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Sample records for metal borides stability

  1. Structures and stability of novel transition-metal (M =Co ,Rh ,Co and Ir ) borides

    NASA Astrophysics Data System (ADS)

    Wang, Yachun; Wu, Lailei; Lin, Yangzheng; Hu, Qingyang; Li, Zhiping; Liu, Hanyu; Zhang, Yunkun; Gou, Huiyang; Yao, Yansun; Zhang, Jingwu; Gao, Faming; Mao, Ho-kwang

    2015-11-01

    Recent progress of high-pressure technology enables the synthesis of novel metal borides with diverse compositions and interesting properties. A precise characterization of these borides, however, is sometimes hindered by multiphase intergrowth and grain-size limitation in the synthesis process. Here, we theoretically explored new transition-metal borides (M =Co , Rh, and Ir) using a global structure searching method and discovered a series of stable compounds in this family. The predicted phases display a rich variety of stoichiometries and distinct boron networks resulting from the electron-deficient environments. Significantly, we identified a new Ir B1.25 structure as the long-sought structure of the first synthesized Ir-B compound. The simulated x-ray diffraction pattern of the proposed Ir B1.25 structure matches well with the experiment, and the convex hull calculation establishes its thermodynamic stability. Results of the present paper should advance the understanding of transition-metal borides and stimulate experimental explorations of these new and promising materials.

  2. Boron diffusion in silicon from metal boride sources

    SciTech Connect

    Ryan, J.G.

    1988-01-01

    Thin films of titanium and lanthanum borides were investigated as potential boron diffusion sources. TiB{sub x} and LaB{sub 6} films exhibited room-temperature film stresses and resistivity values similar to refractory-metal silicides, and acted as boron diffusion sources, producing diffusions with high surface concentrations. The source of boron from TiB{sub x} films appears to be the excess boron present in the metal boride or at the metal boride-silicon substrate interface. Boron surface concentration increases with increasing mole fraction of boron in the metal boride source. Boron surface concentration peaks at 1000{degree}C for furnace-annealed TiB{sub 2.2}, but rises until a plateau is reached at 1050{degree}C for rapid-annealed samples of the same composition. The concentration of electrically active boron was consistently lower than the chemical concentration in these studies. The stability of the boride films on silicon substrates was found to be dependent on boride source composition. LaB{sub 6} and TiB films reacted with the silicon substrate. Although the TiB{sub 2.1}, TiB{sub 2.2}, and TiB{sub 2.9} films did not decompose or allow Si to diffuse into them, a silicon boride surface layer was formed in the silicon substrate caused by boron out-diffusing from these sources during furnace annealing.

  3. Ultra-fast boriding of metal surfaces for improved properties

    SciTech Connect

    Timur, Servet; Kartal, Guldem; Eryilmaz, Osman L.; Erdemir, Ali

    2015-02-10

    A method of ultra-fast boriding of a metal surface. The method includes the step of providing a metal component, providing a molten electrolyte having boron components therein, providing an electrochemical boriding system including an induction furnace, operating the induction furnace to establish a high temperature for the molten electrolyte, and boriding the metal surface to achieve a boride layer on the metal surface.

  4. An unusual variation of stability and hardness in molybdenum borides

    NASA Astrophysics Data System (ADS)

    Liang, Yongcheng; Yuan, Xun; Fu, Zhao; Li, Yuan; Zhong, Zheng

    2012-10-01

    Molybdenum borides are currently raising great expectations for superhard materials, but their crystal structures and mechanical behaviors are still under discussion. Here, we report an unexpected reduction of stability and hardness from porous hP16-MoB3 and hR18-MoB2 to dense hP20-MoB4 and hR21-Mo2B5, respectively. Furthermore, we demonstrate that this anomalous variation has its electronic origin. These findings not only manifest that the long-recognized hP20-MoB4 (hP3-MoB2) and hR21-Mo2B5 should be hP16-MoB3 and hR18-MoB2, respectively, but also challenge the general design principle for ultrahard materials only pursuing the dense transition-metal borides with high boron content.

  5. 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).

  6. Metal borohydride formation from aluminium boride and metal hydrides.

    PubMed

    Møller, Kasper T; Fogh, Alexander S; Paskevicius, Mark; Skibsted, Jørgen; Jensen, Torben R

    2016-10-05

    Metal borides are often decomposition products from metal borohydrides and thus play a role in the reverse reaction where hydrogen is absorbed. In this work, aluminium boride, AlB2, has been investigated as a boron source for the formation of borohydrides under hydrogen pressures of p(H2) = 100 or 600 bar at elevated temperatures (350 or 400 °C). The systems AlB2-MHx (M = Li, Na, Mg, Ca) have been investigated, producing LiBH4, NaBH4 and Ca(BH4)2, whereas the formation of Mg(BH4)2 was not observed at T = 400 °C and p(H2) = 600 bar. The formation of the metal borohydrides is confirmed by powder X-ray diffraction and infrared spectroscopy and the fraction of boron in AlB2 and M(BH4)x is determined quantitatively by (11)B MAS NMR. Hydrogenation for 12 h at T = 350-400 °C and p(H2) = 600 bar leads to the formation of substantial amounts of LiBH4 (38.6 mol%), NaBH4 (83.0 mol%) and Ca(BH4)2 (43.6 mol%).

  7. Discovery of elusive structures of multifunctional transition-metal borides

    NASA Astrophysics Data System (ADS)

    Liang, Yongcheng; Wu, Zhaobing; Yuan, Xun; Zhang, Wenqing; Zhang, Peihong

    2015-12-01

    A definitive determination of crystal structures is an important prerequisite for designing and exploiting new functional materials. Even though tungsten and molybdenum borides (TMBx) are the prototype for transition-metal light-element compounds with multiple functionalities, their elusive crystal structures have puzzled scientists for decades. Here, we discover that the long-assumed TMB2 phases with the simple hP3 structure (hP3-TMB2) are in fact a family of complex TMB3 polytypes with a nanoscale ordering along the axial direction. Compared with the energetically unfavorable and dynamically unstable hP3-TMB2 phase, the energetically more favorable and dynamically stable TMB3 polytypes explain the experimental structural parameters, mechanical properties, and X-ray diffraction (XRD) patterns better. We demonstrate that such a structural and compositional modification from the hP3-TMB2 phases to the TMB3 polytypes originates from the relief of the strong antibonding interaction between d electrons by removing one third of metal atoms systematically. These results resolve the longstanding structural mystery of this class of metal borides and uncover a hidden family of polytypic structures. Moreover, these polytypic structures provide an additional hardening mechanism by forming nanoscale interlocks that may strongly hinder the interlayer sliding movements, which promises to open a new avenue towards designing novel superhard nanocomposite materials by exploiting the coexistence of various polytypes.

  8. Synthesis of Binary Transition Metal Nitrides, Carbides and Borides from the Elements in the Laser-Heated Diamond Anvil Cell and Their Structure-Property Relations

    PubMed Central

    Friedrich, Alexandra; Winkler, Björn; Juarez-Arellano, Erick A.; Bayarjargal, Lkhamsuren

    2011-01-01

    Transition metal nitrides, carbides and borides have a high potential for industrial applications as they not only have a high melting point but are generally harder and less compressible than the pure metals. Here we summarize recent advances in the synthesis of binary transition metal nitrides, carbides and borides focusing on the reaction of the elements at extreme conditions generated within the laser-heated diamond anvil cell. The current knowledge of their structures and high-pressure properties like high-(p,T) stability, compressibility and hardness is described as obtained from experiments. PMID:28824101

  9. Structural and mechanical properties of transition metal borides Nb2MB2 (M=Tc, Ru, and Os) under pressure

    NASA Astrophysics Data System (ADS)

    Li, Xiaofeng; Yan, Haiyan; Wei, Qun

    2016-10-01

    First-principle total energy calculations are employed to provide a fundamental understanding of the structural, mechanical, and electronic properties of transition metal borides Nb2MB2 (M=Tc, Ru, and Os) within the tetragonal superstructure P4/mnc structure. The mechanically and dynamically stabilities of three borides have been demonstrated by the elastic constants and phonons calculations under pressure. Among these three compounds, Nb2TcB2 exhibits the biggest bulk and Young's modulus, smallest Poission's ratio, and highest harness. Density of states of them revealed that the strong B-B, Nb-B and M-B covalent bonds are major driving forces for their high bulk and shear moduli as well as small Poisson's ratio.

  10. Characterization of novel borides in Ti-Nb-Zr-Ta + 2B metal-matrix composites

    SciTech Connect

    Nag, Soumya; Samuel, Sonia; Puthucode, Anantha; Banerjee, Rajarshi

    2009-02-15

    Metal-matrix composites consisting of a complex quaternary Ti-35Nb-7Zr-5Ta alloy reinforced by borides have been successfully deposited from a powder feedstock consisting of a blend of elemental titanium, niobium, zirconium, tantalum, and, titanium diboride (TiB{sub 2}) powders, using the laser engineered net-shaping (LENS{sup TM}) process. The microstructures of the as-deposited composites have been characterized using scanning electron microscopy, orientation microscopy, and, transmission electron microscopy. Both primary and eutectic boride precipitates, exhibiting the orthorhombic B27 structure, are observed in these as-deposited composites. The complex primary borides exhibit an unusual compositional variation within the same precipitate, which has been investigated in detail using site-specific characterization with a transmission electron microscope. The ability to form near-net shape components using the Laser Engineered Net Shaping process makes these laser-deposited composites promising candidates for wear-resistant applications in biomedical implants.

  11. The structural stabilities, mechanical properties and hardness of chromium tetraboride: Compared with low-B borides

    NASA Astrophysics Data System (ADS)

    Zhong, Ming-Min; Huang, Cheng; Tian, Chun-Ling

    2016-10-01

    Using the first-principles calculations, we provide a systemic understanding of the structural features and phase stability, mechanical and electronic properties, as well as the roles of boron (B) atom arrangement in the hardness for chromium borides. The structural and relative energy searches together with formation enthalpy confirm the most stable Cr2B with an orthorhombic Fddd symmetry, CrB with an orthorhombic Cmcm symmetry, CrB2 with a hexagonal P63/mmc symmetry and chromium tetraboride (CrB4) with an orthorhombic Pnnm symmetry. The shear modulus, Young’s modulus and C44 increase with the boron content, while the Poisson’s ratio and B/G ratio have an opposite tendency. Moreover, due to higher B content, strong three-dimensional (3D) covalent B networks and lower metallic contribution, CrB4 with Pnnm symmetry has the largest hardness value (46.8 GPa), exceeding the superhard limit, indicating its superhard nature.

  12. Metal-boride phase formation on tungsten carbide (WC-Co) during microwave plasma chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Johnston, Jamin M.; Catledge, Shane A.

    2016-02-01

    Strengthening of cemented tungsten carbide by boriding is used to improve the wear resistance and lifetime of carbide tools; however, many conventional boriding techniques render the bulk carbide too brittle for extreme conditions, such as hard rock drilling. This research explored the variation in metal-boride phase formation during the microwave plasma enhanced chemical vapor deposition process at surface temperatures from 700 to 1100 °C. We showed several well-adhered metal-boride surface layers consisting of WCoB, CoB and/or W2CoB2 with average hardness from 23 to 27 GPa and average elastic modulus of 600-730 GPa. The metal-boride interlayer was shown to be an effective diffusion barrier against elemental cobalt; migration of elemental cobalt to the surface of the interlayer was significantly reduced. A combination of glancing angle X-ray diffraction, electron dispersive spectroscopy, nanoindentation and scratch testing was used to evaluate the surface composition and material properties. An evaluation of the material properties shows that plasma enhanced chemical vapor deposited borides formed at substrate temperatures of 800 °C, 850 °C, 900 °C and 1000 °C strengthen the material by increasing the hardness and elastic modulus of cemented tungsten carbide. Additionally, these boride surface layers may offer potential for adhesion of ultra-hard carbon coatings.

  13. Selection of peptides binding to metallic borides by screening M13 phage display libraries

    PubMed Central

    2014-01-01

    Background Metal borides are a class of inorganic solids that is much less known and investigated than for example metal oxides or intermetallics. At the same time it is a highly versatile and interesting class of compounds in terms of physical and chemical properties, like semiconductivity, ferromagnetism, or catalytic activity. This makes these substances attractive for the generation of new materials. Very little is known about the interaction between organic materials and borides. To generate nanostructured and composite materials which consist of metal borides and organic modifiers it is necessary to develop new synthetic strategies. Phage peptide display libraries are commonly used to select peptides that bind specifically to metals, metal oxides, and semiconductors. Further, these binding peptides can serve as templates to control the nucleation and growth of inorganic nanoparticles. Additionally, the combination of two different binding motifs into a single bifunctional phage could be useful for the generation of new composite materials. Results In this study, we have identified a unique set of sequences that bind to amorphous and crystalline nickel boride (Ni3B) nanoparticles, from a random peptide library using the phage display technique. Using this technique, strong binders were identified that are selective for nickel boride. Sequence analysis of the peptides revealed that the sequences exhibit similar, yet subtle different patterns of amino acid usage. Although a predominant binding motif was not observed, certain charged amino acids emerged as essential in specific binding to both substrates. The 7-mer peptide sequence LGFREKE, isolated on amorphous Ni3B emerged as the best binder for both substrates. Fluorescence microscopy and atomic force microscopy confirmed the specific binding affinity of LGFREKE expressing phage to amorphous and crystalline Ni3B nanoparticles. Conclusions This study is, to our knowledge, the first to identify peptides that

  14. Low temperature route for the synthesis of rare earth transition metal borides and their hydrides

    SciTech Connect

    Kramp, S.; Febri, M.; Joubert, J.C.

