encapsulated in a metal oxide cell using self-assembly reactions, hydrolysis, and simultaneous chemical oxidation at various temperatures.

  14. Solution-Phase Epitaxial Growth of Quasi-Monocrystalline Cuprous Oxide on Metal Nanowires

    PubMed Central

    2014-01-01

    The epitaxial growth of monocrystalline semiconductors on metal nanostructures is interesting from both fundamental and applied perspectives. The realization of nanostructures with excellent interfaces and material properties that also have controlled optical resonances can be very challenging. Here we report the synthesis and characterization of metal–semiconductor core–shell nanowires. We demonstrate a solution-phase route to obtain stable core–shell metal–Cu2O nanowires with outstanding control over the resulting structure, in which the noble metal nanowire is used as the nucleation site for epitaxial growth of quasi-monocrystalline Cu2O shells at room temperature in aqueous solution. We use X-ray and electron diffraction, high-resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, photoluminescence spectroscopy, and absorption spectroscopy, as well as density functional theory calculations, to characterize the core–shell nanowires and verify their structure. Metal–semiconductor core–shell nanowires offer several potential advantages over thin film and traditional nanowire architectures as building blocks for photovoltaics, including efficient carrier collection in radial nanowire junctions and strong optical resonances that can be tuned to maximize absorption. PMID:25233392

  15. Constant phase uniform current loop for detection of metallic objects using longitudinal magnetic field projection

    NASA Astrophysics Data System (ADS)

    Heinz, Daniel C.; Melber, Adam W.; Brennan, Michael L.

    2013-06-01

    Currents on remote metallic objects such as landmines can be induced by projecting strong magnetic fields. These currents result in electromagnetic fields that can be subsequently detected. The magnetic field varies slowly as it passes from air into the ground and is sufficient to excite currents in buried metallic objects. Traditionally strong magnetic fields are produced using short-range transformer like inductive coupling, or as a component of powerful propagating electromagnetic fields. The strength of the magnetic component of the propagating electromagnetic field is restricted by regulatory limits on the total radiated radio frequency power. There is a need for a means to produce forward projected strong magnetic field at medium ranges with low-level propagation. This paper reports on a non-radiating loop antenna which maintains a constant amplitude and phase current around the loop and projects a strong magnetic field. The radiated field is small and results from the relativistic time-of-flight effect from one side of the loop to the other. The result is that a very strong magnetic field is produced in the near- to mid-field region, up to one wavelength away from the loop. Experiments with a prototype antenna and modeling show that the H-field is very high, radiated electromagnetic fields are negligible, and the drop off in field strength is inversely proportional to the distance squared. This agreement between experiments and modeling allows for a design based on computer simulations.

  16. Active metal oxides and polymer hybrids as biomaterials

    NASA Astrophysics Data System (ADS)

    Jarrell, John D.

    Bone anchored prosthetic attachments, like other percutaneous devices, suffer from poor soft tissue integration, seen as chronic inflammation, infection, epithelial downgrowth and regression. We looked at the use of metal oxides as bioactive agents that elicit different bioresponses, ranging from cell attachment, tissue integration and reduction of inflammation to modulation of cell proliferation, morphology and microbe killing. This study presents a novel method for creating titanium oxide and polydimethylsiloxane (PDMS) hybrid coated microplates for high throughput biological, bacterial and photocatalytic screening that overcomes several limitations of using bulk metal samples. Titanium oxide coatings were doped with silver, zinc, vanadium, aluminum, calcium and phosphorous, while PDMS was doped with titanium, vanadium and silver and subjected to hydrothermal heat treatment to determine the influence of chemistry and crystallinity on the viability, proliferation and adhesion of human fibroblasts, keratinocytes and Hela cells. Also explored was the influence of Ag and Zn doping on E. coli proliferation. We determined how titanium concentration in hybrids and silver doping influenced the photocatalytic degradation of methylene blue by coatings. A combined sub/percutaneous, polyurethane device was developed and implanted into the backs of CD hairless rats to investigate how optimized coatings influenced soft tissue integration in vivo. We demonstrate that the bioresponse of cells to coatings is controlled by elemental doping (V & Ag) and that planktonic bacterial growth was greatly reduced or stopped by Ag, but not Zn doping. Hydrothermal heat treatments (65 °C and 121 °C) did not greatly influence cellular bioresponse to coatings. We discovered a range of temperature resistant (up to 400 °C), solid state dispersions with enhanced ability to block full spectrum photon transmission and degrade methylene using medical x-rays, UV, visible and infrared photons. We

  17. Signatures of a quantum Griffiths phase in a d-metal alloy close to its ferromagnetic quantum critical point.

    PubMed

    Schroeder, Almut; Ubaid-Kassis, Sara; Vojta, Thomas

    2011-03-09

    We report magnetization measurements close to the ferromagnetic quantum phase transition of the d-metal alloy Ni(1 - x)V(x) at a vanadium concentration of x(c)≈11.4%. In the diluted regime (x > x(c)), the temperature (T) and magnetic field (H) dependences of the magnetization are characterized by nonuniversal power laws and display H/T scaling in a wide temperature and field range. The exponents vary strongly with x and follow the predictions of a quantum Griffiths phase. We also discuss the deviations and limits of the quantum Griffiths phase as well as the phase boundaries due to bulk and cluster physics.

  18. Vapor Phase Ketonization of Acetic Acid on Ceria Based Metal Oxides

    SciTech Connect

    Liu, Changjun; Karim, Ayman M.; Lebarbier, Vanessa M.; Mei, Donghai; Wang, Yong

    2013-06-27

    The activities of CeO2, Mn2O3-CeO2 and ZrO2-CeO2 were measured for acetic acid ketonization under reaction conditions relevant to pyrolysis vapor upgrading. We show that the catalyst ranking changed depending on the reaction conditions. Mn2O3-CeO2 was the most active catalyst at 350 oC, while ZrO2 - CeO2 was the most active catalyst at 450 oC. Under high CO2 and steam concentration in the reactants, Mn2O3-CeO2 was the most active catalyst at 350 and 450 °C. The binding energies of steam and CO2 with the active phase were calculated to provide the insight into the tolerance of Mn2O3-CeO2 to steam and CO2.

  19. Calculation of metallic and insulating phases of V{sub 2}O{sub 3} by hybrid density functionals

    SciTech Connect

    Guo, Yuzheng; Robertson, John; Clark, Stewart J.

    2014-02-07

    The electronic structure of vanadium sesquioxide V{sub 2}O{sub 3} in its different phases has been calculated using the screened exchange hybrid density functional. The hybrid functional accurately reproduces the experimental electronic properties of all three phases, the paramagnetic metal (PM) phase, the anti-ferromagnetic insulating phase, and the Cr-doped paramagnetic insulating (PI) phase. We find that a fully relaxed supercell model of the Cr-doped PI phase based on the corundum structure has a monoclinic-like local strain around the substitutional Cr atoms. This is found to drive the PI-PM transition, consistent with a Peierls-Mott transition. The PI phase has a calculated band gap of 0.15 eV, in good agreement with experiment.

  20. Enhanced x-ray imaging for a thin film cochlear implant with metal artefacts using phase retrieval tomography

    SciTech Connect

    Arhatari, B. D.; Harris, A. R.; Paolini, A. G.; Peele, A. G.

    2012-06-01

    Phase retrieval tomography has been successfully used to enhance imaging in systems that exhibit poor absorption contrast. However, when highly absorbing regions are present in a sample, so-called metal artefacts can appear in the tomographic reconstruction. We demonstrate that straightforward approaches for metal artefact reconstruction, developed in absorption contrast tomography, can be applied when using phase retrieval. Using a prototype thin film cochlear implant that has high and low absorption components made from iridium (or platinum) and plastic, respectively, we show that segmentation of the various components is possible and hence measurement of the electrode geometry and relative location to other regions of interest can be achieved.

  1. Electronic and thermal effects in the insulator-metal phase transition in VO{sub 2} nano-gap junctions

    SciTech Connect

    Joushaghani, Arash; Jeong, Junho; Stewart Aitchison, J.; Poon, Joyce K. S.; Paradis, Suzanne; Alain, David

    2014-12-08

    By controlling the thermal transport of VO{sub 2} nano-gap junctions using device geometry, contact material, and applied voltage waveforms, the electronically induced insulator-metal phase transition is investigated in the adiabatic heating and transient carrier injection regimes. With a gradual ramping of an applied voltage on a microsecond time scale, the transition electric field threshold can be directly reduced by the Joule heating. With an abrupt applied voltage, the transition threshold is initiated by carriers injected within the first tens of nanoseconds, but the complete insulator-metal phase transition is limited by thermal redistribution times to hundreds of nanoseconds.

  2. Devitrification kinetics and phase selection mechanisms in copper-zirconium metallic glasses

    NASA Astrophysics Data System (ADS)

    Kalay, Ilkay

    Metallic glasses have been a promising class of materials since their discovery in the 1960s. Indeed, remarkable chemical, mechanical and physical properties have attracted considerable attention, and several excellent reviews are available. Moreover, the special group of glass forming alloys known as the bulk metallic glasses (BMG) become amorphous solids even at relatively low cooling rates, allowing them to be cast in large cross sections, opening the scope of potential applications to include bulk forms and net shape structural applications. Recent studies have been reported for new bulk metallic glasses produced with lower cooling rates, from 0.1 to several hundred K/s. Some of the application products of BMGs include sporting goods, high performance springs and medical devices. Several rapid solidification techniques, including melt-spinning, atomization and surface melting have been developed to produce amorphous alloys. The aim of all these methods is to solidify the liquid phase rapidly enough to suppress the nucleation and growth of crystalline phases. Furthermore, the production of amorphous/crystalline composite (ACC) materials by partial crystallization of amorphous precursor has recently given rise to materials that provide better mechanical and magnetic properties than the monolithic amorphous or crystalline alloys. In addition, these advances illustrate the broad untapped potential of using the glassy state as an intermediate stage in the processing of new materials and nanostructures. These advances underlie the necessity of investigations on prediction and control of phase stability and microstructural dynamics during both solidification and devitrification processes. This research presented in this dissertation is mainly focused on Cu-Zr and Cu-Zr-Al alloy systems. The Cu-Zr binary system has high glass forming ability in a wide compositional range (35-70 at.% Cu). Thereby, Cu-Zr based alloys have attracted much attention according to fundamental

  3. Devitrification kinetics and phase selection mechanisms in Cu-Zr metallic glasses

    SciTech Connect

    Kalay, Ilkay

    2010-01-01

    Metallic glasses have been a promising class of materials since their discovery in the 1960s. Indeed, remarkable chemical, mechanical and physical properties have attracted considerable attention, and several excellent reviews are available. Moreover, the special group of glass forming alloys known as the bulk metallic glasses (BMG) become amorphous solids even at relatively low cooling rates, allowing them to be cast in large cross sections, opening the scope of potential applications to include bulk forms and net shape structural applications. Recent studies have been reported for new bulk metallic glasses produced with lower cooling rates, from 0.1 to several hundred K/s. Some of the application products of BMGs include sporting goods, high performance springs and medical devices. Several rapid solidification techniques, including melt-spinning, atomization and surface melting have been developed to produce amorphous alloys. The aim of all these methods is to solidify the liquid phase rapidly enough to suppress the nucleation and growth of crystalline phases. Furthermore, the production of amorphous/crystalline composite (ACC) materials by partial crystallization of amorphous precursor has recently given rise to materials that provide better mechanical and magnetic properties than the monolithic amorphous or crystalline alloys. In addition, these advances illustrate the broad untapped potential of using the glassy state as an intermediate stage in the processing of new materials and nanostructures. These advances underlie the necessity of investigations on prediction and control of phase stability and microstructural dynamics during both solidification and devitrification processes. This research presented in this dissertation is mainly focused on Cu-Zr and Cu-Zr-Al alloy systems. The Cu-Zr binary system has high glass forming ability in a wide compositional range (35-70 at.% Cu). Thereby, Cu-Zr based alloys have attracted much attention according to fundamental

  4. EXOPLANET ALBEDO SPECTRA AND COLORS AS A FUNCTION OF PLANET PHASE, SEPARATION, AND METALLICITY

    SciTech Connect

    Cahoy, Kerri L.; Marley, Mark S.; Fortney, Jonathan J.

    2010-11-20

    First generation space-based optical coronagraphic telescopes will obtain images of cool gas- and ice-giant exoplanets around nearby stars. Exoplanets lying at planet-star separations larger than about 1 AU-where an exoplanet can be resolved from its parent star-have spectra that are dominated by reflected light to beyond 1 {mu}m and punctuated by molecular absorption features. Here, we consider how exoplanet albedo spectra and colors vary as a function of planet-star separation, metallicity, mass, and observed phase for Jupiter and Neptune analogs from 0.35 to 1 {mu}m. We model Jupiter analogs with 1x and 3x the solar abundance of heavy elements, and Neptune analogs with 10x and 30x the solar abundance of heavy elements. Our model planets orbit a solar analog parent star at separations of 0.8 AU, 2 AU, 5 AU, and 10 AU. We use a radiative-convective model to compute temperature-pressure profiles. The giant exoplanets are found to be cloud-free at 0.8 AU, possess H{sub 2}O clouds at 2 AU, and have both NH{sub 3} and H{sub 2}O clouds at 5 AU and 10 AU. For each model planet we compute moderate resolution (R = {lambda}/{Delta}{lambda} {approx} 800) albedo spectra as a function of phase. We also consider low-resolution spectra and colors that are more consistent with the capabilities of early direct imaging capabilities. As expected, the presence and vertical structure of clouds strongly influence the albedo spectra since cloud particles not only affect optical depth but also have highly directional scattering properties. Observations at different phases also probe different volumes of atmosphere as the source-observer geometry changes. Because the images of the planets themselves will be unresolved, their phase will not necessarily be immediately obvious, and multiple observations will be needed to discriminate between the effects of planet-star separation, metallicity, and phase on the observed albedo spectra. We consider the range of these combined effects on

  5. On the origin of high activity of hcp metals for ammonia synthesis.

    PubMed

    Ahmadi, Shideh; Kaghazchi, Payam

    2016-02-21

    Structure and activity of nanoparticles of hexagonal close-packed (hcp) metals are studied using first-principles calculations. Results show that, in contact with a nitrogen environment, high-index {134[combining macron]2} facets are formed on hcp metal nanoparticles. Nitrogen molecules dissociate easily at kink sites on these high-index facets (activation barriers of <0.2 eV). Analysis of the site blocking effect and adsorption energies on {134[combining macron]2} facets explains the order of activity of hcp metals for ammonia synthesis: Re < Os < Ru. Our results indicate that the high activity of hcp metals for ammonia synthesis is due to the N-induced formation of {134[combining macron]2} facets with high activity for the dissociation of nitrogen molecules. However, quite different behavior for adsorption of dissociated N atoms leads to distinctive activity of hcp metals.

  6. Monitoring the dissolution process of metals in the gas phase: reactions of nanoscale Al and Ga metal atom clusters and their relationship to similar metalloid clusters.

    PubMed

    Burgert, Ralf; Schnöckel, Hansgeorg

    2008-05-14

    Formation and dissolution of metals are two of the oldest technical chemical processes. On the atomic scale, these processes are based on the formation and cleavage of metal-metal bonds. During the past 15 years we have studied intensively the intermediates during the formation process of metals, i.e. the formation of compounds containing many metal-metal bonds between naked metal atoms in the center and ligand-bearing metal atoms at the surface. We have called the clusters metalloid or, more generally, elementoid clusters. Via a retrosynthetic route, the many different Al and Ga metalloid clusters which have been structurally characterized allow us to understand also the dissolution process; i.e. the cleavage of metal-metal (M-M) bonds. However, this process can be detected much more directly by the reaction of single metal atom clusters in the gas phase under high vacuum conditions. A suitable tool to monitor the dissolution process of a metal cluster in the gas phase is FT-ICR (Fourier transform ion cyclotron resonance) mass spectrometry. Snapshots during these cleavage processes are possible because only every 1-10 s is there a contact between a cluster molecule and an oxidizing molecule (e.g. Cl2). This period is long, i.e. the formation of the primary product (a smaller metal atom cluster) is finished before the next collision happens. We have studied three different types of reaction:(1) Step-by-step fragmentation of a structurally known metalloid cluster allows us to understand the bonding principle of these clusters because in every step only the weakest bond is broken.(2) There are three oxidation reactions of an Al13(-) cluster molecule with Cl2, HCl and O2 central to this review. These three reactions represent three different reaction types, (a) an exothermic reaction (Cl2), (b) an endothermic reaction (HCl), and (c) a kinetically limited reaction based on spin conservation rules (O2).(3) Finally, we present the reaction of a metalloid cluster with Cl2

  7. Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts

    PubMed Central

    Varnell, Jason A.; Tse, Edmund C. M.; Schulz, Charles E.; Fister, Tim T.; Haasch, Richard T.; Timoshenko, Janis; Frenkel, Anatoly I.; Gewirth, Andrew A.

    2016-01-01

    The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites. PMID:27538720

  8. Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts.

    PubMed

    Varnell, Jason A; Tse, Edmund C M; Schulz, Charles E; Fister, Tim T; Haasch, Richard T; Timoshenko, Janis; Frenkel, Anatoly I; Gewirth, Andrew A

    2016-08-19

    The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites.

  9. Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts

    NASA Astrophysics Data System (ADS)

    Varnell, Jason A.; Tse, Edmund C. M.; Schulz, Charles E.; Fister, Tim T.; Haasch, Richard T.; Timoshenko, Janis; Frenkel, Anatoly I.; Gewirth, Andrew A.

    2016-08-01

    The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites.

  10. Characterization of AN Actively Cooled Metal Foil Thermal Radiation Shield

    NASA Astrophysics Data System (ADS)

    Feller, J. R.; Kashani, A.; Helvensteijn, B. P. M.; Salerno, L. J.

    2010-04-01

    Zero boil-off (ZBO) or reduced boil-off (RBO) systems that involve active cooling of large cryogenic propellant tanks will most likely be required for future space exploration missions. For liquid oxygen or methane, such systems could be implemented using existing high technology readiness level (TRL) cryocoolers. However, for liquid hydrogen temperatures (˜20 K) no such coolers exist. In order to partially circumvent this technology gap, the concept of broad area cooling (BAC) has been developed, whereby a low mass thermal radiation shield could be maintained at temperatures around 100 K by steady circulation of cold pressurized gas through a network of narrow tubes. By this method it is possible to dramatically reduce the radiative heat leak to the 20 K tank. A series of experiments, designed to investigate the heat transfer capabilities of BAC systems, have been conducted at NASA Ames Research Center (ARC). Results of the final experiment in this series, investigating heat transfer from a metal foil film to a distributed cooling line, are presented here.

  11. CHARACTERIZATION OF AN ACTIVELY COOLED METAL FOIL THERMAL RADIATION SHIELD

    SciTech Connect

    Feller, J. R.; Salerno, L. J.; Kashani, A.; Helvensteijn, B. P. M.

    2010-04-09

    Zero boil-off (ZBO) or reduced boil-off (RBO) systems that involve active cooling of large cryogenic propellant tanks will most likely be required for future space exploration missions. For liquid oxygen or methane, such systems could be implemented using existing high technology readiness level (TRL) cryocoolers. However, for liquid hydrogen temperatures (approx20 K) no such coolers exist. In order to partially circumvent this technology gap, the concept of broad area cooling (BAC) has been developed, whereby a low mass thermal radiation shield could be maintained at temperatures around 100 K by steady circulation of cold pressurized gas through a network of narrow tubes. By this method it is possible to dramatically reduce the radiative heat leak to the 20 K tank. A series of experiments, designed to investigate the heat transfer capabilities of BAC systems, have been conducted at NASA Ames Research Center (ARC). Results of the final experiment in this series, investigating heat transfer from a metal foil film to a distributed cooling line, are presented here.

  12. High internal ionic liquid phase emulsion stabilized by metal-organic frameworks.

    PubMed

    Li, Zhihao; Zhang, Jianling; Luo, Tian; Tan, Xiuniang; Liu, Chengcheng; Sang, Xinxin; Ma, Xue; Han, Buxing; Yang, Guanying

    2016-11-04

    The emulsification of metal-organic frameworks (MOFs) for the two immiscible phases of water and ionic liquid (IL) was investigated for the first time. It was found that Ni-BDC (BDC = 1,4-dicarboxybenzene) can emulsify water and ILs and favor the formation of high internal phase emulsions (HIPEs) under certain experimental conditions. The microstructures of the HIPEs were characterized by confocal laser scanning microscopy using a fluorescent dye Rhodamine B, which proves that the HIPEs are the IL-in-water type. Further results reveal that the HIPE forms during the IL-in-water to water-in-IL emulsion inversion. The possibilities of the HIPE formation by other MOFs (Cu-BDC and Zn-BDC) were explored and the mechanism for HIPE formation was discussed. The MOF-stabilized HIPE was applied to the in situ synthesis of a MOF/polymer composite by HIPE polymerization. The macroporous MOF/polyacrylamide network and MOF/polystyrene microspheres were obtained from the HIPEs, respectively.

  13. Composition induced metal-insulator quantum phase transition in the Heusler type Fe2VAl

    NASA Astrophysics Data System (ADS)

    Naka, Takashi; Nikitin, Artem M.; Pan, Yu; de Visser, Anne; Nakane, Takayuki; Ishikawa, Fumihiro; Yamada, Yuh; Imai, Motoharu; Matsushita, Akiyuki

    2016-07-01

    We report the magnetism and transport properties of the Heusler compound Fe2+x V1-x Al at  -0.10  ⩽  x  ⩽  0.20 under pressure and a magnetic field. A metal-insulator quantum phase transition occurred at x  ≈  -0.05. Application of pressure or a magnetic field facilitated the emergence of finite zero-temperature conductivity σ 0 around the critical point, which scaled approximately according to the power law (P  -  P c ) γ . At x  ⩽  -0.05, a localized paramagnetic spin appeared, whereas above the ferromagnetic quantum critical point at x  ≈  0.05, itinerant ferromagnetism was established. At the quantum critical points at x  =  -0.05 and 0.05, the resistivity and specific heat exhibited singularities characteristic of a Griffiths phase appearing as an inhomogeneous electronic state.

  14. Structures of the metallic and superconducting high pressure phases of solid CS2

    PubMed Central

    Zarifi, Niloofar; Liu, Hanyu; Tse, John S.

    2015-01-01

    First principles structural prediction and molecular dynamics (MD) calculations have been performed to examine the structures responsible for the recently reported metallic and superconducting phases of highly compressed CS2. The low pressure experimental molecular crystal structure was found to be metastable and transformed into a disordered structure above 10 GPa. At 60 GPa, the predicted low energy structures show molecular CS2 is separated into C and S dominant regions. A crystalline structure with the P21/m symmetry was found to be most stable from 60 to 120 GPa. The structure is formed from alternate layers of hexagonal C rings and S 2D-square-nets linked by C-S bonds. A non-crystalline structure with similar features structure is also predicted by MD calculations. Electron-phonon coupling calculations show this crystalline phase is superconductive. Contrary to the suggestions made from the experiments, no magnetism was found in all predicted low enthalpy high pressure structures. Moreover, the theoretical results do not support the proposal on the existence of hypervalent 6-coordinated carbon at 120 GPa. PMID:25982346

  15. Growth behavior of GaSb by metal organic vapor-phase epitaxy

    NASA Astrophysics Data System (ADS)

    Rathi, Manish K.; Hawkins, Brian E.; Kuech, Thomas F.

    2006-11-01

    The growth mechanisms of GaSb in a metal-organic vapor-phase epitaxy (MOVPE) system were studied for both trimethyl gallium (TMG)/trimethyl antimony (TMSb) and triethyl gallium (TEG)/TMSb growth chemistries. The effect of growth temperature and precursor mole fractions on GaSb growth rate was determined experimentally. Numerical analysis of the reactor and growth process was described in a combined chemical-thermal-fluid flow model. A Langmuir-Hinshelwood-type mechanism involving a surface reaction between adsorbed monomethyl gallium (MMG) and adsorbed monomethyl antimony (MMSb) or adsorbed Ga and adsorbed MMSb was proposed for the growth of GaSb by MOVPE using TMG or TEG and TMSb chemistries, respectively. The chemical model for TMG/TMSb chemistry included bounds on the surface chemistry derived for the range of V/III precursor ratio which were observed to lead to a second phase, i.e., elemental Ga or Sb, formation. Two growth regimes were observed for TMG/TMSb chemistry: above 575 °C the growth rate was mass transfer controlled whereas for lower temperatures it is kinetically limited. No such temperature dependence has been found for the TEG/TMSb chemistry over all experimental employed ranges of growth parameters.

  16. Structures of the metallic and superconducting high pressure phases of solid CS2.

    PubMed

    Zarifi, Niloofar; Liu, Hanyu; Tse, John S

    2015-05-18

    First principles structural prediction and molecular dynamics (MD) calculations have been performed to examine the structures responsible for the recently reported metallic and superconducting phases of highly compressed CS2. The low pressure experimental molecular crystal structure was found to be metastable and transformed into a disordered structure above 10 GPa. At 60 GPa, the predicted low energy structures show molecular CS2 is separated into C and S dominant regions. A crystalline structure with the P21/m symmetry was found to be most stable from 60 to 120 GPa. The structure is formed from alternate layers of hexagonal C rings and S 2D-square-nets linked by C-S bonds. A non-crystalline structure with similar features structure is also predicted by MD calculations. Electron-phonon coupling calculations show this crystalline phase is superconductive. Contrary to the suggestions made from the experiments, no magnetism was found in all predicted low enthalpy high pressure structures. Moreover, the theoretical results do not support the proposal on the existence of hypervalent 6-coordinated carbon at 120 GPa.

  17. Prediction of different crystal structure phases in metal borides: A lithium monoboride analog to MgB2

    NASA Astrophysics Data System (ADS)

    Kolmogorov, Aleksey N.; Curtarolo, Stefano

    2006-05-01

    Modern compound prediction methods can efficiently screen large numbers of crystal structure phases and direct the experimental search for new materials. One of the most challenging problems in alloy theory is the identification of stable phases with a never seen prototype; such predictions do not always follow rational strategies. While performing ab initio data mining of intermetallic compounds we made an unexpected discovery: even in such a well-studied class of systems as metal borides there are previously unknown layered phases comparable in energy to the existing ones. With ab initio calculations we show that the new metal-sandwich (MS) lithium monoboride phases are marginally stable under ambient conditions but become favored over the known stoichiometric compounds under moderate pressures. The MS lithium monoboride exhibits electronic features similar to those in magnesium diboride and is expected to be a good superconductor.