    1997-10-01

    Synthesis of rare earth-based alloys by the ORD technique consists in the reduction of rare earth oxides in a melt of calcium under argon, and simultaneous diffusion-reaction of the just formed rare earth metal with the other elements. This method has been applied with success to numerous ternary borides containing transition metals such as the magnetic alloys Y{sub 2}Co{sub 14}B, LnCo{sub 4}B, and YCo{sub 3}B{sub 2}. By using a small excess of Ca, boride particles grow in a viscous slurry media containing unreacted (melted) Ca and nanosize CaO particles. Single phase boride alloys can be obtained at 1000{degrees}C as loose micrometer-size particles of very high crystal quality as confirmed by the sharp diffraction peaks on the corresponding X-ray diagrams. Particles can be easily recovered by gentle wishing in diluted weak acid solution, and dried under vacuum at room temperature. This rather low temperature technique is particularly adapted to the synthesis of incongruent melting phases, as well as for the alloys containing volatile rare earth elements (Sm, Yb, Tb,...).

  15. A Low Temperature Route for the Synthesis of Rare Earth Transition Metal Borides and Their Hydrides

    NASA Astrophysics Data System (ADS)

    Kramp, S.; Febri, M.; Joubert, J. C.

    1997-10-01

    Synthesis of rare earth-based alloys by the ORD technique consists in the reduction of rare earth oxides in a melt of calcium under argon, and simultaneous diffusion-reaction of the just formed rare earth metal with the other elements. This method has been applied with success to numerous ternary borides containing transition metals such as the magnetic alloys Y2Co14B, LnCo4B, and YCo3B2. By using a small excess of Ca, boride particles grow in a viscous slurry media containing unreacted (melted) Ca and nanosize CaO particles. Single phase boride alloys can be obtained at 1000°C as loose micrometer-size particles of very high crystal quality as confirmed by the sharp diffraction peaks on the corresponding X-ray diagrams. Particles can be easily recovered by gentle washing in diluted weak acid solution, and dried under vacuum at room temperature. This rather low temperature technique is particularly adapted to the synthesis of incongruent melting phases, as well as for the alloys containing volatile rare earth elements (Sm, Yb, Tb,…).

  16. Method for ultra-fast boriding

    DOEpatents

    Erdemir, Ali; Sista, Vivekanand; Kahvecioglu, Ozgenur; Eryilmaz, Osman Levent

    2017-01-31

    An article of manufacture and method of forming a borided material. An electrochemical cell is used to process a substrate to deposit a plurality of borided layers on the substrate. The plurality of layers are co-deposited such that a refractory metal boride layer is disposed on a substrate and a rare earth metal boride conforming layer is disposed on the refractory metal boride layer.

  17. Mechanistic considerations of the pyrolytic formation of metal boride thin films by chemical vapor deposition from borane precursors

    SciTech Connect

    Tan, Y.; Kher, S.S.; Spencer, J.T.

    1995-12-31

    The formation of metal boride thin films by CVD is an area of potentially significant technological consequence. Interest in these materials is primarily due to their breadth of unique physical properties and to their wide structural diversity. Recently, we have explored the use of a number of boron-containing CVC precursors to prepare a wide variety of both pure metal and metal boride thin film materials. The highly efficient formation of polycrystalline transition metal and lanthanide metal boride thin films from borane precursors has now been well demonstrated through this CVD chemistry. The fundamentally important chemical processes and reactions in the CVD of boranes in forming metal boride films has, however, remained mostly a mystery. In order to rationally design new precursors and tailor the deposited solid state materials, an understanding of these fundamental processes is critical. In our recent work, which will be reported here, we have begun detailed mechanistic studies into the CVD of metal borides. These reactions have been found to occur both in the gas phase and on the surface of the reactor. A variety of studies have provided valuable insights into these complexes chemical reactions including labeling, thermal, product distribution, surface analysis, kinetic and other investigations.

  18. Phase stability and elastic properties of chromium borides with various stoichiometries.

    PubMed

    Wang, Bing; Wang, De Yu; Cheng, Zhenxiang; Wang, Xiaolin; Wang, Yuan Xu

    2013-04-15

    Phase stability is important to the application of materials. By first-principles calculations, we establish the phase stability of chromium borides with various stoichiometries. Moreover, the phases of CrB3 and CrB4 have been predicted by using a newly developed particle swarm optimization (PSO) algorithm. Formation enthalpy-pressure diagrams reveal that the MoB-type structure is more energetically favorable than the TiI-type structure for CrB. For CrB2, the WB2-type structure is preferred at zero pressure. The predicted new phase of CrB3 belongs to the hexagonal P-6m2 space group and it transforms into an orthorhombic phase as the pressure exceeds 93 GPa. The predicted CrB4 (space group: Pnnm) phase is more energetically favorable than the previously proposed Immm structure. The mechanical and thermodynamic stabilities of predicted CrB3 and CrB4 are verified by the calculated elastic constants and formation enthalpies. The full phonon dispersion calculations confirm the dynamic stability of WB2 -type CrB2 and predicted CrB3. The large shear moduli, large Young's moduli, low Poisson ratios, and low bulk and shear modulus ratios of CrB4-PSC and CrB4-PSD indicate that they are potential hard materials. Analyses of Debye temperature, electronic localization function, and electronic structure provide further understanding of the chemical and physical properties of these borides.

  19. Synthesis and characterization of noble metal borides: RuB{sub x}(x > 1)

    SciTech Connect

    Li, Zhifang; Zheng, Dafang; Ding, Zhanhui; Li, Yongfeng; Yao, Bin; Li, Yongsheng; Zhao, Xudong; Yu, Guichuan; Tang, Yang; Zheng, Weitao; Liu, Xiaoyang

    2016-02-15

    Highlights: • Hexagonal RuB{sub 1.1} were synthesized using ruthenium and boron powders as raw materials during ball milling process. • Orthorhombic RuB{sub 2} were synthesized under high pressure (5 GPa) and high temperature (1000 °C) conditions. • Hexagonal Ru{sub 2}B{sub 3} have been synthesized under 5 GPa and 1200 °C. - Abstract: Noble metal borides RuB{sub 1.1}, RuB{sub 2} and Ru{sub 2}B{sub 3} have been synthesized by mechanical alloying and high pressure sintering methods using ruthenium (Ru) and boron (B) powders as raw materials. The crystal structures of borides were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results shown that only RuB{sub 1.1} with hexagonal crystal structure was synthesized during the ball milling process, the orthorhombic RuB{sub 2} was synthesized under high pressure (5 GPa) and high temperature (1000 °C) conditions, while the hexagonal Ru{sub 2}B{sub 3} can be synthesized under 5 GPa and 1200 °C. The mechanism of synthesis for the ruthenium borides (RuB{sub x}) are discussed in details.

  20. Infiltration processing of boron carbide-, boron-, and boride-reactive metal cermets

    DOEpatents

    Halverson, Danny C.; Landingham, Richard L.

    1988-01-01

    A chemical pretreatment method is used to produce boron carbide-, boron-, and boride-reactive metal composites by an infiltration process. The boron carbide or other starting constituents, in powder form, are immersed in various alcohols, or other chemical agents, to change the surface chemistry of the starting constituents. The chemically treated starting constituents are consolidated into a porous ceramic precursor which is then infiltrated by molten aluminum or other metal by heating to wetting conditions. Chemical treatment of the starting constituents allows infiltration to full density. The infiltrated precursor is further heat treated to produce a tailorable microstructure. The process at low cost produces composites with improved characteristics, including increased toughness, strength.

  1. Superconductivity in the Metal Rich Li-Pd-B Ternary Boride

    NASA Astrophysics Data System (ADS)

    Togano, K.; Badica, P.; Nakamori, Y.; Orimo, S.; Takeya, H.; Hirata, K.

    2004-12-01

    Superconductivity at about 8K was observed in the metal-rich Li-Pd-B ternary system. Structural, microstructural, electrical, and magnetic investigations for various compositions proved that the Li2Pd3B compound, which has an antiperovskite cubic structure composed of distorted Pd6B octahedrons, is responsible for the superconductivity. This is the first observation of superconductivity in metal-rich ternary borides containing alkaline metal and Pd as a late transition metal. The compound prepared by arc melting has a high density and is relatively stable in the air. The upper critical fields Hc2(0) estimated by linear extrapolation and the Werthamer-Helfand-Hohenberg theory are 6.2 and 4.8T, respectively.

  2. Phase stability and incompressibility of tungsten boride (WB) researched by in-situ high pressure x-ray diffraction

    NASA Astrophysics Data System (ADS)

    Fan, Cong; Liu, Chenji; Peng, Fang; Tan, Ning; Tang, Mingjun; Zhang, Qiang; Wang, Qiming; Li, Fengjiao; Wang, Jianghua; Chen, Ying; Liang, Hao; Guan, Shixue; Yang, Ke; Liu, Jing

    2017-09-01

    The binary tungsten boride, WB, has potential industrial applications as it not only has a high melting point but is generally harder and less compressible than the pure metals. Here, the physical and mechanical properties (phase stability, bulk modulus and compressibility) of WB were investigated by in situ high-pressure x-ray diffraction and theoretical calculations. Its crystal structure still remains stable even at the highest pressure of 63.7 GPa and room temperature for the diamond-anvil cell experiments. The pressure-volume (P-V) data were fitted using the Birch-Murnaghan EOS and the Vinet EOS to obtain the isothermal bulk modulus, K0 = 452 (4) GPa and 451(3) GPa and its pressure derivative, K0‧ = 4 (fixed) in the two sets of experiments with two different pressure transmitting mediums (PTMs), respectively. The excellent bulk modulus (K0) is attributed to the high valence electron density of W atom, the layered and chain-like crystal structure of WB and the strong chemical bonds formed by W and B atoms. Besides, anisotropic compression behavior of the unit-cell axes (a- and c-axes) of WB is manifested by experimental observations and theoretical calculations. This remarkably elastic property is closely related to the strongly directional bonding between W and B atoms.

  3. Phase stability and mechanical properties of tungsten borides from first principles calculations.

    PubMed

    Zhao, Erjun; Meng, Jian; Ma, Yanming; Wu, Zhijian

    2010-10-28

    The phase stability and mechanical properties of tungsten borides W(2)B, WB, WB(2), W(2)B(5) and WB(4) were extensively studied by first-principles calculations within density functional theory. The thermodynamic and mechanical stabilities were examined. Our calculations on the enthalpy-pressure relationship and convex hulls have demonstrated that at zero pressure, the experimentally observed W(2)B-W(2)B (W(2)B-W(2)B represents W(2)B in W(2)B structure type, the same hereinafter) and WB-WB, and assumed WB(2)-ReB(2) phases are stable against decomposition into other components. The estimated hardness of WB(2)-ReB(2) is 39.4 GPa, suggesting that it is a potentially hard compound. At 60 GPa, the most stable phases are WB-WB and WB(2)-WB(2). WB-WB, WB(2)-AlB(2) and WB(4) are the ground state phases at 100 GPa. The phase transition mechanism for WB(2) was discussed. The synthesis of WB(2)-AlB(2) could be conducted at high pressures.

  4. Transition metal carbides, nitrides and borides, and their oxygen containing analogs useful as water gas shift catalysts

    DOEpatents

    Thompson, Levi T.; Patt, Jeremy; Moon, Dong Ju; Phillips, Cory

    2003-09-23

    Mono- and bimetallic transition metal carbides, nitrides and borides, and their oxygen containing analogs (e.g. oxycarbides) for use as water gas shift catalysts are described. In a preferred embodiment, the catalysts have the general formula of M1.sub.A M2.sub.B Z.sub.C O.sub.D, wherein M1 is selected from the group consisting of Mo, W, and combinations thereof; M2 is selected from the group consisting of Fe, Ni, Cu, Co, and combinations thereof; Z is selected from the group consisting of carbon, nitrogen, boron, and combinations thereof; A is an integer; B is 0 or an integer greater than 0; C is an integer; O is oxygen; and D is 0 or an integer greater than 0. The catalysts exhibit good reactivity, stability, and sulfur tolerance, as compared to conventional water shift gas catalysts. These catalysts hold promise for use in conjunction with proton exchange membrane fuel cell powered systems.