  18. Switchable Ultrathin Quarter-wave Plate in Terahertz Using Active Phase-change Metasurface

    PubMed Central

    Wang, Dacheng; Zhang, Lingchao; Gu, Yinghong; Mehmood, M. Q.; Gong, Yandong; Srivastava, Amar; Jian, Linke; Venkatesan, T.; Qiu, Cheng-Wei; Hong, Minghui

    2015-01-01

    Metamaterials open up various exotic means to control electromagnetic waves and among them polarization manipulations with metamaterials have attracted intense attention. As of today, static responses of resonators in metamaterials lead to a narrow-band and single-function operation. Extension of the working frequency relies on multilayer metamaterials or different unit cells, which hinder the development of ultra-compact optical systems. In this work, we demonstrate a switchable ultrathin terahertz quarter-wave plate by hybridizing a phase change material, vanadium dioxide (VO2), with a metasurface. Before the phase transition, VO2 behaves as a semiconductor and the metasurface operates as a quarter-wave plate at 0.468 THz. After the transition to metal phase, the quarter-wave plate operates at 0.502 THz. At the corresponding operating frequencies, the metasurface converts a linearly polarized light into a circularly polarized light. This work reveals the feasibility to realize tunable/active and extremely low-profile polarization manipulation devices in the terahertz regime through the incorporation of such phase-change metasurfaces, enabling novel applications of ultrathin terahertz meta-devices. PMID:26442614

  19. Spatial homogeneity criteria for active media of cataphoresis repetitively pulsed metal vapour lasers

    SciTech Connect

    Chebotarev, Gennady D; Prutsakov, Oleg O; Latush, Evgeny L

    2005-07-31

    The formation of the transverse distribution of the metal vapour concentration in repetitively pulsed lasers is analysed. The criterion for the homogeneity of this distribution is found. The optimal conditions for excitation of the active media of cataphoresis repetitively pulsed metal vapour lasers are determined under which a high degree of both longitudinal and transverse homogeneity is achieved. (active media)

  20. New chelating reagents for preconcentration, separation, determination of metal complexes by high performance liquid chromatography and solid phase extraction

    SciTech Connect

    Qian, Yan wen

    1991-12-03

    A general scheme is outlined for rapid determination of metal cations by complexation and subsequent HPLC separation. The synthesis and general properties are described for several new thiohydrazone chelating reagents. Solubility considerations suggest that the metal complexes have a positive charge. Excellent chromatographic separations are obtained for mixtures of up to seven metal complexes. Addition of a positively charged additive to the eluent is shown to have a significant effect on both the retention times and sharpness of the chromatographic peaks. Separation of the metal complexes on resins with a permanent charge is also shown to be feasible. Two new hydrazone reagents have been synthesized and characterized. Trace metal ions in aqueous solution are complexed by one of the hydrazones and the resulting metal complexes are solid phase extracted onto a mini cation-exchange or polymeric column. The uptake of metal complexes is complete and the elution step is fast and complete. The quantitative recoveries of metal ions determined by both spectrophotometric method and ICP-MS are very satisfactory and agree with each other.

  1. A comparative study of optical absorption and photocatalytic properties of nanocrystalline single-phase anatase and rutile TiO{sub 2} doped with transition metal cations

    SciTech Connect

    Kernazhitsky, L.; Shymanovska, V.; Gavrilko, T.; Naumov, V.; Kshnyakin, V.; Khalyavka, T.

    2013-02-15

    The effect of nanocrystalline TiO{sub 2} doping with transition metal cations (Cu{sup 2+}, Fe{sup 3+}, Co{sup 2+}, Cr{sup 3+}) on their optical absorption and photocatalytic properties was investigated. The obtained metal-doped TiO{sub 2} samples were characterized by X-ray diffraction, scanning electron microscopy, and UV-vis absorption spectroscopy. It is shown that doping effect on anatase (A) and rutile (R) properties is quite different, being much stronger and complicated on A than on R. Contrary to doped R, doped A revealed a significant red shift of the absorption edge along with the band gap narrowing. Photocatalytic activity of anatase increases upon doping in the order: Aactivity of rutile samples decreases upon doping in the series R>R/Co>R/Cu>R/Fe>R/Cr, indicating the inhibitory effect of impurity cations. This fact correlates with the decrease in the UV absorption of the doped rutile in the region of the Hg-lamp irradiation at 4.88 eV. - Graphical abstract: A red shift of the absorption edge of nanocrystalline single-phase anatase after doping with transition metal cations. Highlights: Black-Right-Pointing-Pointer Single-phase anatase and rutile powders surface-doped with transition metal cations. Black-Right-Pointing-Pointer Absorption edge and band gap of rutile do not change with surface doping. Black-Right-Pointing-Pointer Band gap of surface-doped anatase reduces being the lowest for A/Fe. Black-Right-Pointing-Pointer The surface-doping improves photocatalytic activity of anatase. Black-Right-Pointing-Pointer The surface-doping inhibits photocatalytic activity of rutile.

  2. Solubility Behavior and Phase Stability of Transition Metal Oxides in Alkaline Hydrothermal Environments

    SciTech Connect

    S.E. Ziemniak

    2000-05-18

    The solubility behavior of transition metal oxides in high temperature water is interpreted by recognizing three types of chemical reaction equilibria: metal oxide hydration/dehydration, metal oxide dissolution and metal ion hydroxocomplex formation. The equilibria are quantified using thermodynamic concepts and the thermochemical properties of the metal oxides/ions representative of the most common constituents of construction metal alloys, i.e., element shaving atomic numbers between Z = 22 (Ti) and Z = 30 (Zn), are summarized on the basis of metal oxide solubility studies conducted in the laboratory. Particular attention is devoted to the uncharged metal ion hydrocomplex, M{sup Z}(OH){sub Z}(aq), since its thermochemical properties define minimum solubilities of the metal oxide at a given temperature. Experimentally-extracted values of standard partial molal entropy (S{sup 0}) for the transition metal ion neutral hydroxocomplex are shown to be influenced by ligand field stabilization energies and complex symmetry.

  3. Adsorption of metal ions by pecan shell-based granular activated carbons.

    PubMed

    Bansode, R R; Losso, J N; Marshall, W E; Rao, R M; Portier, R J

    2003-09-01

    The present investigation was undertaken to evaluate the adsorption effectiveness of pecan shell-based granular activated carbons (GACs) in removing metal ions (Cu(2+), Pb(2+), Zn(2+)) commonly found in municipal and industrial wastewater. Pecan shells were activated by phosphoric acid, steam or carbon dioxide activation methods. Metal ion adsorption of shell-based GACs was compared to the metal ion adsorption of a commercial carbon, namely, Calgon's Filtrasorb 200. Adsorption experiments were conducted using solutions containing all three metal ions in order to investigate the competitive effects of the metal ions as would occur in contaminated wastewater. The results obtained from this study showed that acid-activated pecan shell carbon adsorbed more lead ion and zinc ion than any of the other carbons, especially at carbon doses of 0.2-1.0%. However, steam-activated pecan shell carbon adsorbed more copper ion than the other carbons, particularly using carbon doses above 0.2%. In general, Filtrasorb 200 and carbon dioxide-activated pecan shell carbons were poor metal ion adsorbents. The results indicate that acid- and steam-activated pecan shell-based GACs are effective metal ion adsorbents and can potentially replace typical coal-based GACs in treatment of metal contaminated wastewater.

  4. Active Phase and Amplitude Fluctuations of Flagellar Beating

    NASA Astrophysics Data System (ADS)

    Ma, Rui; Klindt, Gary S.; Riedel-Kruse, Ingmar H.; Jülicher, Frank; Friedrich, Benjamin M.

    2014-07-01

    The eukaryotic flagellum beats periodically, driven by the oscillatory dynamics of molecular motors, to propel cells and pump fluids. Small but perceivable fluctuations in the beat of individual flagella have physiological implications for synchronization in collections of flagella as well as for hydrodynamic interactions between flagellated swimmers. Here, we characterize phase and amplitude fluctuations of flagellar bending waves using shape mode analysis and limit-cycle reconstruction. We report a quality factor of flagellar oscillations Q =38.0±16.7 (mean±s.e.). Our analysis shows that flagellar fluctuations are dominantly of active origin. Using a minimal model of collective motor oscillations, we demonstrate how the stochastic dynamics of individual motors can give rise to active small-number fluctuations in motor-cytoskeleton systems.

  5. Carbon nanotubes as solid-phase extraction sorbents prior to atomic spectrometric determination of metal species: a review.

    PubMed

    Herrero Latorre, C; Álvarez Méndez, J; Barciela García, J; García Martín, S; Peña Crecente, R M

    2012-10-24

    New materials have significant impact on the development of new methods and instrumentation for chemical analysis. From the discovery of carbon nanotubes in 1991, single and multi-walled carbon nanotubes--due to their high adsorption and desorption capacities--have been employed as sorption substrates in solid-phase extraction for the preconcentration of metal species from diverse matrices. Looking for successive improvements in sensitivity and selectivity, in the past few years, carbon nanotubes have been utilized as sorbents for solid phase extraction in three different ways: like as-grown, oxidized and functionalized nanotubes. In the present paper, an overview of the recent trends in the use of carbon nanotubes for solid phase extraction of metal species in environmental, biological and food samples is presented. The determination procedures involved the adsorption of metals on the nanotube surface, their quantitative desorption and subsequent measurement by means of atomic spectrometric techniques such as flame atomic absorption spectrometry, electrothermal atomic absorption spectrometry or inductively coupled plasma atomic emission spectrometry/mass spectrometry, among others. Synthesis, purification and types of carbon nanotubes, as well as the diverse chemical and physical strategies for their functionalization are described. Based on 140 references, the performance and general properties of the applications of solid phase extraction based on carbon nanotubes for metal species atomic spectrometric determination are discussed.

  6. Monitoring the formation of carbide crystal phases during the thermal decomposition of 3d transition metal dicarboxylate complexes

    SciTech Connect

    Huba, ZJ; Carpenter, EE

    2014-06-06

    Single molecule precursors can help to simplify the synthesis of complex alloys by minimizing the amount of necessary starting reagents. However, single molecule precursors are time consuming to prepare with very few being commercially available. In this study, a simple precipitation method is used to prepare Fe, Co, and Ni fumarate and succinate complexes. These complexes were then thermally decomposed in an inert atmosphere to test their efficiency as single molecule precursors for the formation of metal carbide phases. Elevated temperature X-ray diffraction was used to identify the crystal phases produced upon decomposition of the metal dicarboxylate complexes. Thermogravimetric analysis coupled with an infrared detector was used to identify the developed gaseous decomposition products. All complexes tested showed a reduction from the starting M2+ oxidation state to the M oxidation state, upon decomposition. Also, each complex tested showed CO2 and H2O as gaseous decomposition products. Nickel succinate, iron succinate, and iron fumarate complexes were found to form carbide phases upon decomposition. This proves that transition metal dicarboxylate salts can be employed as efficient single molecule precursors for the formation of metal carbide crystal phases.

  7. The Analysis and Modeling of Phase Stability and Multiphase Designs in High Temperature Refractory Metal-Silicon-Boron Alloys

    DTIC Science & Technology

    2006-01-01

    7 2.4. Alloying Strategy in Refractory M etal Silicides and Borosilicides...11 2.4.2. Silicide Phase Structures ...................................................................................................... 12 2.4.3...environments that require a material to display an inherent oxidation protection that can be enhanced further by coating [79Mai]. In terms of metallic system

  8. Blanket and Patterned Growth of CdTe on (211)Si Substrates by Metal-Organic Vapor Phase Epitaxy

    DTIC Science & Technology

    2012-05-15

    Vapor Deposition, Epitaxial Lateral Overgrowth, Selective Epitaxy, CdTe Ishwara B. Bhat*,1, , Sunil R. Rao1, , Shashidhar Shintri2, , Randolph N...growth of CdTe on (211)Si substrates by metal- organic vapor phase epitaxy Ishwara B. Bhat*,1, Sunil R. Rao1, Shashidhar Shintri2, and Randolph N

  9. Near-Field Nanoscopy of Metal-Insulator Phase Transitions Towards Synthesis of Novel Correlated Transition Metal Oxides and Their Interaction with Plasmon Resonances

    DTIC Science & Technology

    2016-01-05

    most exciting discoveries in the past few years in condensed matter research is the theoretical foundations of topological insulating electronic...Figure 1b–d) show bright and dark optical contrast due to the coexisting insulating ( dark ) and metallic (bright) phases affecting the nanoscale...separated by a dark contrast from the inner bright surface of the structure. Such an edge fringe is missing in the near-field amplitude image taken