  5. Corrosion Resistance of Nanopowders of Borides and Carbides of IV-VIB Group Metals in the Nickeling Electrolytes

    NASA Astrophysics Data System (ADS)

    Shakhnin, Dmytro; Malyshev, Viktor; Kuschevskaya, Nina; Gab, Angelina

    2017-07-01

    The corrosion resistance of nanopowders of borides and carbides of metals of IV-VIB groups, as well as of silicon carbide, was studied in the standard nickeling electrolytes. As objects of study, nanopowders with the content of the main phase 91.8-97.6% and with the average particle size 32-78 nm were used. Their corrosion resistance was evaluated depending on the acidity of the electrolyte, temperature, and duration of the interaction. It was found that, by the corrosion resistance in the electrolytes solutions, nanopowders of borides and carbides within each group of compounds are similar and characterized by unlimited period of induction in alkaline media. An exception is the nanopowder of silicon carbide which is resistant to the solution of any acidity.

  6. Nanosized Borides and Carbides for Electroplating. Metal-Matrix Coatings: Specifications, Performance Evaluation

    NASA Astrophysics Data System (ADS)

    Galevskiy, G. V.; Rudneva, V. V.; Galevskiy, S. G.; Il'yashchenko, D. P.; Kartsev, D. S.

    2016-04-01

    This paper summarizes experience of application of nano-sized carbides and borides of titanium and chromium, silicon carbide as components of electro-depositable coating compositions based on nickel, zinc, and chromium. Basic physical and mechanical properties of the coatings are determined. Technological and economic evaluation is completed; practicability of high-cost nano-diamonds substitution for nano-sized borides and carbides is justified.

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

    SciTech Connect

    Klemppa, Ole J.

    2000-10-01

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

  8. 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.

  9. Interlayer utilization (including metal borides) for subsequent deposition of NSD films via microwave plasma CVD on 316 and 440C stainless steels

    NASA Astrophysics Data System (ADS)

    Ballinger, Jared

    . Surface boriding was implemented using the novel method of microwave plasma CVD with a mixture of hydrogen and diborane gases. On 440C bearings, dual phase boride layers of Fe2B and FeB were formed which supported adhered nanostructured diamond films. Continuity of the films was not seamless with limited regions remaining uncoated potentially corresponding to delamination of the film as evidenced by the presence of tubular structures presumably composed of sp2 bonded carbon. Surface boriding of 316 stainless steel discs was conducted at various powers and pressures to achieve temperatures ranging from 550-800 °C. The substrate boriding temperature was found to substantially influence the resultant interlayer by altering the metal boride(s) present. The lowest temperatures produced an interlayer where CrB was the single detected phase, higher temperatures yielded the presence of only Fe2B, and a combination of the two phases resulted from an intermediate boriding temperature. Compared with the more common, commercialized boriding methods, this a profound result given the problems posed by the FeB phase in addition to other advantages offered by CVD processes and microwave generated plasmas in general. Indentation testing of the boride layers revealed excellent adhesion strength for all borided interlayers, and above all, no evidence of cracking was observed for a sole Fe2B phase. As with boriding of 440C bearings, subsequent diamond deposition was achieved on these interlayers with substantially improved adhesion strength relative to diamond coated TiN interlayers. Both XRD and Raman spectroscopy confirmed a nanostructured diamond film with interfacial chromium carbides responsible for enhanced adhesion strength. Interlayers consisting solely of Fe2B have displayed an ability to support fully continuous nanostructured diamond films, yet additional study is required for consistent reproduction. This is in good agreement with initial work on pack borided high alloy steels

  10. 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.

  11. Rediscovering the Crystal Chemistry of Borides.

    PubMed

    Akopov, Georgiy; Yeung, Michael T; Kaner, Richard B

    2017-03-21

    For decades, borides have been primarily studied as crystallographic oddities. With such a wide variety of structures (a quick survey of the Inorganic Crystal Structure Database counts 1253 entries for binary boron compounds!), it is surprising that the applications of borides have been quite limited despite a great deal of fundamental research. If anything, the rich crystal chemistry found in borides could well provide the right tool for almost any application. The interplay between metals and the boron results in even more varied material's properties, many of which can be tuned via chemistry. Thus, the aim of this review is to reintroduce to the scientific community the developments in boride crystal chemistry over the past 60 years. We tie structures to material properties, and furthermore, elaborate on convenient synthetic routes toward preparing borides.

  12. Superconductivity and spin fluctuations in the actinoid-platinum metal borides {Th ,U } Pt3B

    NASA Astrophysics Data System (ADS)

    Bauer, E.; Royanian, E.; Michor, H.; Sologub, O.; Scheidt, E.-W.; Gonçalves, A. P.; Bursik, J.; Wolf, W.; Reith, D.; Blaas-Schenner, C.; Moser, R.; Podloucky, R.; Rogl, P.

    2015-07-01

    Investigating the phase relations of the system {Th ,U } -Pt-B at 900 °C the formation of two compounds has been observed: cubic ThPt3B with P m 3 ¯m structure as a representative of the perovskites, and tetragonal UPt3B with P 4 m m structure being isotypic to the noncentrosymmetric structure of CePt3B . The crystal structures of the two compounds are defined by combined x-ray diffraction and transmission electron microscopy. Characterization of physical properties for ThPt3B reveals a superconducting transition at 0.75 K and an upper critical field at T =0 exceeding 0.4 T. For nonsuperconducting UPt3B a metallic resistivity behavior was found in the entire temperature range; at very low temperatures spin fluctuations become evident and the resistivity ρ (T ) follows non-Fermi liquid characteristics, ρ =ρ0+A T n with n =1.6 . Density functional theory (DFT) calculations were performed for both compounds for both types of structures. They predict that the experimentally claimed cubic structure of ThPt3B is thermodynamically not stable in comparison to a tetragonal phase, with a very large enthalpy difference of 25 kJ/mol, which cannot be explained by the formation energy of B vacancies. However, the presence of random boron vacancies possibly stabilizes the cubic structure via a local strain compensation mechanism during the growth of the crystal. For UPt3B the DFT results agree well with the experimental findings.

  13. Pre-irradiation spatial distribution and stability of boride particles in rapidly solidified boron-doped stainless steels

    SciTech Connect

    Kanani, N.; Arnberg, L.; Harling, O.K.

    1981-01-01

    The time temperature behavior of boride particles has been studied in rapidly solidified ultra low carbon and nitrogen modified 316 stainless steel with 0.088% boron and 0.45% zirconium. The results show that the as-splat-cooled specimens exhibit precipitates at the grain boundaries and triple junctions. For temperatures up to about 750/sup 0/C no significant microstructural changes occur for short heat treatment times. In the temperature range of 750 to 950/sup 0/C, however, particles typically 100 to 500 A in diameter containing Zr and B are formed within the grains. Higher temperatures enhance the formation of such particles and give rise to particle networks. The results show that a fine and uniform distribution of the boride particles almost exclusively within the grains can be achieved if proper annealing conditions are chosen. This type of distribution is an important requirement for the homogeneous production of helium during neutron irradiation in fast reactors.

  14. Magnesium Aluminum Borides as Explosive Materials

    DTIC Science & Technology

    2011-12-20

    Analog to MgB2,” Phys. Rev. B, 73[18] 180501-4 (2006). 29. Handbook of Chemistry and Physics, 63rd Edition ( CRC Press, Boca Raton, 1982). 30. R. Naslain...Engineering Properties of Borides,” Engineered Materials Handbook , Ceramics and Glasses, Vol. 4 (ASM, Metals Park, PA. 1991). 2. G. V. Samsonov and...I. M. Vinitskii, Handbook of Refractory Compounds (Plenum Press, 1980). 3. T. Lundstrom, “Transition Metal Borides,” pp. 351-376 in Boron and

  15. Combustion front dynamics in the combustion synthesis of refractory metal carbides and di-borides using time-resolved X-ray diffraction.

    PubMed

    Wong, Joe; Larson, E M; Waide, P A; Frahm, R

    2006-07-01

    A compact diffraction-reaction chamber, using a 2-inch photodiode array detector, has been employed to investigate the chemical dynamics at the combustion front of a selected series of refractory metal carbides and di-borides from their constituent element reactants as well as binary products from B4C as a reactant. These systems are denoted as (i) M + C --> MC; (ii) M + 2B --> MB2; and (iii) 3M + B4C --> 2MB2 + MC, where M = Ti, Zr, Nb, Hf or Ta. Time-resolved X-ray diffraction using intense synchrotron radiation at frame rates up to 10 frames s(-1) (or 100 ms frame(-1)) was employed. The combustion reactions were found to complete within 200-400 ms. In contrast to the Ta + C --> TaC combustion system studied earlier, in which a discernible intermediate sub-carbide phase was first formed, reacted further and disappeared to yield the final TaC product, no intermediate sub-carbide or sub-boride was detected in the current systems. Combustion for the Ti, Zr and Hf systems involved a liquid phase, in which the adiabatic temperatures Tad are well above the melting points of the respective reactant metals and have a typical combustion front velocity of 5-6 mm s(-1). The Nb and Ta systems have lower Tad, involving no liquid phase. These are truly solid combustion systems and have a lower combustion front velocity of 1-2 mm s(-1). The current study opens up a new avenue to chemical dynamics and macrokinetic investigations of high-temperature solid-state reactions.

  16. Metallic Borides, La 2 Re 3 B 7 and La 3 Re 2 B 5 , Featuring Extensive Boron–Boron Bonding

    DOE PAGES

    Bugaris, Daniel E.; Malliakas, Christos D.; Chung, Duck Young; ...

    2016-01-26

    We synthesized La2Re3B7 and La3Re2B5 in single-crystalline form from a molten La/Ni eutectic at 1000°C, in the first example of the flux crystal growth of ternary rare-earth rhenium borides. Both compounds crystallize in their own orthorhombic structure types, with La2Re3B7 (space group Pcca) having lattice parameters a = 7.657(2) Å, b = 6.755(1) Å, and c = 11.617(2) Å, and La3Re2B5 (space group Pmma) having lattice parameters a = 10.809(2) Å, b = 5.287(1) Å, and c = 5.747(1) Å. Furthermore, the compounds possess three-dimensional framework structures that are built up from rhenium boride polyhedra and boron-boron bonding. La3Re2B5 featuresmore » fairly common B2 dumbbells, whereas La2Re3B7 has unique one-dimensional subunits composed of alternating triangular B3 and trans-B4 zigzag chain fragments. Also observed in La3Re2B5 is an unusual coordination of B by an octahedron of La atoms. Electronic band structure calculations predict that La2Re3B7 is a semimetal, which is observed in the electrical resistivity data as measured on single crystals, with behavior obeying the Bloch-Grüneisen model and a room-temperature resistivity ρ300K of ~ 375 μΩ cm. The electronic band structure calculations also suggest that La3Re2B5 is a regular metal.« less

  17. Metallic Borides, La2Re3B7 and La3Re2B5, Featuring Extensive Boron-Boron Bonding.

    PubMed

    Bugaris, Daniel E; Malliakas, Christos D; Chung, Duck Young; Kanatzidis, Mercouri G

    2016-02-15

    La2Re3B7 and La3Re2B5 have been synthesized in single-crystalline form from a molten La/Ni eutectic at 1000 °C in the first example of the flux crystal growth of ternary rare-earth rhenium borides. Both compounds crystallize in their own orthorhombic structure types, with La2Re3B7 (space group Pcca) having lattice parameters a = 7.657(2) Å, b = 6.755(1) Å, and c = 11.617(2) Å, and La3Re2B5 (space group Pmma) having lattice parameters a = 10.809(2) Å, b = 5.287(1) Å, and c = 5.747(1) Å. The compounds possess three-dimensional framework structures that are built up from rhenium boride polyhedra and boron-boron bonding. La3Re2B5 features fairly common B2 dumbbells, whereas La2Re3B7 has unique one-dimensional subunits composed of alternating triangular B3 and trans-B4 zigzag chain fragments. Also observed in La3Re2B5 is an unusual coordination of B by an octahedron of La atoms. Electronic band structure calculations predict that La2Re3B7 is a semimetal, which is observed in the electrical resistivity data as measured on single crystals, with behavior obeying the Bloch-Grüneisen model and a room-temperature resistivity ρ300 K of ∼375 μΩ cm. The electronic band structure calculations also suggest that La3Re2B5 is a regular metal.

  18. Stability and crystal chemistry of the ternary borides M2(Ni21-xMx)B6 (M tbnd Ti, Zr, Hf)

    NASA Astrophysics Data System (ADS)

    Artini, C.; Provino, A.; Valenza, F.; Pani, M.; Cacciamani, G.

    2016-01-01

    A crystallochemical study was undertaken to investigate the structural stability and the compositional extent of the ternary borides M2(Ni21-xMx)B6 (M tbnd Ti, Zr, Hf). This phase often occurs during the production of MB2 joints by means of Ni-B brazing alloys. Samples with the nominal compositions M2Ni21B6 and M3Ni20B6 were synthesized by arc melting and characterized by optical and electron microscopy, and X-ray diffraction. Crystal structure refinements were performed by the Rietveld method. The compositional boundaries of the ternary phases were experimentally determined and found strictly related to the M/Ni size ratio. The stability of this structure is mainly determined by the capability of the structure to expand under the effect of the Ni substitution by the M atom. The CALPHAD modeling of the three M-Ni-B ternary systems in the Ni-rich corner of the phase diagram, performed on the basis of the obtained structural data, shows a good agreement with experimental results.

  19. The complex metal-rich boride Ti{sub 1+x}Rh{sub 2-x+y}Ir{sub 3-y}B{sub 3} (x=0.68, y=1.06) with a new structure type containing B{sub 4} zigzag fragments: Synthesis, crystal chemistry and theoretical calculations

    SciTech Connect

    Goerens, Christian; Fokwa, Boniface P.T.

    2012-08-15

    : Black-Right-Pointing-Pointer Synthesis of a new metal-rich complex boride. Black-Right-Pointing-Pointer New structure type containing isolated boron and trans zigzag B{sub 4} units. Black-Right-Pointing-Pointer Crystallographic parameters and bond length well reproduced by theory. Black-Right-Pointing-Pointer Strong boron-boron and metal-boron interactions responsible for structural stability. Black-Right-Pointing-Pointer Three-dimensional metallic network responsible for metallic behavior.

  20. First Principles Search for New Superconducting Layered Borides

    NASA Astrophysics Data System (ADS)

    Curtarolo, Stefano

    2007-11-01

    The identification of novel crystal structures is a fundamental step for predicting new stable compounds in alloys. While performing ab initio data mining of intermetallic compounds [1], we discover a new family of layered metal borides [2], of which MgB2 is one particular element (the new phases are called Metal Sandwich (MS)). Thermodynamic stability and electronic properties of these MS phases are investigated in details, leading to the prediction of a hypothetical novel superconductor MS-LiB [2,3]. Calculations show that the MS phases in the Li-B system exhibit electronic features similar to those of MgB2 [2,3] and CaC6 [4]. Although the predicted critical temperature of LiB is lower than that of MgB2 (references [4] and [5] for MS2-LiB and MS1-LiB, respectively), the peculiarities of MS-LiB in terms of electronic structure, layer arrangements and doping capabilities allow a lot of freedom in the search for higher Tc systems [5,6]. We acknowledge the Teragrid-Partnership for computational resources. Research supported by ONR and NSF. [1] Phys. Rev. Lett. 91, 135503 (2003). [2] Phys. Rev. B 73, 180501(R) (2006). [3] Phys. Rev. B 74, 224507 (2006). [4] Phys. Rev. B 75, 064510 (2007). [5] Phys. Rev. B 75, 144506 (2007). [6] A. N. Kolmogorov, M. Calandra, and S. Curtarolo, Engineering superconductors with ab initio methods: ternary metal borides, (2007).

  1. Gradient boride layers formed by diffusion carburizing and laser boriding

    NASA Astrophysics Data System (ADS)

    Kulka, M.; Makuch, N.; Dziarski, P.; Mikołajczak, D.; Przestacki, D.

    2015-04-01

    Laser boriding, instead of diffusion boriding, was proposed to formation of gradient borocarburized layers. The microstructure and properties of these layers were compared to those-obtained after typical diffusion borocarburizing. First method of treatment consists in diffusion carburizing and laser boriding only. In microstructure three zones are present: laser borided zone, hardened carburized zone and carburized layer without heat treatment. However, the violent decrease in the microhardness was observed below the laser borided zone. Additionally, these layers were characterized by a changeable value of mass wear intensity factor thus by a changeable abrasive wear resistance. Although at the beginning of friction the very low values of mass wear intensity factor Imw were obtained, these values increased during the next stages of friction. It can be caused by the fluctuations in the microhardness of the hardened carburized zone (HAZ). The use of through hardening after carburizing and laser boriding eliminated these fluctuations. Two zones characterized the microstructure of this layer: laser borided zone and hardened carburized zone. Mass wear intensity factor obtained a constant value for this layer and was comparable to that-obtained in case of diffusion borocarburizing and through hardening. Therefore, the diffusion boriding could be replaced by the laser boriding, when the high abrasive wear resistance is required. However, the possibilities of application of laser boriding instead of diffusion process were limited. In case of elements, which needed high fatigue strength, the substitution of diffusion boriding by laser boriding was not advisable. The surface cracks formed during laser re-melting were the reason for relatively quickly first fatigue crack. The preheating of the laser treated surface before laser beam action would prevent the surface cracks and cause the improved fatigue strength. Although the cohesion of laser borided carburized layer was

  2. Electronic, structural and magnetic studies of niobium borides of group 8 transition metals, Nb{sub 2}MB{sub 2} (M=Fe, Ru, Os) from first principles calculations

    SciTech Connect

    Touzani, Rachid St.; Fokwa, Boniface P.T.

    2014-03-15

    The Nb{sub 2}FeB{sub 2} phase (U{sub 3}Si{sub 2}-type, space group P4/mbm, no. 127) is known for almost 50 years, but until now its magnetic properties have not been investigated. While the synthesis of Nb{sub 2}OsB{sub 2} (space group P4/mnc, no. 128, a twofold superstructure of U{sub 3}Si{sub 2}-type) with distorted Nb-layers and Os{sub 2}-dumbbells was recently achieved, “Nb{sub 2}RuB{sub 2}” is still not synthesized and its crystal structure is yet to be revealed. Our first principles density functional theory (DFT) calculations have confirmed not only the experimental structures of Nb{sub 2}FeB{sub 2} and Nb{sub 2}OsB{sub 2}, but also predict “Nb{sub 2}RuB{sub 2}” to crystalize with the Nb{sub 2}OsB{sub 2} structure type. According to chemical bonding analysis, the homoatomic B–B interactions are optimized and very strong, but relatively strong heteroatomic M–B, B–Nb and M–Nb bonds (M=Fe, Ru, Os) are also found. These interactions, which together build a three-dimensional network, are mainly responsible for the structural stability of these ternary borides. The density-of-states at the Fermi level predicts metallic behavior, as expected, from metal-rich borides. Analysis of possible magnetic structures concluded preferred antiferromagnetic ordering for Nb{sub 2}FeB{sub 2}, originating from ferromagnetic interactions within iron chains and antiferromagnetic exchange interactions between them. -- Graphical abstract: Nb{sub 2}FeB{sub 2} (U{sub 3}Si{sub 2} structure type, space group P4/mbm, no. 127) is predicted to order antiferromagnetically, due to the presence of iron chains which show ferromagnetic interactions in the chains and antiferromagnetic interactions between them. “Nb{sub 2}RuB{sub 2}” is predicted to crystallize with the recently discovered Nb{sub 2}OsB{sub 2} twofold superstructure (space group P4/mnc, no. 128) of U{sub 3}Si{sub 2} structure type. The building of ruthenium dumbbells instead of chains along [001] is found to be

  3. Metallic alloy stability studies

    NASA Technical Reports Server (NTRS)

    Firth, G. C.

    1983-01-01

    The dimensional stability of candidate cryogenic wind tunnel model materials was investigated. Flat specimens of candidate materials were fabricated and cryo-cycled to assess relative dimensional stability. Existing 2-dimensional airfoil models as well as models in various stages of manufacture were also cryo-cycled. The tests indicate that 18 Ni maraging steel offers the greatest dimensional stability and that PH 13-8 Mo stainless steel is the most stable of the stainless steels. Dimensional stability is influenced primarily by metallurgical transformations (austenitic to martensitic) and manufacturing-induced stresses. These factors can be minimized by utilization of stable alloys, refinement of existing manufacturing techniques, and incorporation of new manufacturing technologies.

  4. Development and application of high strength ternary boride base cermets

    SciTech Connect

    Takagi, Ken-ichi . E-mail: u4381@toyokohan.co.jp

    2006-09-15

    Reaction boronizing sintering is a novel strategy to form a ternary boride coexisting with a metal matrix in a cermet during liquid phase sintering. This new sintering technique has successfully developed world first ternary boride base cermets with excellent mechanical properties such as Mo{sub 2}FeB{sub 2}, Mo{sub 2}NiB{sub 2} and WCoB base ones. In these cermets Mo{sub 2}FeB{sub 2} and Mo{sub 2}NiB{sub 2} base ones consist of a tetragonal M {sub 3}B{sub 2} (M: metal)-type complex boride as a hard phase and a transition metal base matrix. The cermets have already been applied to wear resistant applications such as injection molding machine parts, can making tools, and hot copper extruding dies, etc. This paper focuses on the characteristics, effects of the additional elements on the mechanical properties and structure, and practical applications of the ternary boride base cermets. - Graphical abstract: TRS and hardness of Ni-5B-51Mo-17.5Cr and Ni-5B-51Mo-12.5Cr-5V-xMn mass% cermets as functions of Mn content (Fig. 17)

  5. Morphology and structure of borides in as-cast titanium and gamma-titanium aluminide-based alloys

    NASA Astrophysics Data System (ADS)

    Kitkamthorn, Usanee

    In this study, the morphology and structure of the borides in boron-modified Ti- and gamma-TiAl-based alloys have been investigated using SEM, TEM, and HRTEM. A variety of different boride morphologies was observed including plates, needles, and ribbons. For the plate and needle borides, the major boride phase is B27 TiB. The needle borides have their major axis parallel to [010], and are bounded by (100) and {101} type-facets. The plate borides develop the same types of facets as the needles and have habit planes parallel to the (100). There are high densities of intrinsic stacking faults on (100) in these borides and these correspond to thin embedded layers of the Bf structure. The plate borides do not exhibit well-defined ORs with respect to the surrounding phases, suggesting that they develop in the liquid melt and were then trapped by the growing solid. Needle borides are observed mostly at boundaries between lamellar colonies: these needles tend to occur in groups lying nearly parallel to one another and, in some cases, to adopt well-defined ORs with respect to the surrounding phases. Cored borides with metallic phases such as beta, alpha, o and alpha 2+gamma in the center are frequently observed, especially in the Ti-based alloy. These core phases usually adopt well-defined ORs with respect to the surrounding boride which enable low-energy coherent interfaces to form between the phases. The ribbon borides are comprised of thin boride flakes interspersed with thin metallic layers. The major boride phase in these flakes is Bf TiB. The habit plane of the flakes is (010) and there are high densities of faults on this plane corresponding to intergrowths of the Ti3B 4 and TiB2 phases, together with thin layers or occluded pockets of metallic B2 phase. Occasional faults are observed on {110} corresponding to embedded slabs of B27 TiB. There is a well-defined OR between the boride flakes and the B2 phase within the ribbons, but not with the surrounding matrix. The

  6. Carbide and boride laser modification of steels

    NASA Astrophysics Data System (ADS)

    Major, Boguslaw; Ebner, Reinhold

    1997-10-01

    Microstructure modification by laser remelting or laser alloying was studied on carbon Ck45 and high speed steels. Laser remelting of Ck45 by overlapping laser tracks led to a great refinement of martensitic structure, especially in the heat affected zone of subsequent laser track. High speed steel (HSS) M2 after laser remelting showed, beside the tetragonal martensite, the diffraction lines of cubic carbides of the M6C and M12C types. Laser alloying of M2 HSS using vanadium carbide (VC) additions caused increasing of eutectic in the interdendritic space, which was accompanied with reduction of the M6C and rising of the MC. M2 HSS laser alloyed with molybdenum carbide (Mo2C) showed formation of the M6C for the hipereutectic compositions while at the highest concentrations of molybdenum, primary dendrites of the M2C and stabilized ferrite were stated. High additions of borides: CrB or VB2; developed formation of the primary borides of blocky type containing a high amount of W, Cr or W, V, respectively. Laser alloying of Ck45 by means of: CrB, VB2 and B4C showed: in the case of CrB an eutectic (alpha) '/M3(C,B)/M2B as well as primary precipitates of the M2B phase for hipereutectic compositions; by adding VB2, the M3B2 and M2B phases were identified experimentally for hipereutectic concentrations; for alloying using B4C, the cellular dendritic structure together with primary borides of the (tau) -M23(C,B)6 phase were stated for hipereutectic compositions. The phase diagrams of M2 HSS + (VC or Mo2C) as well as Ck45 + B4C systems were calculated to predict changes of the constitutions due to laser alloying. Comparison of the solidification structures established experimentally with the calculated phase diagrams revealed a good correlation for the carbides, especially.

  7. 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.