  10. Generation, Detection and characterization of Gas-Phase Transition Metal containing Molecules

    SciTech Connect

    Steimle, Timothy

    2015-12-15

    The objective of this project was to generate, detect, and characterize small, gas-phase, metal containing molecules. In addition to being relevant to high temperature chemical environments (e.g. plasmas and combustion), gas-phase experiments on metal containing molecules serve as the most direct link to a molecular-level theoretical model for catalysis. Catalysis (i.e. the addition of a small about of recoverable material to control the rate and direction of a chemical reaction) is critical to the petroleum and pharmaceutical industries as well as environmental remediation. Currently, the majority of catalytic materials are based on very expensive metals such as platinum (Pt), palladium (Pd), iridium (Ir,) rhenium (Re), and rhodium (Rh). For example, the catalyst used for converting linear hydrocarbon molecules (e.g. hexane) to cyclic molecules (e.g. cyclohexane) is a mixture of Pt and Re suspended on alumina. It enables straight chain alkanes to be converted into branched-chain alkanes, cyclohexanes and aromatic hydrocarbons which are used, amongst other things, to enhance the octane number of petrol. A second example is the heterogeneous catalysis used in automobile exhaust systems to: a) decrease nitrogen oxide; b) reduce carbon monoxide; and c) oxidize unburned hydrocarbons. The exhaust is vented through a high-surface area chamber lined with Pt, Pd, and Rh. For example, the carbon monoxide is catalytically converted to carbon dioxide by reaction with oxygen. The research results from this work have been published in readily accessible journals1-28. The ground and excited electronic state properties of small metal containing molecules that we determine were: a) electronic state distributions and lifetimes, b) vibrational frequencies, c) bond lengths and angles, d) hyperfine interactions, e) permanent electric dipole moments, mel, and f) magnetic dipoles, μm. In general terms, μel, gives insight into the charge distribution and mm into

  11. Feedback-induced phase transitions in active heterogeneous conductors.

    PubMed

    Ocko, Samuel A; Mahadevan, L

    2015-04-03

    An active conducting medium is one where the resistance (conductance) of the medium is modified by the current (flow) and in turn modifies the flow, so that the classical linear laws relating current and resistance, e.g., Ohm's law or Darcy's law, are modified over time as the system itself evolves. We consider a minimal model for this feedback coupling in terms of two parameters that characterize the way in which addition or removal of matter follows a simple local (or nonlocal) feedback rule corresponding to either flow-seeking or flow-avoiding behavior. Using numerical simulations and a continuum mean field theory, we show that flow-avoiding feedback causes an initially uniform system to become strongly heterogeneous via a tunneling (channel-building) phase separation; flow-seeking feedback leads to an immuring (wall-building) phase separation. Our results provide a qualitative explanation for the patterning of active conducting media in natural systems, while suggesting ways to realize complex architectures using simple rules in engineered systems.

  12. Metal hydride/chemical heat-pump development project. Phase I. Final report

    SciTech Connect

    Argabright, T.A.

    1982-02-01

    The metal hydride/chemical heat pump (MHHP) is a chemical heat pump containing two hydrides for the storage and/or recovery of thermal energy. It utilizes the heat of reaction of hydrogen with specific metal alloys. The MHHP design can be tailored to provide heating and/or cooling or temperature upgrading over a wide range of input and ambient temperatures. The system can thus be used with a variety of heat sources including waste heat, solar energy or a fossil fuel. The conceptual design of the MHHP was developed. A national market survey including a study of applications and market sectors was conducted. The technical tasks including conceptual development, thermal and mechanical design, laboratory verification of design and material performance, cost analysis and the detailed design of the Engineering Development Test Unit (EDTU) were performed. As a result of the market study, the temperature upgrade cycle of the MHHP was chosen for development. Operating temperature ranges for the upgrader were selected to be from 70 to 110/sup 0/C (160 to 230/sup 0/F) for the source heat and 140 to 190/sup 0/C (280 to 375/sup 0/F) for the product heat. These ranges are applicable to many processes in industries such as food, textile, paper and pulp, and chemical. The hydride pair well suited for these temperatures is LaNi/sub 5//LaNi/sub 4/ /sub 5/Al/sub 0/ /sub 5/. The EDTU was designed for the upgrade cycle. It is a compact finned tube arrangement enclosed in a pressure vessel. This design incorporates high heat transfer and low thermal mass in a system which maximizes the coefficient of performance (COP). It will be constructed in Phase II. Continuation of this effort is recommended.

  13. Poultry litter-based activated carbon for removing heavy metal ions in water.

    PubMed

    Guo, Mingxin; Qiu, Guannan; Song, Weiping

    2010-02-01

    Utilization of poultry litter as a precursor material to manufacture activated carbon for treating heavy metal-contaminated water is a value-added strategy for recycling the organic waste. Batch adsorption experiments were conducted to investigate kinetics, isotherms, and capacity of poultry litter-based activated carbon for removing heavy metal ions in water. It was revealed that poultry litter-based activated carbon possessed significantly higher adsorption affinity and capacity for heavy metals than commercial activated carbons derived from bituminous coal and coconut shell. Adsorption of metal ions onto poultry litter-based carbon was rapid and followed Sigmoidal Chapman patterns as a function of contact time. Adsorption isotherms could be described by different models such as Langmuir and Freundlich equations, depending on the metal species and the coexistence of other metal ions. Potentially 404 mmol of Cu2+, 945 mmol of Pb2+, 236 mmol of Zn2+, and 250-300 mmol of Cd2+ would be adsorbed per kg of poultry litter-derived activated carbon. Releases of nutrients and metal ions from litter-derived carbon did not pose secondary water contamination risks. The study suggests that poultry litter can be utilized as a precursor material for economically manufacturing granular activated carbon that is to be used in wastewater treatment for removing heavy metals.

  14. Performance and modeling of active metal-matrix composites manufactured by ultrasonic additive manufacturing

    NASA Astrophysics Data System (ADS)

    Hahnlen, Ryan; Dapino, Marcelo J.

    2011-04-01

    This paper presents the development and characterization of active aluminum-matrix composites manufactured by Ultrasonic Additive Manufacturing (UAM), an emerging rapid prototyping process based on ultrasonic metal welding. The primary benefit of UAM over other metal-matrix fabrication processes is the low process temperatures, as low as 25 °C. UAM thus provides unprecedented opportunities to develop adaptive structures with seamlessly embedded smart materials and electronic components without degrading the properties that make these materials and components attractive. The objective of this research is to develop UAM composites with aluminum matrices and embedded shape memory NiTi, magnetostrictive Galfenol (FeGa), and polyvinylidene fluoride (PVDF) phases. The paper is focused on the thermally induced strain response and stiffness behavior of NiTi-Al composites, the actuation properties of FeGa-Al composites, and the embedded sensing capabilities of PVDF-Al composites. We observe up to a 10% increase over room temperature stiffness for NiTi-Al composites and a magnetomechanical response in the FeGa-Al composite up to 52.4 μɛ. The response of the PVDF-Al composite to harmonic loads is observed over a frequency range of 10 to 1000 Hz.

  15. Role of Metal Ions on the Activity of Mycobacterium tuberculosis Pyrazinamidase

    PubMed Central

    Sheen, Patricia; Ferrer, Patricia; Gilman, Robert H.; Christiansen, Gina; Moreno-Román, Paola; Gutiérrez, Andrés H.; Sotelo, Jun; Evangelista, Wilfredo; Fuentes, Patricia; Rueda, Daniel; Flores, Myra; Olivera, Paula; Solis, José; Pesaresi, Alessandro; Lamba, Doriano; Zimic, Mirko

    2012-01-01

    Pyrazinamidase of Mycobacterium tuberculosis catalyzes the conversion of pyrazinamide to the active molecule pyrazinoic acid. Reduction of pyrazinamidase activity results in a level of pyrazinamide resistance. Previous studies have suggested that pyrazinamidase has a metal-binding site and that a divalent metal cofactor is required for activity. To determine the effect of divalent metals on the pyrazinamidase, the recombinant wild-type pyrazinamidase corresponding to the H37Rv pyrazinamide-susceptible reference strain was expressed in Escherichia coli with and without a carboxy terminal. His-tagged pyrazinamidase was inactivated by metal depletion and reactivated by titration with divalent metals. Although Co2+, Mn2+, and Zn2+ restored pyrazinamidase activity, only Co2+ enhanced the enzymatic activity to levels higher than the wild-type pyrazinamidase. Cu2+, Fe2+, Fe3+, and Mg2+ did not restore the activity under the conditions tested. Various recombinant mutated pyrazinamidases with appropriate folding but different enzymatic activities showed a differential pattern of recovered activity. X-ray fluorescence and atomic absorbance spectroscopy showed that recombinant wild-type pyrazinamidase expressed in E. coli most likely contained Zn. In conclusion, this study suggests that M. tuberculosis pyrazinamidase is a metalloenzyme that is able to coordinate several ions, but in vivo, it is more likely to coordinate Zn2+. However, in vitro, the metal-depleted enzyme could be reactivated by several divalent metals with higher efficiency than Zn. PMID:22764307

  16. Novel metallic alloys as phase change materials for heat storage in direct steam generation applications

    NASA Astrophysics Data System (ADS)

    Nieto-Maestre, J.; Iparraguirre-Torres, I.; Velasco, Z. Amondarain; Kaltzakorta, I.; Zubieta, M. Merchan

    2016-05-01

    of these proposed eutectic alloys are too high for currently available DSG solar fields, for instance the Mg49-Zn51 alloy melts at 342°C requiring saturated steam pressures above 160 bar to charge the TES unit. Being aware of this, novel eutectic metallic alloys have been designed reducing the Tms to the range between 285°C and 330°C (79bar and 145bar of charging steam pressure respectively) with ΔHfs between 150 and 170 J/g, and thus achieving metallic Phase Change Materials (PCM) suitable for the available DSG technologies.

  17. Thermodynamics of the ferromagnetic phase transition in nearly half metallic CoS2 at high pressures

    SciTech Connect

    Elkin, F. S.; Zibrov, I. P.; Novikov, A. P.; Khasanov, S. S.; Sidorov, V. A.; Petrova, A. E.; Lograsso, Thomas A.; Thompson, J. D.; Stishov, S. M.

    2013-12-06

    The volume change and heat capacity at the ferromagnetic phase transition in COS2 were measured at high pressures using X-rays generated by the Argonne synchrotron light source and by ac-calorimetry, respectively. The transition entropy, calculated on the basis of these experimental data, drops along the transition line due to quantum degradation, as required by Nernst's law. The volume change increases strongly along the transition line, which is explained by specifics of the compressibility difference of coexisting phases that results from nearly half metallic nature of the ferromagnetic phase of COS2. (C) 2013 Elsevier Ltd. All rights reserved.

  18. Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts

    PubMed Central

    Sahraie, Nastaran Ranjbar; Kramm, Ulrike I.; Steinberg, Julian; Zhang, Yuanjian; Thomas, Arne; Reier, Tobias; Paraknowitsch, Jens-Peter; Strasser, Peter

    2015-01-01

    Carbon materials doped with transition metal and nitrogen are highly active, non-precious metal catalysts for the electrochemical conversion of molecular oxygen in fuel cells, metal air batteries, and electrolytic processes. However, accurate measurement of their intrinsic turn-over frequency and active-site density based on metal centres in bulk and surface has remained difficult to date, which has hampered a more rational catalyst design. Here we report a successful quantification of bulk and surface-based active-site density and associated turn-over frequency values of mono- and bimetallic Fe/N-doped carbons using a combination of chemisorption, desorption and 57Fe Mössbauer spectroscopy techniques. Our general approach yields an experimental descriptor for the intrinsic activity and the active-site utilization, aiding in the catalyst development process and enabling a previously unachieved level of understanding of reactivity trends owing to a deconvolution of site density and intrinsic activity. PMID:26486465

  19. Induction of metallothionein I by phenolic antioxidants requires metal-activated transcription factor 1 (MTF-1) and zinc.

    PubMed Central

    Bi, Yongyi; Palmiter, Richard D; Wood, Kristi M; Ma, Qiang

    2004-01-01

    Phenolic antioxidants, such as tBHQ [2,5-di-(t-butyl)-1,4-hydroquinone], induce Mt1 (metallothionein 1) gene expression and accumulation of MT protein. Induction of Mt1 mRNA does not depend on protein synthesis, and correlates with oxidation-reduction functions of the antioxidants. In the present study, we analysed the biochemical pathway of the induction. Induction depends on the presence of MTF-1 (metal-activated transcription factor 1), a transcription factor that is required for metal-induced transcription of Mt1, but does not require nuclear factor erythroid 2-related factor 2, a tBHQ-activated CNC bZip (cap 'n' collar basic leucine zipper) protein, that is responsible for regulating genes encoding phase II drug-metabolizing enzymes. Moreover, tBHQ induces the expression of MRE-beta Geo, a reporter gene driven by five metal response elements that constitute an optimal MTF-1 binding site. Reconstitution of Mtf1 -null cells with MTF-1 restores induction by both zinc and tBHQ. Unlike activation of phase II genes by tBHQ, induction of Mt1 expression does not occur in the presence of EDTA, when cells are cultured in zinc-depleted medium, or in cells with reduced intracellular 'free' zinc due to overexpression of ZnT1, a zinc-efflux transporter, indicating that induction requires zinc. In addition, fluorescence imaging reveals that tBHQ increases cytoplasmic free zinc concentration by mobilizing intracellular zinc pools. These findings establish that phenolic antioxidants activate Mt1 transcription by a zinc-dependent mechanism, which involves MTF-1 binding to metal regulator elements in the Mt1 gene promoter. PMID:14998373

  20. A metal organic framework-polyaniline nanocomposite as a fiber coating for solid phase microextraction.

    PubMed

    Bagheri, Habib; Javanmardi, Hasan; Abbasi, Alireza; Banihashemi, Solmaz

    2016-01-29

    A metal organic framework-polyaniline (MOF/PANI) nanocomposite was electrodeposited on a stainless steel wire and used as a solid phase microextraction (SPME) fiber coating. The electropolymerization process was carried out under a constant deposition potential and applied to the corresponding aqueous electrolyte containing aniline and MOF particles. The employment of MOFs with their large and small cages and 3-D structures in synthesizing a nanocomposite was assumed to be efficient constitutes to induce more non-smooth and porous structures, approved by scanning electron microscopy (SEM) images. Three different MOFs were incorporated to synthesize the desired nanocomposites and the preliminary experiments showed that all of them, particularly the one containing MOF2, have higher extraction performances in compared with PANI. The applicability of the new fiber coating was examined by headspace-solid phase microextraction (HS-SPME) of some chlorobenzenes (CBs) from aqueous samples. Influencing parameters on the synthesize and extraction processes including the electrodeposition voltage and its duration time, the weight ratio of PANI and MOF, the ionic strength, desorption temperature and time, and extraction time and temperature were optimized. The developed method was validated by analyzing the spiked distilled water and gas chromatography-mass spectrometry (GC-MS). Under optimum condition, the relative standard deviation (RSD%) values for a double distilled water spiked with the selected CBs at 20ngL(-1) were 5-8% (n=3) and the detection limits were below 0.2ngL(-1). The linear dynamic range (LDR) of the method was in the concentration range of 0.5-1000ngL(-1) (R(2)>0.9994). The fiber-to-fiber reproducibility was found to be in the range of 4-7%. Eventually, various real-water samples were analyzed by the MOF/PANI-based HS-SPME and GC-MS and the relative recovery values were found to be in the range of 92-98%.

  1. Are cyclopentadienylberyllium, magnesium and calcium hydrides carbon or metal acids in the gas phase?

    PubMed

    Hurtado, Marcela; Lamsabhi, Al-Mokhtar; Mó, Otilia; Yáñez, Manuel; Guillemin, Jean-Claude

    2010-05-21

    The structure and bonding of cyclopentadienylberyllium (CpBeH), magnesium (CpMgH), and calcium (CpCaH) hydrides as well as those of their deprotonated species have been investigated by means of B3LYP/6-311+G(3df,2p)//B3LYP/6-311+G(d,p) and B3LYP/6-311+G(3df,2p)//QCISD/6-311+G(d,p) density functional theory (DFT) calculations. The three compounds exhibit C(5v) equilibrium conformations in their ground states. For CpBeH the agreement between the calculated geometry and that determined by MW spectroscopy is excellent. CpMgH and CpCaH can be viewed almost as the result of the interaction between a C₅H₅⁻ anion and a XH(+) (X = Mg, Ca) cation. Conversely, for CpBeH the interaction between the C₅H₅ and the BeH subunits is significantly covalent. These compounds exhibit a significant aromaticity, usually named three-dimension aromaticity, in contrast with the unsubstituted cyclopentadiene compound. The CpBeH derivative behaves as a C acid in the gas phase and is less acidic than cyclopentadiene. More importantly, CpMgH and CpCaH, in spite of the X(+δ)H(-δ) polarity exhibited by the X-H bond in the neutral systems, are predicted to be metal acids in the gas phase. Also surprisingly, both the Mg and the Ca derivatives are stronger acids than the Be analogue, and only slightly weaker acids than cyclopentadiene. This somewhat unexpected result is the consequence of two concomitant facts: the lower dissociation energy of the X-H (X = Mg, Ca) bonds with respect to the C-H bonds, and the significantly high electron affinity of the C₅H₅X* (X = Mg, Ca) radicals.

  2. Study of seismic activity during the ascending and descending phases of solar activity

    NASA Astrophysics Data System (ADS)

    Sukma, Indriani; Abidin, Zamri Zainal

    2016-12-01

    The study of the solar cycle and geomagnetic index associated with the seismic activity from the year 1901 to the end of 2015 has been done for an area that covers the majority of China and its bordering countries. Data of sunspot number, solar wind speed, daily storm time index and earthquake number are collected from NOAA, NASA, WDC, OMNI and USGS databases and websites. The earthquakes are classified into small (M < 5) and large (M ≥ 5) magnitudes (in Richter scale). We investigated the variation of earthquake activities with the geomagnetic storm index due to the solar wind. We focused on their variation in the ascending and descending phases of solar cycle. From our study, we conclude that there is a correlation between the phases' geomagnetic index and solar wind speed. We have also suggested that there is a certain degree of correlation between solar activity and seismicity in these phases. For every solar cycle, we find that there is a trend for earthquakes to occur in greater numbers during the descending phase. This can be explained by the increment in the solar wind speed and geomagnetic storm index during this phase.

  3. Spinodal decomposition in amorphous metal-silicate thin films: Phase diagram analysis and interface effects on kinetics

    NASA Astrophysics Data System (ADS)

    Kim, H.; McIntyre, P. C.

    2002-11-01

    Among several metal silicate candidates for high permittivity gate dielectric applications, the mixing thermodynamics of the ZrO2-SiO2 system were analyzed, based on previously published experimental phase diagrams. The driving force for spinodal decomposition was investigated in an amorphous silicate that was treated as a supercooled liquid solution. A subregular model was used for the excess free energy of mixing of the liquid, and measured invariant points were adopted for the calculations. The resulting simulated ZrO2-SiO2 phase diagram matched the experimental results reasonably well and indicated that a driving force exists for amorphous Zr-silicate compositions between approx40 mol % and approx90 mol % SiO2 to decompose into a ZrO2-rich phase (approx20 mol % SiO2) and SiO2-rich phase (>98 mol % SiO2) through diffusional phase separation at a temperature of 900 degC. These predictions are consistent with recent experimental reports of phase separation in amorphous Zr-silicate thin films. Other metal-silicate systems were also investigated and composition ranges for phase separation in amorphous Hf, La, and Y silicates were identified from the published bulk phase diagrams. The kinetics of one-dimensional spinodal decomposition normal to the plane of the film were simulated for an initially homogeneous Zr-silicate dielectric layer. We examined the effects that local stresses and the capillary driving force for component segregation to the interface have on the rate of spinodal decomposition in amorphous metal-silicate thin films.

  4. Lag Phase Is a Distinct Growth Phase That Prepares Bacteria for Exponential Growth and Involves Transient Metal Accumulation

    PubMed Central

    Rolfe, Matthew D.; Rice, Christopher J.; Lucchini, Sacha; Pin, Carmen; Thompson, Arthur; Cameron, Andrew D. S.; Alston, Mark; Stringer, Michael F.; Betts, Roy P.; Baranyi, József; Peck, Michael W.

    2012-01-01

    Lag phase represents the earliest and most poorly understood stage of the bacterial growth cycle. We developed a reproducible experimental system and conducted functional genomic and physiological analyses of a 2-h lag phase in Salmonella enterica serovar Typhimurium. Adaptation began within 4 min of inoculation into fresh LB medium with the transient expression of genes involved in phosphate uptake. The main lag-phase transcriptional program initiated at 20 min with the upregulation of 945 genes encoding processes such as transcription, translation, iron-sulfur protein assembly, nucleotide metabolism, LPS biosynthesis, and aerobic respiration. ChIP-chip revealed that RNA polymerase was not “poised” upstream of the bacterial genes that are rapidly induced at the beginning of lag phase, suggesting a mechanism that involves de novo partitioning of RNA polymerase to transcribe 522 bacterial genes within 4 min of leaving stationary phase. We used inductively coupled plasma mass spectrometry (ICP-MS) to discover that iron, calcium, and manganese are accumulated by S. Typhimurium during lag phase, while levels of cobalt, nickel, and sodium showed distinct growth-phase-specific patterns. The high concentration of iron during lag phase was associated with transient sensitivity to oxidative stress. The study of lag phase promises to identify the physiological and regulatory processes responsible for adaptation to new environments. PMID:22139505

  5. Lag phase is a distinct growth phase that prepares bacteria for exponential growth and involves transient metal accumulation.

    PubMed

    Rolfe, Matthew D; Rice, Christopher J; Lucchini, Sacha; Pin, Carmen; Thompson, Arthur; Cameron, Andrew D S; Alston, Mark; Stringer, Michael F; Betts, Roy P; Baranyi, József; Peck, Michael W; Hinton, Jay C D

    2012-02-01

    Lag phase represents the earliest and most poorly understood stage of the bacterial growth cycle. We developed a reproducible experimental system and conducted functional genomic and physiological analyses of a 2-h lag phase in Salmonella enterica serovar Typhimurium. Adaptation began within 4 min of inoculation into fresh LB medium with the transient expression of genes involved in phosphate uptake. The main lag-phase transcriptional program initiated at 20 min with the upregulation of 945 genes encoding processes such as transcription, translation, iron-sulfur protein assembly, nucleotide metabolism, LPS biosynthesis, and aerobic respiration. ChIP-chip revealed that RNA polymerase was not "poised" upstream of the bacterial genes that are rapidly induced at the beginning of lag phase, suggesting a mechanism that involves de novo partitioning of RNA polymerase to transcribe 522 bacterial genes within 4 min of leaving stationary phase. We used inductively coupled plasma mass spectrometry (ICP-MS) to discover that iron, calcium, and manganese are accumulated by S. Typhimurium during lag phase, while levels of cobalt, nickel, and sodium showed distinct growth-phase-specific patterns. The high concentration of iron during lag phase was associated with transient sensitivity to oxidative stress. The study of lag phase promises to identify the physiological and regulatory processes responsible for adaptation to new environments.

  6. Metallic phases of cobalt-based catalysts in ethanol steam reforming: The effect of cerium oxide

    SciTech Connect

    Lin, Sean S.-Y.; Kim, Do Heui; Ha, Su Y.

    2009-02-28

    The catalytic activity of cobalt in the production of hydrogen via ethanol steam reforming has been investigated in its relation to the crystalline structure of metallic cobalt. At a reaction temperature of 350 8C, the specific hydrogen production rates show that hexagonal close-packed (hcp) cobalt possesses higher activity than face-centered cubic (fcc) cobalt. However, at typical reaction temperatures (400– 500 8C) for ethanol steam reforming, hcp cobalt is transformed to less active fcc cobalt, as confirmed by in situ X-ray diffractometry (XRD). The addition of CeO2 promoter (10 wt.%) stabilizes the hcp cobalt structure at reforming temperatures up to 600 8C. Moreover, during the pre-reduction process, CeO2 promoter prevents sintering during the transformation of Co3O4 to hcp cobalt. Both reforming experiments and in situ diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS) showed that the surface reactions were modified by CeO2 promoter on 10% Ce–Co (hcp) to give a lower CO selectivity and a higher H2 yield as compared with the unpromoted hcp Co.

  7. Phase-field simulation of stripe arrays on metal bcc(110) surfaces.

    PubMed

    Yu, Yan-Mei; Backofen, Rainer; Voigt, Axel

    2008-05-01

    By using a phase-field model, we simulate formation and growth of stripe arrays starting with anisotropic growth of islands under the Ehrlich-Schwoebel barrier on metal bcc(110) surfaces. The anisotropy is incorporated in terms of attachment kinetics that is locally limited at the island edge aligned to the y axis (or 100 ) and instantaneous at the island edge aligned to the x axis (or 110 ). By reproducing the stripe arrays under various anisotropy magnitudes, we investigate dynamics of formation and growth of the stripe arrays. While enhancing coarsening in the y direction, the anisotropy suppresses coarsening in the x direction at the early stage, which contributes to formation of stripe arrays. At long times, the stripe arrays develop the quasiperiodic uniaxial structure with the selected transversal slope and the decreasing longitudinal slope as consequence of competition between coarsening and roughening. At the case of the large anisotropy magnitude, the fast roughening is caused by the strongly limited attachment kinetics, where the transversal coarsening turns fast and then the uniaxial growth is broken finally. For the weak roughening at the case of the reduced anisotropy magnitude, the slow transversal coarsening is achieved with the fast longitudinal coarsening, which contributes to the stripe arrays of the regular period and the increasing uniaxial length. Such arrays have the potential to be used as templates to grow one-dimensional nanostructures.

  8. Bi-modal nanoheteroepitaxy of GaAs on Si by metal organic vapor phase epitaxy.

    PubMed

    Prieto, Ivan; Kozak, Roksolana; Skibitzki, Oliver; Rossell, Marta D; Zaumseil, Peter; Capellini, Giovanni; Gini, Emilio; Kunze, Karsten; Rojas Dasilva, Yadira Arroyo; Erni, Rolf; Schroeder, Thomas; Känel, Hans von

    2017-03-01

    Nano-heteroepitaxial growth of GaAs on Si(001) by metal organic vapor phase epitaxy was investigated to study emerging materials phenomena on the nano-scale of III-V/Si interaction. Arrays of Si nano-tips (NTs) embedded in a SiO2 matrix were used as substrates. The NTs had top Si openings of 50-90 nm serving as seeds for the selective growth of GaAs nano-crystals (NCs). The structural and morphological properties were investigated by high resolution scanning electron microscopy, atomic force microscopy, electron backscatter diffraction, x-ray diffraction, and high resolution scanning transmission electron microscopy. The GaAs growth led to epitaxial NCs featuring a bi-modal distribution of size and morphology. NCs of small size exhibited high structural quality and well-defined {111}-{100} faceting. Larger clusters had less regular shapes and contained twins. The present work shows that the growth of high quality GaAs NCs on Si NTs is feasible and can provide an alternate way to the integration of compound semiconductors with Si micro- and opto-electronics technology.