  8. Structure stability and spectroscopy of metal clusters

    SciTech Connect

    Not Available

    1993-01-01

    Theory based on self-consistent field-linear combinations of atomic orbitals-molecular orbital theory was applied to clusters. Four areas were covered: electronic structure, equilibrium geometries, and stability of charged clusters, interaction of metal clusters with H and halogen atoms, thermal stability of isolated clusters, and stability and optical properties of hetero-atomic clusters. (DLC)

  9. THE STABILITY AND REVERSIBILITY OF METALLIC BOROHYDRIDES

    SciTech Connect

    Au, M

    2007-07-27

    In effort to develop reversible metallic borohydrides with high hydrogen storage capacity and low dehydriding temperature, several new materials have been synthesized by modifying LiBH{sub 4} with various metal halides and hydrides. The investigation shows that the halide modification effectively reduced the dehydriding temperature through ion exchange interaction. The effective halides are TiCl{sub 3}, TiF{sub 3}, ZnF{sub 2} and AlF{sub 3}. The material LiBH{sub 4}+0.1TiF{sub 3} desorbs 3.5wt% and 8.5wt% hydrogen at 150 C and 450 C respectively. It re-absorbed 6wt% hydrogen at 500 C and 70 bar after dehydrogenation. The XRD of the rehydrided samples confirmed the formation of LiBH{sub 4}. It indicates that the materials are reversible at the conditions given. However, a number of other halides: MgF{sub 2}, MgCl{sub 2}, CaCl{sub 2}, SrCl{sub 2} and FeCl{sub 3}, did not reduce dehydriding temperature of LiBH{sub 4} significantly. TGA-RGA analysis indicated that some halide modified lithium borohydrides such as LiBH{sub 4}+0.1ZnF{sub 2} evolved diborane during dehydrogenation, but some did not such as LiBH{sub 4}+0.1TiCl{sub 3}. The formation of diborane caused unrecoverable capacity loss resulting in irreversibility. It is suggested that the lithium borohydrides modified by the halides containing the metals that can not form metal borides with boron are likely to evolve diborane during dehydriding. It was discovered that halide modification reduces sensitivity of LiBH{sub 4}. The materials such as LiBH{sub 4}+0.1TiCl{sub 3} and LiBH{sub 4}+0.5TiCl{sub 3} can be handled in open air without visible reaction.

  10. Plasma boriding of a cobalt-chromium alloy as an interlayer for nanostructured diamond growth

    NASA Astrophysics Data System (ADS)

    Johnston, Jamin M.; Jubinsky, Matthew; Catledge, Shane A.

    2015-02-01

    Chemical vapor deposited (CVD) diamond coatings can potentially improve the wear resistance of cobalt-chromium medical implant surfaces, but the high cobalt content in these alloys acts as a catalyst to form graphitic carbon. Boriding by high temperature liquid baths and powder packing has been shown to improve CVD diamond compatibility with cobalt alloys. We use the microwave plasma-enhanced (PE) CVD process to deposit interlayers composed primarily of the borides of cobalt and chromium. The use of diborane (B2H6) in the plasma feedgas allows for the formation of a robust boride interlayer for suppressing graphitic carbon during subsequent CVD of nano-structured diamond (NSD). This metal-boride interlayer is shown to be an effective diffusion barrier against elemental cobalt for improving nucleation and adhesion of NSD coatings on a CoCrMo alloy. Migration of elemental cobalt to the surface of the interlayer is significantly reduced and undetectable on the surface of the subsequently-grown NSD coating. The effects of PECVD boriding are compared for a range of substrate temperatures and deposition times and are evaluated using glancing-angle X-ray diffraction (XRD), cross-sectional scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and micro-Raman spectroscopy. Boriding of CoCrMo results in adhered nanostructured diamond coatings with low surface roughness.

  11. Metallic Borides, La 2 Re 3 B 7 and La 3 Re 2 B 5 , Featuring Extensive Boron–Boron Bonding

    SciTech Connect

    Bugaris, Daniel E.; Malliakas, Christos D.; Chung, Duck Young; Kanatzidis, Mercouri G.

    2016-01-26

    We synthesized La2Re3B7 and La3Re2B5 in single-crystalline form from a molten La/Ni eutectic at 1000°C, in the first example of the flux crystal growth of ternary rare-earth rhenium borides. Both compounds crystallize in their own orthorhombic structure types, with La2Re3B7 (space group Pcca) having lattice parameters a = 7.657(2) Å, b = 6.755(1) Å, and c = 11.617(2) Å, and La3Re2B5 (space group Pmma) having lattice parameters a = 10.809(2) Å, b = 5.287(1) Å, and c = 5.747(1) Å. Furthermore, the compounds possess three-dimensional framework structures that are built up from rhenium boride polyhedra and boron-boron bonding. La3Re2B5 features fairly common B2 dumbbells, whereas La2Re3B7 has unique one-dimensional subunits composed of alternating triangular B3 and trans-B4 zigzag chain fragments. Also observed in La3Re2B5 is an unusual coordination of B by an octahedron of La atoms. Electronic band structure calculations predict that La2Re3B7 is a semimetal, which is observed in the electrical resistivity data as measured on single crystals, with behavior obeying the Bloch-Grüneisen model and a room-temperature resistivity ρ300K of ~ 375 μΩ cm. The electronic band structure calculations also suggest that La3Re2B5 is a regular metal.

  12. Stability of metal particle and metal particulate media

    NASA Technical Reports Server (NTRS)

    Okamoto, Kazuhiro

    1992-01-01

    Metal particulate (MP) video tape was launched for 8 mm video tape in 1985. Since then MP tapes have been applied to several consumer formats and instrumental formats because of its superior electrical performance. Recently data storage media, such as DDS and D-8, have started employing MP tape. However, there are serious concerns with archival stability of MP tape particularly in the case of data storage use, as metal particles essentially have problems with chemical instability and are susceptible to oxidation and corrosion. Although there were some studies about the archival stability of metal particles or MP tapes, a clear understanding has yet to be reached. In this paper, we report the stability of magnetic properties of current metal particles, and then discuss the new technologies to improve the stability further.

  13. Metallic nanoshells on porphyrin-stabilized emulsions

    DOEpatents

    Wang, Haorong; Song, Yujiang; Shelnutt, John A; Medforth, Craig J

    2013-10-29

    Metal nanostructures formed by photocatalytic interfacial synthesis using a porphyrin-stabilized emulsion template and the method for making the nanostructures. Catalyst-seeded emulsion droplets are employed as templates for hollow-nanoshell growth. The hollow metal nanospheres may be formed with or without inclusions of other materials.

  14. Boride-based nano-laminates with MAX-phase-like behaviour

    SciTech Connect

    Telle, Rainer . E-mail: telle@ghi.rwth-aachen.de; Momozawa, Ai; Music, Denis; Schneider, Jochen M.

    2006-09-15

    MAX-phases being usually composed of transition metals, group A elements and carbon/nitrogen are considered interesting materials for many applications because of their tremendous bulk modulus, 'reversible' plasticity, and machinability. This is mainly due to their unique kind of bonding comprising covalent, ionic as well as metallic bonds providing 'easy' planes of rupture and deformability due to the layered crystal structures. In transition metal boride systems, similar types of bonding are available. In particular the W{sub 2}B{sub 5}-structure type and its stacking variations allow the synthesis of strongly layered crystal structures exhibiting unique delamination phenomena. The paper presents ab initio calculations showing the similarities of bonding between the ternary carbides and the corresponding ternary or quaternary borides. Formation of boride-based nano-laminates from auxiliary liquid phases, from the melt as well as during sintering and precipitation from supersaturated solid solutions will be discussed by means of SEM and TEM studies. The role of impurities weakening the interlayer bonding will be addressed in particular. The pronounced cleavage parallel to the basal plane gives rise for crack deflection and pull-out mechanisms if the laminates are dispersed in brittle matrices such as boron carbide, silicon carbide or other transition metal borides. - Graphical abstract: Some transition metal borides crystallise in a layered structure of alternating stacks of metal and boron atoms giving rise for strongly anisotropic properties. Their preferred cleavage parallel and the deformability perpendicular to the basal plan are similar to the peculiar mechanical behaviour recently described for MAX-phases. Ab initio calculations of the crystal structure prove the weak bonds between the layers for a variety of borides which can be used to reinforce ceramic materials on a nano-scale level.

  15. Ultrahigh stability of atomically thin metallic glasses

    SciTech Connect

    Cao, C. R.; Huang, K. Q.; Zhao, N. J.; Sun, Y. T.; Bai, H. Y.; Gu, L. E-mail: dzheng@iphy.ac.cn Zheng, D. N. E-mail: dzheng@iphy.ac.cn Wang, W. H. E-mail: dzheng@iphy.ac.cn

    2014-07-07

    We report the fabrication and study of thermal stability of atomically thin ZrCu-based metallic glass films. The ultrathin films exhibit striking dynamic properties, ultrahigh thermal stability, and unique crystallization behavior with discrete crystalline nanoparticles sizes. The mechanisms for the remarkable high stability and crystallization behaviors are attributed to the dewetting process of the ultrathin film. We demonstrated a promising avenue for understanding some fundamental issues such as glassy structure, crystallization, deformation, and glass formation through atomic resolution imaging of the two dimensional like metallic glasses.

  16. In{sub 3}Ir{sub 3}B, In{sub 3}Rh{sub 3}B and In{sub 5}Ir{sub 9}B{sub 4}, the first indium platinum metal borides

    SciTech Connect

    Kluenter, Wilhelm; Jung, Walter . E-mail: walter.jung@uni-koeln.de

    2006-09-15

    The first indium platinum metal borides have been synthesized and structurally characterized by single crystal X-ray diffraction data. In{sub 3}Ir{sub 3}B and In{sub 3}Rh{sub 3}B are isotypic. They crystallize with the hexagonal space group P6-bar 2m and Z=1. The lattice constants are a=685.78(1)pm, c=287.30(1)pm for In{sub 3}Ir{sub 3}B and a=678.47(3)pm, c=288.61(6)pm for In{sub 3}Rh{sub 3}B. The structure which is derived from the Fe{sub 2}P type is characterized by columns of boron centered triangular platinum metal prisms inserted in a three-dimensional indium matrix. The indium atoms are on split positions. In{sub 5}Ir{sub 9}B{sub 4} (hexagonal, space group P6-bar 2m, a=559.0(2)pm, c=1032.6(3)pm, Z=1) crystallizes with a structure derived from the CeCo{sub 3}B{sub 2} type. The structure can be interpreted as a layer as well as a channel structure. In part the indium atoms are arranged at the vertices of a honeycomb net (Schlaefli symbol 6{sup 3}) separating slabs consisting of double layers of triangular Ir{sub 6}B prisms, and in part they form a linear chain in a hexagonal channel formed by iridium prisms and indium atoms of the honeycomb lattice.

  17. Radiation Stability of Metal Nanowires

    NASA Astrophysics Data System (ADS)

    Bedin, S. A.; Makhin’ko, F. F.; Ovchinnikov, V. V.; Gerasimenko, N. N.; Zagorskiy, D. L.

    2017-01-01

    The aim of this work is to investigate the radiation stability of pure nickel and iron– nickel Fe0.56Ni0.44 alloy nanowires fabricated by matrix synthesis using polymer track membranes and Ar+ and Xe+ (E = 20 keV, j = 300 μA/cm2) beam irradiation. The dependence of the stability of nanowires on their diameter, fluence, and type of implanted ions is investigated. The assumption that the thermalized regions of dense cascades of atomic displacements (thermal spikes) play an important role in the nanowire structure change is made. These regions are nanosized zones of explosive energy release and heated to several thousands of degrees.

  18. Field free, directly heated lanthanum boride cathode

    DOEpatents

    Leung, Ka-Ngo; Moussa, D.; Wilde, S.B.

    1987-02-02

    A directly heated cylindrical lanthanum boride cathode assembly is disclosed which minimizes generation of magnetic field which would interfere with electron emission from the cathode. The cathode assembly comprises a lanthanum boride cylinder in electrical contact at one end with a central support shaft which functions as one electrode to carry current to the lanthanum boride cylinder and in electrical contact, at its opposite end with a second electrode which is coaxially position around the central support shaft so that magnetic fields generated by heater current flowing in one direction through the central support shaft are cancelled by an opposite magnetic field generated by current flowing through the lanthanum boride cylinder and the coaxial electrode in a direction opposite to the current flow in the central shaft.

  19. Field free, directly heated lanthanum boride cathode

    DOEpatents

    Leung, Ka-Ngo; Moussa, David; Wilde, Stephen B.

    1991-01-01

    A directly heated cylindrical lanthanum boride cathode assembly is disclosed which minimizes generation of magnetic fields which would interfere with electron emission from the cathode. The cathode assembly comprises a lanthanum boride cylinder in electrical contact at one end with a central support shaft which functions as one electrode to carry current to the lanthanum boride cylinder and in electrical contact, at its opposite end with a second electrode which is coaxially position around the central support shaft so that magnetic fields generated by heater current flowing in one direction through the central support shaft are cancelled by an opposite magnetic field generated by current flowing through the lanthanum boride cylinder and the coaxial electrode in a direction opposite to the current flow in the central shaft.