  9. Luminescent transition metal dichalcogenide nanosheets through one-step liquid phase exfoliation

    NASA Astrophysics Data System (ADS)

    Mar Bernal, M.; Álvarez, Lidia; Giovanelli, Emerson; Arnáiz, Adriana; Ruiz-González, Luisa; Casado, Santiago; Granados, Daniel; Pizarro, Ana M.; Castellanos-Gomez, Andres; Pérez, Emilio M.

    2016-09-01

    Liquid phase exfoliation (LPE) from the bulk is an adequate method for the mass-production of thin nanosheets of transition metal dichalcogenides (TMDCs). However, making suspensions in which the extraordinary properties of mechanically exfoliated TMDCs are observable remains a challenge. We describe a mild LPE method to produce luminescent suspensions of MoS2 and WS2 in N-methylpyrrolidone or isopropanol/water mixtures, without the need for a purification step. The key differences in our experimental procedure compared to previously reported LPE methods are the use of mild bath sonication at controlled temperature and the low initial concentration of the parent TMDC. Spectroscopic and AFM data confirm that an overwhelming majority of the sample is composed of ultrathin nanosheets. HREM data support the formation of the luminescent 2H polytype. The ultrathin nanosheets can be transferred to pure water and cell culture medium. Confocal fluorescence microscopy experiments on MCF-7 breast cancer cells exposed to LPE WS2 show that the cells are viable and the photoluminescence of the nanosheets is detectable.

  10. Metallic phase-change materials for solar dynamic energy storage systems

    SciTech Connect

    Lauf, R.J.; Hamby, C. Jr.

    1990-12-01

    Solar (thermal) dynamic power systems for satellites require a heat storage system that is capable of operating the engine during eclipse. The conventional approach to this thermal storage problem is to use the latent heat of fluoride salts, which would melt during insolation and freeze during eclipse. Although candidate fluorides have large heats of fusion per unit mass, their poor thermal conductivity limits the rate at which energy can be transferred to and from the storage device. System performance is further limited by the high parasitic mass of the superalloy canisters needed to contain the salt. This report describes a new thermal storage system in which the phase-change material (PCM) is a metal (typically germanium) contained in modular graphite canisters. These modules exhibit good thermal conductivity and low parasitic mass, and they are physically and chemically stable. Prototype modules have survived over 600 melt/freeze cycles without degradation. Advanced concepts to further improve performance are described. These concepts include the selection of ternary eutectic alloys to provide a wider range of useful melting temperatures and the use of infiltration to control the location of liquid alloy and to compensate for differences in thermal expansion. 13 refs., 18 figs.

  11. Transition metal doping of GaSe implemented with low temperature liquid phase growth

    NASA Astrophysics Data System (ADS)

    Lei, Nuo; Sato, Youhei; Tanabe, Tadao; Maeda, Kensaku; Oyama, Yutaka

    2017-02-01

    Our group works on improving the conversion efficiencies of terahertz (THz) wave generation using GaSe crystals. The operating principle is based on difference frequency generation (DFG) which has the advantages such as high output power, a single tunable frequency, and room temperature operation. In this study, GaSe crystals were grown by the temperature difference method under controlled vapor pressure (TDM-CVP). It is a liquid phase growth method with temperature 300 °C lower than that of the Bridgman method. Using this method, the point defects concentration is decreased and the polytype can be controlled. The transition metal Ti was used to dope the GaSe in order to suppress free carrier absorption in the low frequency THz region. As a result, a deep acceptor level of 38 meV was confirmed as being formed in GaSe with 1.4 at% Ti doping. Compared with undoped GaSe, a decrease in carrier concentration ( 1014 cm-3) at room temperature was also confirmed. THz wave transmittance measurements reveal the tendency for the absorption coefficient to increase as the amount of dopant is increased. It is expected that there is an optimum amount of dopant.

  12. Plasma sprayed coatings for containment of Cu-Mg-Si metallic phase change material

    SciTech Connect

    Withey, Elizabeth Ann; Kruizenga, Alan Michael; Andraka, Charles E.; Gibbs, Paul J.

    2016-01-01

    In this study, the performance of Y2O3-stabilized ZrO2 (YSZ), Y2O3, and Al2O3 plasma sprayed coatings are investigated for their ability to prevent attack of Haynes 230 by a near-eutectic Cu-Mg-Si metallic phase change material (PCM) in a closed environment at 820 °C. Areas where coatings failed were identified with optical and scanning electron microscopy, while chemical interactions were clarified through elemental mapping using electron microprobe analysis. Despite its susceptibility to reduction by Mg, the Al2O3 coating performed well while the YSZ and Y2O3 coating showed clear areas of attack. These results are attributed to the evolution of gaseous Mg at 820 °C leading to the formation of MgO and MgAl2O4.

  13. Metal-organic framework ZIF-8 nanocrystals as pseudostationary phase for capillary electrokinetic chromatography.

    PubMed

    Li, Li-Man; Wang, He-Fang; Yan, Xiu-Ping

    2012-09-01

    The outstanding properties such as large surface area, diverse structure, and accessible tunnels and cages make metal organic frameworks (MOFs) attractive as novel separation media in separation sciences. However, the utilization of MOFs in EKC has not been reported before. Here we show the exploration of zeolitic imidazolate framework-8 (ZIF-8), one of famous MOFs, as the pseudostationary phase (PSP) in EKC. ZIF-8 nanocrystals were used as the PSP through dispersing in the running buffer (20 mM phosphate solution containing a 1% v/v methanol (pH 9.2)) to enhance the separation of the phenolic isomers (p-benzenediol, m-benzenediol, o-benzenediol, m-nitrophenol, p-nitrophenol, and o-nitrophenol). ZIF-8 nanocrystals in the running buffer were negatively charged, and interacted with the phenolic hydroxyl groups of the analytes, and thus greatly improved the separation of the phenolic isomers. Inclusion of 200 mg L-(1) ZIF-8 in the running buffer as the background electrolyte gave a baseline separation of the phenolic isomers within 4 min. The relative standard deviations for five replicate separations of the phenolic isomers were 0.2-1.1% for migration time and 4.5-9.7% for peak area. The limits of detection varied from 0.44 to 2.0 mg L-(1) . The results show that nanosized MOFs are promising for application in EKC.

  14. Local microstructure evolution at shear bands in metallic glasses with nanoscale phase separation

    PubMed Central

    He, Jie; Kaban, Ivan; Mattern, Norbert; Song, Kaikai; Sun, Baoan; Zhao, Jiuzhou; Kim, Do Hyang; Eckert, Jürgen; Greer, A. Lindsay

    2016-01-01

    At room temperature, plastic flow of metallic glasses (MGs) is sharply localized in shear bands, which are a key feature of the plastic deformation in MGs. Despite their clear importance and decades of study, the conditions for formation of shear bands, their structural evolution and multiplication mechanism are still under debate. In this work, we investigate the local conditions at shear bands in new phase-separated bulk MGs containing glassy nanospheres and exhibiting exceptional plasticity under compression. It is found that the glassy nanospheres within the shear band dissolve through mechanical mixing driven by the sharp strain localization there, while those nearby in the matrix coarsen by Ostwald ripening due to the increased atomic mobility. The experimental evidence demonstrates that there exists an affected zone around the shear band. This zone may arise from low-strain plastic deformation in the matrix between the bands. These results suggest that measured property changes originate not only from the shear bands themselves, but also from the affected zones in the adjacent matrix. This work sheds light on direct visualization of deformation-related effects, in particular increased atomic mobility, in the region around shear bands. PMID:27181922

  15. MD simulation of cluster-surface impacts for metallic phases: soft landing, droplet spreading and implantation

    NASA Astrophysics Data System (ADS)

    Kholmurodov, Kholmirzo; Puzynin, Igor; Smith, William; Yasuoka, Kenji; Ebisuzaki, Toshikazu

    2001-11-01

    An optimized version of the DL_POLY molecular dynamics simulation code [K. Kholmurodov, W. Smith, K. Yasuoka, T. Ebisuzaki, Comput. Phys. Commun. 125 (2000) 167-192] has been used to study the cluster-surface impact processes for metallic phases. The interaction of an energetic cluster of atoms with a solid surface has been investigated using the Finnis-Sinclair many-body potential. The characteristics of the cluster-surface collisions were studied in a wide range of the cluster impact energies ( Einc=0.035-3.5 eV/atom). Modification of the surface, exposed to the cluster-beams, was studied by monitoring the molecular dynamics configurations of the system in real time. The density and temperature distributions in the system under the energetic irradiations has been investigated in detail. The three major channels of the impact yield (viz., soft landing, droplet spreading and implantation) were distinguished and estimated. Based on the density and temperature distributions data the low energy cluster-surface impact has been analyzed and a novel interpretation of droplet spreading process is given.

  16. Bi-modal nanoheteroepitaxy of GaAs on Si by metal organic vapor phase epitaxy

    NASA Astrophysics Data System (ADS)

    Prieto, Ivan; Kozak, Roksolana; Skibitzki, Oliver; Rossell, Marta D.; Zaumseil, Peter; Capellini, Giovanni; Gini, Emilio; Kunze, Karsten; Arroyo Rojas Dasilva, Yadira; Erni, Rolf; Schroeder, Thomas; von Känel, Hans

    2017-03-01

    Nano-heteroepitaxial growth of GaAs on Si(001) by metal organic vapor phase epitaxy was investigated to study emerging materials phenomena on the nano-scale of III–V/Si interaction. Arrays of Si nano-tips (NTs) embedded in a SiO2 matrix were used as substrates. The NTs had top Si openings of 50–90 nm serving as seeds for the selective growth of GaAs nano-crystals (NCs). The structural and morphological properties were investigated by high resolution scanning electron microscopy, atomic force microscopy, electron backscatter diffraction, x-ray diffraction, and high resolution scanning transmission electron microscopy. The GaAs growth led to epitaxial NCs featuring a bi-modal distribution of size and morphology. NCs of small size exhibited high structural quality and well-defined {111}–{100} faceting. Larger clusters had less regular shapes and contained twins. The present work shows that the growth of high quality GaAs NCs on Si NTs is feasible and can provide an alternate way to the integration of compound semiconductors with Si micro- and opto-electronics technology.

  17. Grain Size Dependence of Uniform Elongation in Single-Phase FCC/BCC Metals

    NASA Astrophysics Data System (ADS)

    Liu, Haiting; Shen, Yao; Ma, Jiawei; Zheng, Pengfei; Zhang, Lei

    2016-09-01

    We studied the dependence of uniform elongation on grain size in the range of submicron to millimeter for single-phase FCC/BCC metals by reviewing recent experimental results and applying crystal plasticity finite element method simulation. In the order of increasing grain size, uniform elongation can be divided into three stages, namely low elongation stage, nearly constant elongation stage, and decreased elongation with large scatters stage. Low elongation stage features a dramatic increase near the critical grain size at the end of the stage, which is primarily attributed to the emergence of dislocation cell size transition from ultrafine to mid-size grain. Other factors can be neglected due to their negligible influence on overall variation trend. In nearly constant elongation stage, uniform elongation remains unchanged at a high level in general. As grain size keeps growing, uniform elongation starts decreasing and becomes scattered upon a certain grain size, indicating the initiation of decreased elongation with large scatters stage. It is shown that the increase is not linear or smooth but rather sharp at the end of low elongation stage, leading to a wider range in nearly constant elongation stage. The grain size dependence of uniform elongation can serve as a guiding principle for designing small uniaxial tensile specimens for mechanical testing, where size effect matters in most cases.

  18. Nanometre-sized GaAs wires grown by organo-metallic vapour-phase epitaxy

    NASA Astrophysics Data System (ADS)

    Hiruma, Kenji; Haraguchi, Keiichi; Yazawa, Masamitsu; Madokoro, Yuuichi; Katsuyama, Toshio

    2006-06-01

    We grew GaAs wires as thin as 20 nm on a GaAs(111)B substrate using organo-metallic vapour-phase epitaxy (OMVPE), with Au as a growth catalyst. To investigate the growth characteristics, we compared two methods of depositing Au. In the first, Au was deposited by vacuum evaporation, and the deposition thickness was varied to form a planar Au layer. We found that an Au layer thickness of 1 nm was best for forming cylindrical shaped wires. Next, a new method of injecting Au onto an area of a few micrometres was tested using a focused ion beam (FIB), and this method was found to be effective for growing wires as thin as 30-80 nm. However, the wire width did not depend on the injected density of Au. We based our analysis of the results on an ion implantation model. GaAs wires with a p-n junction along the \\langle 111\\rangle \\mathrm {B} direction were formed by changing dopants from silicon to carbon during growth. We observed an optical emission with a peak intensity at the wavelength of 910-920 nm during continuous current injection into the wires at 300 K. A spectral blue-shift in the light emission and a polarization along the wire growth direction were also revealed at 77 K.