  20. Stabilizing metal nanoparticles for heterogeneous catalysis.

    PubMed

    Cao, Anmin; Lu, Rongwen; Veser, Götz

    2010-11-07

    Metal nanoparticles hold great promise for heterogeneous catalysis due to their high dispersion, large concentration of highly undercoordinated surface sites, and the presence of quantum confinement effects, which can drastically alter their reactivity. However, the poor thermal stability of nano-sized particles limits their use to low temperature conditions and constitutes one of the key hurdles towards industrial application. The present perspective paper briefly reviews the mechanisms underlying nanoparticle sintering, and then gives an overview of emerging approaches towards stabilizing metal nanoparticles for heterogeneous catalysis. We conclude by highlighting the current needs for further developments in the field.

  1. Characterization of AISI 4140 borided steels

    NASA Astrophysics Data System (ADS)

    Campos-Silva, I.; Ortiz-Domínguez, M.; López-Perrusquia, N.; Meneses-Amador, A.; Escobar-Galindo, R.; Martínez-Trinidad, J.

    2010-02-01

    The present study characterizes the surface of AISI 4140 steels exposed to the paste-boriding process. The formation of Fe 2B hard coatings was obtained in the temperature range 1123-1273 K with different exposure times, using a 4 mm thick layer of boron carbide paste over the material surface. First, the growth kinetics of boride layers at the surface of AISI 4140 steels was evaluated. Second, the presence and distribution of alloying elements on the Fe 2B phase was measured using the Glow Discharge Optical Emission Spectrometry (GDOES) technique. Further, thermal residual stresses produced on the borided phase were evaluated by X-ray diffraction (XRD) analysis. The fracture toughness of the iron boride layer of the AISI 4140 borided steels was estimated using a Vickers microindentation induced-fracture testing at a constant distance of 25 μm from the surface. The force criterion of fracture toughness was determined from the extent of brittle cracks, both parallel and perpendicular to the surface, originating at the tips of an indenter impression. The fracture toughness values obtained by the Palmqvist crack model are expressed in the form KC( π/2) > KC > KC(0) for the different applied loads and experimental parameters of the boriding process.

  2. New examples of ternary rare-earth metal boride carbides containing finite boron carbon chains: The crystal and electronic structure of RE15B6C20 (RE=Pr, Nd)

    NASA Astrophysics Data System (ADS)

    Babizhetskyy, Volodymyr; Mattausch, Hansjürgen; Simon, Arndt; Hiebl, Kurt; Ben Yahia, Mouna; Gautier, Régis; Halet, Jean-François

    2008-08-01

    The ternary rare-earth metal boride carbides RE15B6C20 (RE=Pr, Nd) were synthesized by co-melting the elements. They exist above 1270 K. Their crystal structures were determined from single-crystal X-ray diffraction data. Both crystallize in the space group P1¯, Z=1, a=8.3431(8) Å, b=9.2492(9) Å, c=8.3581(8) Å, α=84.72(1)°, β=89.68(1)°, γ =84.23(1)° (R1=0.041 (wR2=0.10) for 3291 reflections with Io>2σ(Io)) for Pr15B6C20, and a=8.284(1) Å, b=9.228(1) Å, c=8.309(1) Å, α=84.74(1)°, β=89.68(1)°, γ=84.17(2)° (R1=0.033 (wR2=0.049) for 2970 reflections with Io>2σ(Io)) for Nd15B6C20. Their structure consists of a three-dimensional framework of rare-earth metal atoms resulting from the stacking of slightly corrugated and distorted square nets, leading to cavities filled with unprecedented B2C4 finite chains, disordered C3 entities and isolated carbon atoms, respectively. Structural and theoretical analyses suggest the ionic formulation (RE3+)15([B2C4]6-)3([C3]4-)2(C4-)2·11ē. Accordingly, density functional theory calculations indicate that the compounds are metallic. Both structural arguments as well as energy calculations on different boron vs. carbon distributions in the B2C4 chains support the presence of a CBCCBC unit. Pr15B6C18 exhibits antiferromagnetic order at TN=7.9 K, followed by a meta-magnetic transition above a critical external field B>0.03 T. On the other hand, Nd15B6C18 is a ferromagnet below TC≈40 K.

  3. A kinetic model for the borided layers by the paste-boriding process

    NASA Astrophysics Data System (ADS)

    Keddam, M.

    2004-09-01

    This work is dedicated to the study of the growth kinetics of the borided layers obtained by the paste-boriding process. A diffusion model based on Fick's laws and coupled with a thermodynamic description of the Fe-B binary system was suggested to simulate the growth kinetics of the borided layers consisting only of Fe 2B phase and containing 8.83 wt.% B onto the iron substrate within the temperature range of 1223-1323 K. The validation of the diffusion model was achieved by comparing the simulation results with the experimental data taken from the literature and a good agreement was observed. Furthermore, the model was able to predict the boron-depth-concentration profile for Fe 2B phase as well as the thickness of the borided layers depending on the boriding parameters.

  4. Stabilize heavy metals in soils and sludges

    SciTech Connect

    1995-03-01

    To stabilize heavy metals in soils, sludges, ash from incinerators and power plants, and baghouse dusts, Solucorp Industries (Saddle Brook, N.J.) has developed the Molecular Bonding System (MBS). Using a patented mix of chemical additives, the MBS process bonds highly reactive metal ions to form non-leachable molecules, rendering the metals inert. The chemical reactions are said to be permanent, and for each application, the additive mix is specially formulated to meet site-specific conditions. Recently, the MBS process was accepted into the US Environmental Protection Agency`s Site Demonstration Program as an innovative technology for stabilizing heavy metals. Bench-scale and pilot tests have proven the effectiveness of the MBS process for a wide array of metals, including arsenic, cadmium, chromium, copper, lead, mercury, nickel, silver and zinc. The process is designed for wastes classified as D004 through D011, as well as K-listed wastes associated with metal-plating operations. It can treat waste in drums or in bulk, says the firm, but is not suitable for liquid streams.

  5. Electron momentum distribution and electronic response of ceramic borides

    NASA Astrophysics Data System (ADS)

    Heda, N. L.; Meena, B. S.; Mund, H. S.; Sahariya, Jagrati; Kumar, Kishor; Ahuja, B. L.

    2017-03-01

    Isotropic Compton profiles of transition metal based ceramics TaB and VB have been measured using 137Cs (661.65 keV) γ-ray Compton spectrometer. The experimental momentum densities are compared with those deduced using linear combination of atomic orbitals (LCAO) with Hartree-Fock (HF), density functional theory (DFT) with Wu-Cohen generalized gradient approximation (WCGGA) and also the hybridization of HF and DFT (namely B3PW and PBE0) schemes. It is found that LCAO-DFT-WCGGA scheme based profiles give an overall better agreement with the experimental data, for both the borides. In addition, we have computed the Mulliken's population (MP) charge transfer data, energy bands, density of states and Fermi surface topology of both the borides using full potential-linearized augmented plane wave (FP-LAPW) and LCAO methods with DFT-WCGGA scheme. Cross-overs of Fermi level by the energy bands corresponding to B-2p and valence d-states of transition metals lead to metallic character in both the compounds. Equal-valence-electron-density profiles and MP analysis suggest more ionic character of VB than that of TaB.

  6. Flexible amorphous metal films with high stability

    NASA Astrophysics Data System (ADS)

    Liu, M.; Cao, C. R.; Lu, Y. M.; Wang, W. H.; Bai, H. Y.

    2017-01-01

    We report the formation of amorphous Cu50Zr50 films with a large-area of more than 100 cm2. The films were fabricated by ion beam assisted deposition with a slow deposition rate at moderate temperature. The amorphous films have markedly enhanced thermal stability, excellent flexibility, and high reflectivity with atomic level smoothness. The multifunctional properties of the amorphous films are favorites in the promising applications of smart skin or wearable devices. The method of preparing highly stable amorphous metal films by tuning the deposition rate instead of deposition temperature could pave a way for exploring amorphous metal films with unique properties.

  7. Structure and Energy Stability of Metal Nanoparticles

    NASA Astrophysics Data System (ADS)

    Barron, Hector; Palomares-Baez, Juan Pedro; Velazquez-Salazar, Jesus; Rodriguez-Lopez, Jose Luis; Jose-Yacaman, Miguel; University of Texas at San Antonio Collaboration; Instituto Potosino de Investigacion Cientufica y Tecnologica Collaboration

    2011-03-01

    In this work we present a theoretical model for the structural evolution and energy stability for metal nanoparticles from the small (1-2 nm) to the big (~ 50 nm) size ranges. We have found that the appearances of structural lattice defects as well as surface reconstructions are important factors that highly influence the growth process. A simple assembly model for a path transformation for metal nanoparticles is presented and compare with experimental evidence. Acknowledgements: Financial support from National Science Foundation Grant DMR-0934218 is acknowledged, as well as grants for the use of High Performance Computational Resources from the supercomputer center TACC-University of Texas at Austin.

  8. Kinetics of electrochemical boriding of low carbon steel

    NASA Astrophysics Data System (ADS)

    Kartal, G.; Eryilmaz, O. L.; Krumdick, G.; Erdemir, A.; Timur, S.

    2011-05-01

    In this study, the growth kinetics of the boride layers forming on low carbon steel substrates was investigated during electrochemical boriding which was performed at a constant current density of 200 mA/cm 2 in a borax based electrolyte at temperatures ranging from 1123 K to 1273 K for periods of 5-120 min. After boriding, the presence of both FeB and Fe 2B phases were confirmed by the X-ray diffraction method. Cross-sectional microscopy revealed a very dense and thick morphology for both boride phases. Micro hardness testing of the borided steel samples showed a significant increase in the hardness of the borided surfaces (i.e., up to (1700 ± 200) HV), while the hardness of un-borided steel samples was approximately (200 ± 20) HV. Systematic studies over a wide range of boriding time and temperature confirmed that the rate of the boride layer formation is strongly dependent on boriding duration and has a parabolic character. The activation energy of boride layer growth for electrochemical boriding was determined as (172.75 ± 8.6) kJ/mol.

  9. Synthesis of ferromagnetic nanoparticles, formic acid oxidation catalyst nanocomposites, and late-transition metal-boride intermetallics by unique synthetic methods and single-source precursors

    NASA Astrophysics Data System (ADS)

    Wellons, Matthew S.

    The design, synthesis, and characterization of magnetic alloy nanoparticles, supported formic acid oxidation catalysts, and superhard intermetallic composites are presented. Ferromagnetic equatomic alloy nanoparticles of FePt, FePd, and CoPt were synthesized utilizing single-source heteronuclear organometallic precursors supported on an inert water-soluble matrix. Direct conversion of the precursor-support composite to supported ferromagnetic nanoparticles occurs under elevated temperatures and reducing conditions with metal-ion reduction and minimal nanoparticle coalescence. Nanoparticles were easily extracted from the support by addition of water and characterized in structure and magnetic properties. Palladium and platinum based nanoparticles were synthesized with microwave-based and chemical metal-ion reduction strategies, respectively, and tested for catalytic performance in a direct formic acid fuel cell (DFAFC). A study of palladium carbide nanocomposites with various carbonaceous supports was conducted and demonstrated strong activity comparable to commercially available palladium black, but poor catalytic longevity. Platinum-lead alloy nanocomposites synthesized with chemical reduction and supported on Vulcan carbon demonstrated strong activity, excellent catalytic longevity, and were subsequently incorporated into a prototype DFAFC. A new method for the synthesis of superhard ceramics on polymer substrates called Confined Plasma Chemical Deposition (CPCD) was developed. The CPCD method utilizes a tuned Free Electron Laser to selectively decompose the single-source precursor, Re(CO)4(B3H8), in a plasma-like state resulting in the superhard intermetallic ReB2 deposited on polymer substrates. Extension of this method to the synthesis of other hard of superhard ceramics; WB4, RuB2, and B4C was demonstrated. These three areas of research show new synthetic methods and novel materials of technological importance, resulting in a substantial advance in their

  10. Stability of bulk metallic glass structure

    SciTech Connect

    Jain, H.; Williams, D.B.

    2003-06-18

    The fundamental origins of the stability of the (Pd-Ni){sub 80}P{sub 20} bulk metallic glasses (BMGs), a prototype for a whole class of BMG formers, were explored. While much of the properties of their BMGs have been characterized, their glass-stability have not been explained in terms of the atomic and electronic structure. The local structure around all three constituent atoms was obtained, in a complementary way, using extended X-ray absorption fine structure (EXAFS), to probe the nearest neighbor environment of the metals, and extended energy loss fine structure (EXELFS), to investigate the environment around P. The occupied electronic structure was investigated using X-ray photoelectron spectroscopy (XPS). The (Pd-Ni){sub 80}P{sub 20} BMGs receive their stability from cumulative, and interrelated, effects of both atomic and electronic origin. The stability of the (Pd-Ni){sub 80}P{sub 20} BMGs can be explained in terms of the stability of Pd{sub 60}Ni{sub 20}P{sub 20} and Pd{sub 30}Ni{sub 50}P{sub 20}, glasses at the end of BMG formation. The atomic structure in these alloys is very similar to those of the binary phosphide crystals near x=0 and x=80, which are trigonal prisms of Pd or Ni atoms surrounding P atoms. Such structures are known to exist in dense, randomly-packed systems. The structure of the best glass former in this series, Pd{sub 40}Ni{sub 40}P{sub 20} is further described by a weighted average of those of Pd{sub 30}Ni{sub 50}P{sub 20} and Pd{sub 60}Ni{sub 20}P{sub 20}. Bonding states present only in the ternary alloys were found and point to a further stabilization of the system through a negative heat of mixing between Pd and Ni atoms. The Nagel and Tauc criterion, correlating a decrease in the density of states at the Fermi level with an increase in the glass stability, was consistent with greater stability of the Pd{sub x}Ni{sub (80-x)}P{sub 20} glasses with respect to the binary alloys of P. A valence electron concentration of 1.8 e/a, which

  11. Beta cell device using icosahedral boride compounds

    DOEpatents

    Aselage, Terrence L.; Emin, David

    2002-01-01

    A beta cell for converting beta-particle energies into electrical energy having a semiconductor junction that incorporates an icosahedral boride compound selected from B.sub.12 As.sub.2, B.sub.12 P.sub.2, elemental boron having an .alpha.-rhombohedral structure, elemental boron having a .beta.-rhombohedral structure, and boron carbides of the chemical formula B.sub.12-x C.sub.3-x, where 0.15boride compound self-heals, resisting degradation from radiation damage.

  12. A Crossover from High Stiffness to High Hardness: The Case of Osmium and Its Borides

    NASA Astrophysics Data System (ADS)

    Bian, Yongming; Liu, Xiaomei; Li, Anhu; Liang, Yongcheng

    2016-09-01

    Transition-metal light-element compounds are currently raising great expectations for hard and superhard materials. Using the widely attracting osmium (Os) and its borides (OsB, Os2B3 and OsB2) as prototypes, we demonstrate by first-principles calculations that heavy transition metals, which possess high stiffness but low hardness, can be converted into highly hard materials by incorporating of light elements to form compounds. Such a crossover is a manifestation that the underlying sources of high stiffness and high hardness are fundamentally different. The stiffness is related to elastic deformation that is closely associated with valence electron density, whereas the hardness depends strongly on plastic deformation that is determined by bonding nature. Therefore, the incorporation of light atoms into transition metal should be a valid pathway of designing hard and superhard materials. This strategy is in principle also applicable to other transition-metal borides, carbides, and nitrides.

  13. Flexibility and Stability of Metal Coordination Macromolecules.

    PubMed

    Jiang, Heyan; Geng, Diya; Liu, Dapeng; Lanigan, Nicholas; Wang, Xiaosong

    2017-06-16

    The effect of chain structure on flexibility and stability of macromolecules containing weak P-Fe metal coordination bonds is studied. Migration insertion polymerization (MIP) of FpCX Fp (1) and PR2 CY PR2 (2) (Fp: CpFe(CO)2 ; CX and CY : alkyl spacers; P: phosphine; R: phenyl or isopropyl) generates P(1/2), in which the P-Fe and Fe-P bonds with opposite bonding direction are alternatively arranged in the backbone. On the other hand, P(FpCX P) synthesized from AB-type monomers (FpCX P) has P-Fe bonds arranged in the same direction. P(1/2) is more rigid and stable than P(FpCX P), which is attributed to the chain conformation resulting from the P-Fe bonding direction. In addition, the longer spacers render P(1/2) relatively flexible; the phenyl substituents, as compared with the isopropyl groups, improves the rigidity, thermal, and solution stability of P(1/2). It is therefore possible to incorporate weak metal coordination bonds into macromolecules with improved stability and adjustable flexibility for material processing. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. The fracture toughness of borides formed on boronized cold work tool steels

    SciTech Connect

    Sen, Ugur; Sen, Saduman

    2003-06-15

    In this study, the fracture toughness of boride layers of two borided cold work tool steels have been investigated. Boriding was carried out in a salt bath consisting of borax, boric acid, ferro-silicon and aluminum. Boriding was performed at 850 and 950 deg. C for 2 to 7 h. The presence of boride phases were determined by X-ray diffraction (XRD) analysis. Hardness and fracture toughness of borides were measured via Vickers indenter. Increasing of boriding time and temperature leads to reduction of fracture toughness of borides. Metallographic examination showed that boride layer formed on cold work tool steels was compact and smooth.

  15. Stability of metallic foams studied under microgravity

    NASA Astrophysics Data System (ADS)

    Wübben, Th; Stanzick, H.; Banhart, J.; Odenbach, S.

    2003-01-01

    Metal foams are prepared by mixing a metal powder and a gas-releasing blowing agent, by densifying the mix to a dense precursor and finally foaming by melting the powder compact. The foaming process of aluminium foams is monitored in situ by x-ray radioscopy. One observes that foam evolution is accompanied by film rupture processes which lead to foam coalescence. In order to elucidate the importance of oxides for foam stability, lead foams were manufactured from lead powders having two different oxide contents. The two foam types were generated on Earth and under weightlessness during parabolic flights. The measurements show that the main function of oxide particles is to prevent coalescence, while their influence on bulk viscosity of the melt is of secondary importance.

  16. Reactive Boride Brazing on Low-Alloy Automotive Grade Steel

    NASA Astrophysics Data System (ADS)

    Palanisamy, B.; Upadhyaya, A.

    2011-11-01

    Brazing is a widely used process to improve the performance of steels used in automotive applications. The substrate material is often exposed to harsh conditions in these applications and may affect the service life of the component. Reactive boride brazing aims to improve the mechanical properties of the substrate material by forming a ceramic-metal composite coating in a single-step process in situ. In this study, sintered Ancor 4300 low-alloy steel is used as the substrate with chromium-rich braze and chromium-lean braze materials. The mechanical properties of the brazed samples were studied in detail using microindentation hardness measurements and the transverse rupture test. The results indicate that the brazed superlayer has a 10 times higher hardness. There was a significant improvement in the transverse rupture strength of the steel brazed with the chromium-rich boride as compared to the pure substrate material. In an effort to reduce processing time, green compacts of the substrate were also directly brazed and yielded favorable results.

  17. Structure of superhard tungsten tetraboride: a missing link between MB2 and MB12 higher borides.

    PubMed

    Lech, Andrew T; Turner, Christopher L; Mohammadi, Reza; Tolbert, Sarah H; Kaner, Richard B

    2015-03-17

    Superhard metals are of interest as possible replacements with enhanced properties over the metal carbides commonly used in cutting, drilling, and wear-resistant tooling. Of the superhard metals, the highest boride of tungsten--often referred to as WB4 and sometimes as W(1-x)B3--is one of the most promising candidates. The structure of this boride, however, has never been fully resolved, despite the fact that it was discovered in 1961--a fact that severely limits our understanding of its structure-property relationships and has generated increasing controversy in the literature. Here, we present a new crystallographic model of this compound based on refinement against time-of-flight neutron diffraction data. Contrary to previous X-ray-only structural refinements, there is strong evidence for the presence of interstitial arrangements of boron atoms and polyhedral bonding. The formation of these polyhedral--slightly distorted boron cuboctahedra--appears to be dependent upon the defective nature of the tungsten-deficient metal sublattice. This previously unidentified structure type has an intermediary relationship between MB2 and MB12 type boride polymorphs. Manipulation of the fractionally occupied metal and boron sites may provide insight for the rational design of new superhard metals.

  18. Structure of superhard tungsten tetraboride: A missing link between MB2 and MB12 higher borides

    PubMed Central

    Lech, Andrew T.; Turner, Christopher L.; Mohammadi, Reza; Tolbert, Sarah H.; Kaner, Richard B.

    2015-01-01

    Superhard metals are of interest as possible replacements with enhanced properties over the metal carbides commonly used in cutting, drilling, and wear-resistant tooling. Of the superhard metals, the highest boride of tungsten—often referred to as WB4 and sometimes as W1–xB3—is one of the most promising candidates. The structure of this boride, however, has never been fully resolved, despite the fact that it was discovered in 1961—a fact that severely limits our understanding of its structure–property relationships and has generated increasing controversy in the literature. Here, we present a new crystallographic model of this compound based on refinement against time-of-flight neutron diffraction data. Contrary to previous X-ray–only structural refinements, there is strong evidence for the presence of interstitial arrangements of boron atoms and polyhedral bonding. The formation of these polyhedra—slightly distorted boron cuboctahedra—appears to be dependent upon the defective nature of the tungsten-deficient metal sublattice. This previously unidentified structure type has an intermediary relationship between MB2 and MB12 type boride polymorphs. Manipulation of the fractionally occupied metal and boron sites may provide insight for the rational design of new superhard metals. PMID:25733870

  19. Simulation of the growth kinetics of boride layers formed on Fe during gas boriding in H2-BCl3 atmosphere

    NASA Astrophysics Data System (ADS)

    Kulka, M.; Makuch, N.; Pertek, A.; Małdziński, L.

    2013-03-01

    The modeling of the boriding kinetics is considered as a necessary tool to select the suitable process parameters for obtaining boride layer of an adequate thickness. Therefore, the simulation of the growth kinetics of boride layers has gained much attention for last years. The majority of the published works described the kinetics of the pack-boriding or paste-boriding. In this study, the model of growth kinetics of two-phase boride layer (FeB+Fe2B) on pure Fe was proposed for gas boriding. Displacements of the two interfaces (FeB/Fe2B and Fe2B/substrate) resulted from a difference of the arrival flux of interstitial boron atoms to one phase and the departure flux of the boron atoms from this phase to the second phase. The mass balance equations were formulated. The measurements of thickness of both zones (FeB and Fe2B), for different temperature of boriding, were used for calculations. Based on the experimental data, the parabolic growth constants AFeB and B versus the temperature of boriding were determined. The linear relationships were accepted. As a consequence, the activation energies (QFeB and Q) were calculated. The calculated values were comparable to other data derived from gas boriding. The presented model can predict the thicknesses of the FeB and Fe2B zones (XFeB and Y, respectively) formed on pure Fe during gas boriding. Additionally, the diffusion annealing after boriding was analyzed. This process was carried out in order to obtain a single-phase boride layer (Fe2B). The relationship between the reduction in FeB zone (dXFeB) and the growth in Fe2B phase (dY) was determined. The time tXFeB=0, needed for the total elimination of FeB phase in the boride layer was calculated and compared to the experimental data.

  20. Investigation of the fracture mechanics of boride composites

    NASA Technical Reports Server (NTRS)

    Kaufman, L.; Clougherty, E. V.; Nesor, H.

    1971-01-01

    Fracture energies of WC-6Co, Boride 5 (ZrB2+SiC), Boride 8(ZrB2+SiC+C) and Boride 8-M2(ZrB2+SiC+C) were measured by slow bend and impact tests of notched charpy bars. Cobalt bonded tungsten carbide exhibited impact energies of 0.76 ft-lb or 73.9 in-lb/square inch. Boride 5 and the Boride 8 exhibit impact energies one third and one quarter of that observed for WC-6Co comparing favorably with measurements for SiC and Si3N4. Slow bend-notched bar-fracture energies for WC-6Co were near 2.6 in-lb/square inch or 1/20 the impact energies. Slow bend energies for Boride 8-M2, Boride 8 and Boride 5 were 58%, 42% and 25% of the value observed for WC-6Co. Fractograph showed differences for WC-6Co where slow bend testing resulted in smooth transgranular cleavage while samples broken by impact exhibited intergranular failures. By contrast the boride fractures showed no distinction based on testing method. Fabrication studies were conducted to effect alteration of the boride composites by alloying and introduction of graphite cloth.

  1. Stability investigation of laser darkened metal surfaces

    NASA Astrophysics Data System (ADS)

    Hopp, Béla; Smausz, Tomi; Lentner, Márton; Kopniczky, Judit; Tápai, Csaba; Gera, Tamás; Csizmadia, Tamás; Ehrhardt, Martin; Lorenz, Pierre; Zimmer, Klaus

    2017-09-01

    Pulsed laser irradiation-induced reflectivity decrease of metal surfaces is a well-established phenomenon, which is extensively utilized in numerous applications. Since the stability of these black surfaces is often a demand, we investigated the resistance of darkened copper and titanium surfaces against optical and mechanical damages. For optical stability studies, samples were irradiated by a probe laser beam ( λ = 775 nm, FWHM = 150 fs, f = 1 kHz) at different fluences (0-300 mJ/cm2), while the mechanical stability was studied with scratch test using 2.5 µm radius tip and applying normal force in 29.4-147 µN range. The observed reflectivity and morphological changes indicated that the optical damage threshold fluence is 130 and 160 mJ/cm2 for copper and titanium surfaces, respectively. Mechanical damage only in case of copper could be detected in the applied parameter range indicating a scratch hardness of 21.5 MPa.