  19. Effects of humic acid-metal complexes on hepatic carnitine palmitoyltransferase, carnitine acetyltransferase and catalase activities

    SciTech Connect

    Fungjou Lu; Youngshin Chen . Dept. of Biochemistry); Tienshang Huang . Dept. of Medicine)

    1994-03-01

    A significant increase in activities of hepatic carnitine palmitoyltransferase and carnitine acetyltransferase was observed in male Balb/c mice intraperitoneally injected for 40 d with 0.125 mg/0.1 ml/d humic acid-metal complexes. Among these complexes, the humic acid-As complex was relatively effective, whereas humic acid-25 metal complex was more effective, and humic acid-26 metal complex was most effective. However, humic acid or metal mixtures, or metal such as As alone, was not effective. Humic acid-metal complexes also significantly decreased hepatic catalase activity. A marked decrease of 60-kDa polypeptide in liver cytoplasm was also observed on SDS-polyacrylamide gel electrophoresis after the mice had been injected with the complexes. Morphological analysis of a histopathological biopsy of such treated mice revealed several changes in hepatocytes, including focal necrosis and cell infiltration, mild fatty changes, reactive nuclei, and hypertrophy. Humic acid-metal complexes affect activities of metabolic enzymes of fatty acids, and this results in accumulation of hydrogen peroxide and increase of the lipid peroxidation. The products of lipid peroxidation may be responsible for liver damage and possible carcinogenesis. Previous studies in this laboratory had shown that humic acid-metal complex altered the coagulation system and that humic acid, per se, caused vasculopathy. Therefore, humic acid-metal complexes may be main causal factors of not only so-called blackfoot disease, but also the liver cancer prevailing on the southwestern coast of Taiwan.

  20. Synthesis, characterization, and anti-cancer activity of emodin-Mn(II) metal complex.

    PubMed

    Yang, Li; Tan, Jun; Wang, Bo-Chu; Zhu, Lian-Cai

    2014-12-01

    To synthesize and characterize a novel metal complex of Mn (II) with emodin, and evaluate its anti-cancer activity. The elemental analyses, IR, UV-vis, atomic absorption spectroscopy, TG-DSC, (1)H NMR, and (13)C NMR data were used to characterize the structure of the complex. The cytotoxicity of the complex against the human cancer cell lines HepG2, HeLa, MCF-7, B16, and MDA-MB-231 was tested by the MTT assay and flow cytometry. Emodin was coordinated with Mn(II) through the 9-C=O and 1-OH, and the general formula of the complex was Mn(II) (emodin)2·2H2O. In studies of the cytotoxicity, the complex exhibited significant activity, and the IC50 values of the complex against five cancer cell lines improved approximately three-fold compared with those of emodin. The complex could induce cell morphological changes, decrease the percentage of viability, and induce G0/G1 phase arrest and apoptosis in cancer cells. The coordination of emodin with Mn(II) can improve its anticancer activity, and the complex Mn(II) (emodin)2·2H2O could be studied further as a promising anticancer drug.

  1. Microstructure and Interfacial Reactions During Active Metal Brazing of Stainless Steel to Titanium

    NASA Astrophysics Data System (ADS)

    Laik, A.; Shirzadi, A. A.; Tewari, R.; Kumar, Anish; Jayakumar, T.; Dey, G. K.

    2013-05-01

    Microstructural evolution and interfacial reactions during active metal vacuum brazing of Ti (grade-2) and stainless steel (SS 304L) using a Ag-based alloy containing Cu, Ti, and Al was investigated. A Ni-depleted solid solution layer and a discontinuous layer of (Ni,Fe)2TiAl intermetallic compound formed on the SS surface and adjacent to the SS-braze alloy interface, respectively. Three parallel contiguous layers of intermetallic compounds, CuTi, AgTi, and (Ag,Cu)Ti2, formed at the Ti-braze alloy interface. The diffusion path for the reaction at this interface was established. Transmission electron microscopy revealed formation of nanocrystals of Ag-Cu alloy of size ranging between 20 and 30 nm in the unreacted braze alloy layer. The interdiffusion zone of β-Ti(Ag,Cu) solid solution, formed on the Ti side of the joint, showed eutectoid decomposition to lamellar colonies of α-Ti and internally twinned (Cu,Ag)Ti2 intermetallic phase, with an orientation relationship between the two. Bend tests indicated that the failure in the joints occurred by formation and propagation of the crack mostly along the Ti-braze alloy interface, through the (Ag,Cu)Ti2 phase layer.

  2. THE FOSSIL RECORD OF TWO-PHASE GALAXY ASSEMBLY: KINEMATICS AND METALLICITIES IN THE NEAREST S0 GALAXY

    SciTech Connect

    Arnold, Jacob A.; Romanowsky, Aaron J.; Brodie, Jean P.; Spitler, Lee R.; Forbes, Duncan A.; Benson, Andrew J.

    2011-08-01

    We present a global analysis of kinematics and metallicity in the nearest S0 galaxy, NGC 3115, along with implications for its assembly history. The data include high-quality wide-field imaging from Suprime-Cam on the Subaru telescope, and multi-slit spectra of the field stars and globular clusters (GCs) obtained using Keck-DEIMOS/LRIS and Magellan-IMACS. Within two effective radii, the bulge (as traced by the stars and metal-rich GCs) is flattened and rotates rapidly (v/{sigma} {approx}> 1.5). At larger radii, the rotation declines dramatically to v/{sigma} {approx} 0.7, but remains well aligned with the inner regions. The radial decrease in characteristic metallicity of both the metal-rich and metal-poor GC subpopulations produces strong gradients with power-law slopes of -0.17 {+-} 0.04 and -0.38 {+-} 0.06 dex dex{sup -1}, respectively. We argue that this pattern is not naturally explained by a binary major merger, but instead by a two-phase assembly process where the inner regions have formed in an early violent, dissipative phase, followed by the protracted growth of the outer parts via minor mergers with typical mass ratios of {approx}15-20:1.

  3. Complexation-induced phase separation: preparation of composite membranes with a nanometer-thin dense skin loaded with metal ions.

    PubMed

    Villalobos, Luis Francisco; Karunakaran, Madhavan; Peinemann, Klaus-Viktor

    2015-05-13

    We present the development of a facile phase-inversion method for forming asymmetric membranes with a precise high metal ion loading capacity in only the dense layer. The approach combines the use of macromolecule-metal intermolecular complexes to form the dense layer of asymmetric membranes with nonsolvent-induced phase separation to form the porous support. This allows the independent optimization of both the dense layer and porous support while maintaining the simplicity of a phase-inversion process. Moreover, it facilitates control over (i) the thickness of the dense layer throughout several orders of magnitude from less than 15 nm to more than 6 μm, (ii) the type and amount of metal ions loaded in the dense layer, (iii) the morphology of the membrane surface, and (iv) the porosity and structure of the support. This simple and scalable process provides a new platform for building multifunctional membranes with a high loading of well-dispersed metal ions in the dense layer.

  4. Lessons learned with the Active Phasing Experiment: comparison of four optical phasing sensors on a segmented Very Large Telescope

    NASA Astrophysics Data System (ADS)

    Gonte, F.; Surdej, I.

    The adaptive optics capabilities are strongly limited by the quality of the phasing of the primary mirror of the extremely large telescope. Up to date, the Keck telescopes are the only segmented telescope phased with a quality enabling the application of adaptive optics. The Active Phasing Experiment has been installed at the Namyth focus of the Very Large Telescope Melipal during the last 6 months. Its purpose is to understand and compare different technological concepts for an optical phasing sensor dedicated to the European Extremely Large Telescope. The pupil of the telescope is segmented in 61 hexagonal segments by projecting it on an Active Segmented Mirror. The ASM is controlled by a dual wavenlength interferometer made by Fogale Nanotech with a nanometric precision. The segmented pupil is distributed in parallel to four optical phasing sensors. They are a pyramid sensor, a curvature sensor, a phase filtering sensor and a ShackHartmann sensor. They have been developed respectively by Istituto Nazionale di Astrofisica in Florenze, Instituto Astrofisica Canarias in Tenerife, Laboratoire d'Astrophysique de Marseille and ESO. The global behaviour of the optical phasing sensors will be described and preliminary results of the Active Phasing Experiments obtained on sky will be explained. The extrapolation of the results to the EELT and the potential consequences for the adaptive optics will be given. The Active Phasing Experiment has been financed by the European Union and the European Southern Observatory via the Sixth European Union Framework Program for Research and Technological Development under the contract number 011863.

  5. Binding and Activation of N2O at Transition Metal Centers: Recent Mechanistic Insights

    PubMed Central

    Tolman, William B.

    2010-01-01

    No laughing matter, nitrous oxide’s role in stratospheric ozone depletion and as a greenhouse gas has stimulated great interest in developing and understanding its decomposition, particularly through the use of transition metal promoters. Recent advances in our understanding of the reaction pathways for N2O reduction by metal ions in the gas phase and in heterogeneous, homogeneous, and biological catalytic systems have provided provocative ideas about the structure and properties of metal-N2O adducts and derived intermediates. These ideas are likely to inform efforts to design more effective catalysts for N2O remediation. PMID:20058284

  6. Choline Chloride Assisted Synthesis of N and Metal Codoped TiO2 and their Photocatalytic Activity under Visible Light.

    PubMed

    Kaur, Navneet; Shahi, Satwant Kaur; Singh, Vasundhara

    2016-01-01

    A few nanocrystalline N,metal codoped TiO2 (metal = Cr, Mn, Fe, Co, Ni, Cu and Zn) have been synthesized by a simple sol-gel method using choline chloride which is biodegradable, low cost, nontoxic ionic salt both as a structure directing agent and source of nitrogen. The prepared samples were well characterized by XRD, HRTEM, FTIR, DRS, EDX, XPS and BET techniques. The photocatalytic activity of all synthesized N, metal codoped TiO2 has been carried out for the degradation of Reactive Black 5 dye under visible light irradiation and among them, N, Fe codoped TiO2 was found to be the best for the degradation of Reactive Black 5 dye. The effect of incorporated metals on the photocatalytic activity of the various modified TiO2 has been discussed in detail based on the mechanism involved in the degradation of dye and their physico-chemical properties which includes surface area, particle size, defect sites, phase, band gap and electron-hole recombination effect.

  7. Assessing microbial activities in metal contaminated agricultural volcanic soils--An integrative approach.

    PubMed

    Parelho, C; Rodrigues, A S; Barreto, M C; Ferreira, N G C; Garcia, P

    2016-07-01

    Volcanic soils are unique naturally fertile resources, extensively used for agricultural purposes and with particular physicochemical properties that may result in accumulation of toxic substances, such as trace metals. Trace metal contaminated soils have significant effects on soil microbial activities and hence on soil quality. The aim of this study is to determine the soil microbial responses to metal contamination in volcanic soils under different agricultural land use practices (conventional, traditional and organic), based on a three-tier approach: Tier 1 - assess soil microbial activities, Tier 2 - link the microbial activity to soil trace metal contamination and, Tier 3 - integrate the microbial activity in an effect-based soil index (Integrative Biological Response) to score soil health status in metal contaminated agricultural soils. Our results showed that microbial biomass C levels and soil enzymes activities were decreased in all agricultural soils. Dehydrogenase and β-glucosidase activities, soil basal respiration and microbial biomass C were the most sensitive responses to trace metal soil contamination. The Integrative Biological Response value indicated that soil health was ranked as: organic>traditional>conventional, highlighting the importance of integrative biomarker-based strategies for the development of the trace metal "footprint" in Andosols.

  8. Single-step metal-organic vapor-phase diffusion for low-dark-current planar-type avalanche photodiodes

    NASA Astrophysics Data System (ADS)

    Jun, Dong-Hwan; Jeong, Hae Yong; Kim, Youngjo; Shin, Chan-Soo; Park, Kyung Ho; Park, Won-Kyu; Kim, Min-Su; Kim, Sangin; Han, Sang Wook; Moon, Sung

    2016-10-01

    In this paper, a p-type diffusion process based literally on single-step metal-organic vapor-phase diffusion (MOVPD) employing diethyl zinc as the diffusion source in combination with the recessetching technique is developed to improve the dark-current characteristics of planar-type avalanche photodiodes (APDs). The developed single-step MOVPD process exhibits on excellent linear relationship between the diffusion depth and the square root of the diffusion time, which mainly results from maintaining constant source diffusion. The single-step MOVPD process without any additional thermal activation process achieves a surface doping concentration of 1.9 × 1018 cm -3, which is sufficient to form ohmic contact. The measured diffusion profiles of the APDs clearly reveal the presence of a two-dimensional diffusion front formed by the recess-etched and guard-ring regions. The impact of this p-type diffusion process on the performance of the APD devices has also been demonstrated by exhibiting improved dark-current characteristics for the fabricated APDs.

  9. Redox-Active Metal-Organic Composites for Highly Selective Oxygen Separation Applications

    SciTech Connect

    Zhang, Wen; Banerjee, Debasis; Liu, Jian; Schaef, Herbert T.; Crum, Jarrod V.; Fernandez, Carlos A.; Kukkadapu, Ravi K.; Nie, Zimin; Nune, Satish K.; Motkuri, Radha K.; Chapman, Karena W.; Engelhard, Mark H.; Hayes, James C.; Silvers, Kurt L.; Krishna, Rajamani; McGrail, B. Peter; Liu, Jun; Thallapally, Praveen K.

    2016-03-08

    A redox-active metal-organic composite material shows improved and selective O-2 adsorption over N-2 with respect to individual components (MIL-101 and ferrocene). The O-2 sensitivity of the composite material arises due to the formation of maghemite nanoparticles with the pore of the metal-organic framework material.

  10. APE: the Active Phasing Experiment to test new control system and phasing technology for a European Extremely Large Optical Telescope

    NASA Astrophysics Data System (ADS)

    Gonte, F.; Yaitskova, N.; Derie, F.; Constanza, A.; Brast, R.; Buzzoni, B.; Delabre, B.; Dierickx, P.; Dupuy, C.; Esteves, R.; Frank, C.; Guisard, S.; Karban, R.; Koenig, E.; Kolb, J.; Nylund, M.; Noethe, L.; Surdej, I.; Courteville, A.; Wilhelm, R.; Montoya, L.; Reyes, M.; Esposito, S.; Pinna, E.; Dohlen, K.; Ferrari, M.; Langlois, M.

    2005-08-01

    The future European Extremely Large Telescope will be composed of one or two giant segmented mirrors (up to 100 m of diameter) and of several large monolithic mirrors (up to 8 m in diameter). To limit the aberrations due to misalignments and defective surface quality it is necessary to have a proper active optics system. This active optics system must include a phasing system to limit the degradation of the PSF due to misphasing of the segmented mirrors. We will present the lastest design and development of the Active Phasing Experiment that will be tested in laboratory and on-sky connected to a VLT at Paranal in Chile. It includes an active segmented mirror, a static piston plate to simulate a secondary segmented mirror and of four phasing wavefront sensors to measure the piston, tip and tilt of the segments and the aberrations of the VLT. The four phasing sensors are the Diffraction Image Phase Sensing Instrument developed by Instituto de Astrofisica de Canarias, the Pyramid Phasing Sensor developed by Arcetri Astrophysical Observatory, the Shack-Hartmann Phasing Sensor developed by the European Southern Observatory and the Zernike Unit for Segment phasing developed by Laboratoire d'Astrophysique de Marseille. A reference measurement of the segmented mirror is made by an internal metrology developed by Fogale Nanotech. The control system of Active Phasing Experiment will perform the phasing of the segments, the guiding of the VLT and the active optics of the VLT. These activities are included in the Framework Programme 6 of the European Union.

  11. Preparation of functionalized and metal-impregnated activated carbon by a single-step activation method

    NASA Astrophysics Data System (ADS)

    Dastgheib, Seyed A.; Ren, Jianli; Rostam-Abadi, Massoud; Chang, Ramsay

    2014-01-01

    A rapid method to prepare functionalized and metal-impregnated activated carbon from coal is described in this paper. A mixture of ferric chloride and a sub-bituminous coal was used to demonstrate simultaneous coal activation, chlorine functionalization, and iron/iron oxides impregnation in the resulting porous carbon products. The FeCl3 concentration in the mixture, the method to prepare the FeCl3-coal mixture (solid mixing or liquid impregnation), and activation atmosphere and temperature impacted the surface area and porosity development, Cl functionalization, and iron species impregnation and dispersion in the carbon products. Samples activated in nitrogen or a simulated flue gas at 600 or 1000 °C for 1-2 min had surface areas up to ∼800 m2/g, bulk iron contents up to 18 wt%, and surface chlorine contents up to 27 wt%. Potential catalytic and adsorption application of the carbon materials was explored in catalytic wet air oxidation (CWAO) of phenol and adsorption of ionic mercury from aqueous solutions. Results indicated that impregnated activated carbons outperformed their non-impregnated counterparts in both the CWAO and adsorption tests.

  12. Electrophoretic-like gating used to control metal-insulator transitions in electronically phase separated manganite wires.

    PubMed

    Guo, Hangwen; Noh, Joo H; Dong, Shuai; Rack, Philip D; Gai, Zheng; Xu, Xiaoshan; Dagotto, Elbio; Shen, Jian; Ward, T Zac

    2013-08-14

    Electronically phase separated manganite wires are found to exhibit controllable metal-insulator transitions under local electric fields. The switching characteristics are shown to be fully reversible, polarity independent, and highly resistant to thermal breakdown caused by repeated cycling. It is further demonstrated that multiple discrete resistive states can be accessed in a single wire. The results conform to a phenomenological model in which the inherent nanoscale insulating and metallic domains are rearranged through electrophoretic-like processes to open and close percolation channels.

  13. Co-Cu Nanoparticles: Synthesis by Galvanic Replacement and Phase Rearrangement during Catalytic Activation.

    PubMed

    Nafria, Raquel; Genç, Aziz; Ibáñez, Maria; Arbiol, Jordi; de la Piscina, Pilar Ramírez; Homs, Narcís; Cabot, Andreu

    2016-03-08

    The control of the phase distribution in multicomponent nanomaterials is critical to optimize their catalytic performance. In this direction, while impressive advances have been achieved in the past decade in the synthesis of multicomponent nanoparticles and nanocomposites, element rearrangement during catalyst activation has been frequently overseen. Here, we present a facile galvanic replacement-based procedure to synthesize Co@Cu nanoparticles with narrow size and composition distributions. We further characterize their phase arrangement before and after catalytic activation. When oxidized at 350 °C in air to remove organics, Co@Cu core-shell nanostructures oxidize to polycrystalline CuO-Co3O4 nanoparticles with randomly distributed CuO and Co3O4 crystallites. During a posterior reduction treatment in H2 atmosphere, Cu precipitates in a metallic core and Co migrates to the nanoparticle surface to form Cu@Co core-shell nanostructures. The catalytic behavior of such Cu@Co nanoparticles supported on mesoporous silica was further analyzed toward CO2 hydrogenation in real working conditions.

  14. Large-Aperture Membrane Active Phased-Array Antennas

    NASA Technical Reports Server (NTRS)

    Karasik, Boris; McGrath, William; Leduc, Henry

    2009-01-01

    Large-aperture phased-array microwave antennas supported by membranes are being developed for use in spaceborne interferometric synthetic aperture radar systems. There may also be terrestrial uses for such antennas supported on stationary membranes, large balloons, and blimps. These antennas are expected to have areal mass densities of about 2 kg/sq m, satisfying a need for lightweight alternatives to conventional rigid phased-array antennas, which have typical areal mass densities between 8 and 15 kg/sq m. The differences in areal mass densities translate to substantial differences in total mass in contemplated applications involving aperture areas as large as 400 sq m. A membrane phased-array antenna includes patch antenna elements in a repeating pattern. All previously reported membrane antennas were passive antennas; this is the first active membrane antenna that includes transmitting/receiving (T/R) electronic circuits as integral parts. Other integral parts of the antenna include a network of radio-frequency (RF) feed lines (more specifically, a corporate feed network) and of bias and control lines, all in the form of flexible copper strip conductors on flexible polymeric membranes. Each unit cell of a prototype antenna (see Figure 1) contains a patch antenna element and a compact T/R module that is compatible with flexible membrane circuitry. There are two membrane layers separated by a 12.7-mm air gap. Each membrane layer is made from a commercially available flexible circuit material that, as supplied, comprises a 127-micron-thick polyimide dielectric layer clad on both sides with 17.5-micron-thick copper layers. The copper layers are patterned into RF, bias, and control conductors. The T/R module is located on the back side of the ground plane and is RF-coupled to the patch element via a slot. The T/R module is a hybrid multilayer module assembled and packaged independently and attached to the membrane array. At the time of reporting the information for

  15. An in situ vapour phase hydrothermal surface doping approach for fabrication of high performance Co3O4 electrocatalysts with an exceptionally high S-doped active surface.

    PubMed

    Tan, Zhijin; Liu, Porun; Zhang, Haimin; Wang, Yun; Al-Mamun, Mohammad; Yang, Hua Gui; Wang, Dan; Tang, Zhiyong; Zhao, Huijun

    2015-04-04

    A facile in situ vapour phase hydrothermal (VPH) surface doping approach has been developed for fabrication of high performance S-doped Co3O4 electrocatalysts with an unprecedentedly high surface S content (>47%). The demonstrated VPH doping approach could be useful for enrichment of surface active sites for other metal oxide electrocatalysts.

  16. In-flight gas phase growth of metal/multi layer graphene core shell nanoparticles with controllable sizes

    PubMed Central

    Sengar, Saurabh K.; Mehta, B. R.; Kumar, Rakesh; Singh, Vinod

    2013-01-01

    In this report, we present a general method for a continuous gas-phase synthesis of size-selected metal/multi layer graphene (MLG) core shell nanoparticles having a narrow size distribution of metal core and MLG shell for direct deposition onto any desired substrate kept under clean vacuum conditions. Evolution of MLG signature is clearly observed as the metal-carbon agglomerates get transformed to well defined metal/MLG core shell nanoparticles during their flight through the sintering zone. The growth takes place via an intermediate state of alloy nanoparticle (Pd-carbon) or composite nanoparticle (Cu-carbon), depending upon the carbon solubility in the metal and relative surface energy values. It has been also shown that metal/MLG nanoparticles can be converted to graphene shells. This study will have a large impact on how graphene or graphene based composite nanostructures can be grown and deposited in applications requiring controllable dimensions, varied substrate choice, large area and large scale depositions. PMID:24100702

  17. Properties of high-density, well-ordered, and high-energy metallic glass phase designed by pressurized quenching

    NASA Astrophysics Data System (ADS)

    Miyazaki, Narumasa; Lo, Yu-Chieh; Wakeda, Masato; Ogata, Shigenobu

    2016-08-01

    We applied gigapascal-level compressive hydrostatic pressure to the melt-quenching process of metallic glass to obtain a unique high-pressure glass state with high density that is well-ordered yet has high energy. This state contradicts the common understanding that high-density, well-ordered metallic glass states have low energy. Through molecular dynamics simulations, we found that the high-pressure glass state of the metallic glass Zr50Cu40Al10 has a rich anti-free volume and that its relaxation is dominated by the annihilation of full icosahedra and the rich anti-free volume. The aging rate of the high-pressure metallic glass state (energy reduction rate) is almost the same as that of typical high-energy metallic glass, suggesting that it has a lifetime similar to that of a typical high-energy metallic glass that has been experimentally realized and reported previously [Wakeda et al., Sci. Rep. 5, 10545 (2015)]. Thus, the high-pressure phase can be realized even under the experimental cooling rate, suggesting its suitability for practical applications.

  18. Benzene under high pressure: A story of molecular crystals transforming to saturated networks, with a possible intermediate metallic phase

    SciTech Connect

    Wen, Xiao-Dong; Hoffmann, Roald; Ashcroft, N. W.

    2011-01-01

    In a theoretical study, benzene is compressed up to 300 GPa. The transformations found between molecular phases generally match the experimental findings in the moderate pressure regime (<20 GPa): phase I (Pbca) is found to be stable up to 4 GPa, while phase II (P43212) is preferred in a narrow pressure range of 4–7 GPa. Phase III (P21/c) is at lowest enthalpy at higher pressures. Above 50 GPa, phase V (P21 at 0 GPa; P21/c at high pressure) comes into play, slightly more stable than phase III in the range of 50–80 GP, but unstable to rearrangement to a saturated, four-coordinate (at C), one-dimensional polymer. Actually, throughout the entire pressure range, crystals of graphane possess lower enthalpy than molecular benzene structures; a simple thermochemical argument is given for why this is so. In several of the benzene phases there nevertheless are substantial barriers to rearranging the molecules to a saturated polymer, especially at low temperatures. Even at room temperature these barriers should allow one to study the effect of pressure on the metastable molecular phases. Molecular phase III (P21/c) is one such; it remains metastable to higher pressures up to ~200 GPa, at which point it too rearranges spontaneously to a saturated, tetracoordinate CH polymer. At 300 K the isomerization transition occurs at a lower pressure. Nevertheless, there may be a narrow region of pressure, between P = 180 and 200 GPa, where one could find a metallic, molecular benzene state. We explore several lower dimensional models for such a metallic benzene. We also probe the possible first steps in a localized, nucleated benzene polymerization by studying the dimerization of benzene molecules. Several new (C6H6)2 dimers are predicted.

  19. Method for aqueous phase reactions

    DOEpatents

    Elliott, Douglas C.; Hart, Todd R.

    2000-01-01

    A method for converting liquid organic material in a mixture into a product utilizing a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional metal deposited onto the support in a second dispersed phase. The additional metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase without substantially affecting the catalytic activity, thereby increasing the life time of the catalyst.

  20. The effects of hydrogen bonds on metal-mediated O2 activation and related processes

    PubMed Central

    Shook, Ryan L.; Borovik, A. S.

    2009-01-01

    Hydrogen bonds stabilize and direct chemistry performed by metalloenzymes. With inspiration from enzymes, we will utilize an approach that incorporates intramolecular hydrogen bond donors to determine their effects on the stability and reactivity of metal complexes. Our premise is that control of secondary coordination sphere interactions will promote new function in synthetic metal complexes. Multidentate ligands have been developed that create rigid organic structures around metal ions. These ligands place hydrogen bond (H-bond) donors proximal to the metal centers, forming specific microenvironments. One distinguishing attribute of these systems is that site-specific modulations in structure can be readily accomplished, in order to evaluate correlations with reactivity. A focus of this research is consideration of dioxygen binding and activation by metal complexes, including developing structure–function relationships in metal-assisted oxidative catalysis. PMID:19082087