  2. Synthesis, crystal structure investigation and magnetism of the complex metal-rich boride series Cr{sub x}(Rh{sub 1-y}Ru{sub y}){sub 7-x}B{sub 3} (x=0.88-1; y=0-1) with Th{sub 7}Fe{sub 3}-type structure

    SciTech Connect

    Misse, Patrick R.N.; Mbarki, Mohammed; Fokwa, Boniface P.T.

    2012-08-15

    Powder samples and single crystals of the new complex boride series Cr{sub x}(Rh{sub 1-y}Ru{sub y}){sub 7-x}B{sub 3} (x=0.88-1; y=0-1) have been synthesized by arc-melting the elements under purified argon atmosphere on a water-cooled copper crucible. The products, which have metallic luster, were structurally characterized by single-crystal and powder X-ray diffraction as well as EDX measurements. Within the whole solid solution range the hexagonal Th{sub 7}Fe{sub 3} structure type (space group P6{sub 3}mc, no. 186, Z=2) was identified. Single-crystal structure refinement results indicate the presence of chromium at two sites (6c and 2b) of the available three metal Wyckoff sites, with a pronounced preference for the 6c site. An unexpected Rh/Ru site preference was found in the Ru-rich region only, leading to two different magnetic behaviors in the solid solution: The Rh-rich region shows a temperature-independent (Pauli) paramagnetism whereas an additional temperature-dependent paramagnetic component is found in the Ru-rich region. - Graphical abstract: The new complex boride series Cr{sub x}(Rh{sub 1-y}Ru{sub y}){sub 7-x}B{sub 3} (x=0.88-1; y=0-1) has been synthesized by arc melting the elements under purified argon atmosphere. Beside the 3d/4d site preference within the whole solid solution, an unexpected Rh/Ru site preference was found in the Ru-rich region only, leading to two different magnetic behaviors: The Rh-rich region shows a temperature-independent (Pauli) paramagnetism whereas an additional temperature-dependent paramagnetic component is found in the Ru-rich region. Highlights: Black-Right-Pointing-Pointer Synthesis of a new boride series fulfilling Vegard Acute-Accent s rule. Black-Right-Pointing-Pointer 3d/4d site preference. Black-Right-Pointing-Pointer Unexpected Ru/Rh site preference. Black-Right-Pointing-Pointer Rh-rich region is Pauli paramagnetic. Black-Right-Pointing-Pointer Ru-rich region is Pauli and temperature-dependent paramagnetic.

  3. Synthesis and Characterization of an Alumina Forming Nanolaminated Boride: MoAlB

    PubMed Central

    Kota, Sankalp; Zapata-Solvas, Eugenio; Ly, Alexander; Lu, Jun; Elkassabany, Omar; Huon, Amanda; Lee, William E.; Hultman, Lars; May, Steve J.; Barsoum, Michel W.

    2016-01-01

    The ‘MAlB’ phases are nanolaminated, ternary transition metal borides that consist of a transition metal boride sublattice interleaved by monolayers or bilayers of pure aluminum. However, their synthesis and properties remain largely unexplored. Herein, we synthesized dense, predominantly single-phase samples of one such compound, MoAlB, using a reactive hot pressing method. High-resolution scanning transmission electron microscopy confirmed the presence of two Al layers in between a Mo-B sublattice. Unique among the transition metal borides, MoAlB forms a dense, mostly amorphous, alumina scale when heated in air. Like other alumina formers, the oxidation kinetics follow a cubic time-dependence. At room temperature, its resistivity is low (0.36–0.49 μΩm) and – like a metal – drops linearly with decreasing temperatures. It is also a good thermal conductor (35 Wm−1K−1 at 26 °C). In the 25–1300 °C temperature range, its thermal expansion coefficient is 9.5 × 10−6 K−1. Preliminary results suggest the compound is stable to at least 1400 °C in inert atmospheres. Moderately low Vickers hardness values of 10.6 ± 0.3 GPa, compared to other transition metal borides, and ultimate compressive strengths up to 1940 ± 103 MPa were measured at room temperature. These results are encouraging and warrant further study of this compound for potential use at high temperatures. PMID:27220751

  4. Ternary boride product and process

    NASA Technical Reports Server (NTRS)

    Clougherty, Edward V. (Inventor)

    1976-01-01

    A hard, tough, strong ceramic body is formed by hot pressing a mixture of a powdered metal and a powdered metal diboride. The metal employed is zirconium, titanium or hafnium and the diboride is the diboride of a different member of the same group of zirconium, titanium or hafnium to form a ternary composition. During hot pressing at temperatures above about 2,000.degree.F., a substantial proportion of acicular ternary monoboride is formed.

  5. Additive-assisted synthesis of boride, carbide, and nitride micro/nanocrystals

    SciTech Connect

    Chen, Bo; Yang, Lishan; Heng, Hua; Chen, Jingzhong; Zhang, Linfei; Xu, Liqiang; Qian, Yitai; Yang, Jian

    2012-10-15

    General and simple methods for the syntheses of borides, carbides and nitrides are highly desirable, since those materials have unique physical properties and promising applications. Here, a series of boride (TiB{sub 2}, ZrB{sub 2}, NbB{sub 2}, CeB{sub 6}, PrB{sub 6}, SmB{sub 6}, EuB{sub 6}, LaB{sub 6}), carbide (SiC, TiC, NbC, WC) and nitride (TiN, BN, AlN, MgSiN{sub 2}, VN) micro/nanocrystals were prepared from related oxides and amorphous boron/active carbon/NaN{sub 3} with the assistance of metallic Na and elemental S. In-situ temperature monitoring showed that the reaction temperature could increase quickly to {approx}850 Degree-Sign C, once the autoclave was heated to 100 Degree-Sign C. Such a rapid temperature increase was attributed to the intense exothermic reaction between Na and S, which assisted the formation of borides, carbides and nitrides. The as-obtained products were characterized by XRD, SEM, TEM, and HRTEM techniques. Results in this report will greatly benefit the future extension of this approach to other compounds. - Graphical abstract: An additive-assisted approach is successfully developed for the syntheses of borides, carbides and nitrides micro/nanocrystals with the assistance of the exothermic reaction between Na and S. Highlights: Black-Right-Pointing-Pointer An additive-assisted synthesis strategy is developed for a number of borides, carbides and nitrides. Black-Right-Pointing-Pointer The reaction mechanism is demonstrated by the case of SiC nanowires. Black-Right-Pointing-Pointer The formation of SiC nanowires is initiated by the exothermic reaction of Na and S.

  6. Potential and limitations of microanalysis SEM techniques to characterize borides in brazed Ni-based superalloys

    SciTech Connect

    Ruiz-Vargas, J.; Siredey-Schwaller, N.; Noyrez, P.; Mathieu, S.; Bocher, P.; and others

    2014-08-15

    Brazed Ni-based superalloys containing complex phases of different Boron contents remain difficult to characterize at the micrometer scale. Indeed Boron is a light element difficult to measure precisely. The state-of-the-art microanalysis systems have been tested on a single crystal MC2 based metal brazed with BNi-2 alloy to identify boride precipitates. Effort has been made to evaluate the accuracy in Boron quantitation. Energy-dispersive and wavelength-dispersive X-ray spectroscopy attached to a Scanning Electron Microscope have first been used to determine the elemental composition of Boron-free phases, and then applied to various types of borides. Results have been compared to the ones obtained using a dedicated electron probe microanalysis, considered here as the reference technique. The most accurate method to quantify Boron using EDS is definitely by composition difference. A precision of 5 at.% could be achieved with optimized data acquisition and post-processing schemes. Attempts that aimed at directly quantifying Boron with various standards using EDS or coupled EDS/WDS gave less accurate results. Ultimately, Electron Backscatter Diffraction combined with localized EDS analysis has proved invaluable in conclusively identifying micrometer sized boride precipitates; thus further improving the characterization of brazed Ni-based superalloys. - Highlights: • We attempt to accurately identify Boron-rich phases in Ni-based superalloys. • EDS, WDS, EBSD systems are tested for accurate identification of these borides. • Results are compared with those obtained by electron probe microanalysis. • Boron was measured with EDS by composition difference with a precision of 5 at. %. • Additional EBSD in phase identification mode conclusively identifies the borides.

  7. Univerality, Scaling, and Stability of Metallic Nanowires

    NASA Astrophysics Data System (ADS)

    Stafford, Charles

    2001-03-01

    A remarkably quantitative understanding of the electrical and mechanical properties of simple metal nanowires has been obtained within the free-electron model.^2-4 The force required to pull a gold wire apart exhibits steps of approximately 1nN, which are synchronized with steps of order G_0=2e^2/h in the wire's electrical conductance. Using a Gutzwiller sum over classical periodic orbits,(C. A. Stafford, F. Kassubek, J. Bürki, and H. Grabert, Phys. Rev. Lett. 83), 4836 (1999). we were able to explain why the characteristic size of the force steps is universal, i.e., insensitive to the size and shape of the wire, and of order \\varepsilon_F/λ_F. The statistics of conductance and shot noise in gold nanowires can also be understood quantitatively using a model of quantum-confined electrons including disorder.(J. Bürki, C. A. Stafford, X. Zotos, and D. Baeriswyl, Phys. Rev. B 60), 5000 (1999); J. Bürki and C. A. Stafford, Phys. Rev. Lett. 83, 3342 (1999). A linear stability analysis(F. Kassubek, C. A. Stafford, H. Grabert, and R. E. Goldstein, Nonlinearity 14), 167 (2001). shows that the classical instability of a long wire under surface tension can be completely suppressed by quantum effects, leading to stable cylindrical configurations whose electrical conductance is a magic number 1, 3, 5, 6,... times G_0, providing a possible theoretical explanation for the remarkable stability of long chains of gold atoms, and for the supershell structure observed in the conductance statistics of alkali metal nanowires.

  8. Stabilization process of metallic mercury by sulphur

    SciTech Connect

    Vaudey, Claire-Emilie; Bardy, Maud; Huc, Christelle

    2013-07-01

    The technical field of this subject can be described as the treatment of mercury based wastes in order to stock or eliminate them. Toxic mercury vapours prevent from directly stocking or incinerating the wastes. Therefore, some processes have already been implemented to reduce the mercury mobility. Those immobilization processes are created to avoid mercury release in the atmosphere by volatilization or in the soil by leaching. Among the 3 current processes: encapsulation, amalgamation and stabilization, we took an interest on the last one. Stabilization can be defined as an immobilization due to a combination between a molecule and motionless particles to reduce the release of dangerous elements in the atmosphere or the biosphere. The most common technique of metallic mercury stabilization found in readings is the sulphur amalgamation technique. It consists in the chemical reaction: Hg + S → HgS. A mercury sulphide is then produced and is very insoluble in the water. A 386 deg. C heating transforms it in red sulphide. The obtained mixture can be easily and safely stored in a waste storage. In this context, solid sulphur is added in wide excess compared to the liquid mercury to cause the reaction: Hg(l) + S(s) → HgS(s) with a molar ratio between 1/6.5 and 1/19. The main drawback of this technique is the generation of an important waste quantity: a mixture of HgS and sulphur. Moreover there's no guarantee about the absence of mercury vapours. Therefore there's a real need to improve the ratio and the safety of the reaction, which is the purpose of this study. The volume of the created product is greatly reduced in this case and authorizes significant savings on storage costs. The other experimental parameters discussed in this study are temperature, volume, flask type and mixing speed. (authors)

  9. Heat capacity and thermal expansion of icosahedral lutetium boride LuB66

    SciTech Connect

    Novikov, V V; Avdashchenko, D V; Matovnikov, A V; Mitroshenkov, N V; Bud’ko, S L

    2014-01-07

    The experimental values of heat capacity and thermal expansion for lutetium boride LuB66 in the temperature range of 2-300 K were analysed in the Debye-Einstein approximation. It was found that the vibration of the boron sub-lattice can be considered within the Debye model with high characteristic temperatures; low-frequency vibration of weakly connected metal atoms is described by the Einstein model.

  10. Boron-Based Hydrogen Storage: Ternary Borides and Beyond

    SciTech Connect

    Vajo, John J.

    2016-04-28

    DOE continues to seek reversible solid-state hydrogen materials with hydrogen densities of ≥11 wt% and ≥80 g/L that can deliver hydrogen and be recharged at moderate temperatures (≤100 °C) and pressures (≤100 bar) enabling incorporation into hydrogen storage systems suitable for transportation applications. Boron-based hydrogen storage materials have the potential to meet the density requirements given boron’s low atomic weight, high chemical valance, and versatile chemistry. However, the rates of hydrogen exchange in boron-based compounds are thus far much too slow for practical applications. Although contributing to the high hydrogen densities, the high valance of boron also leads to slow rates of hydrogen exchange due to extensive boron-boron atom rearrangements during hydrogen cycling. This rearrangement often leads to multiple solid phases occurring over hydrogen release and recharge cycles. These phases must nucleate and react with each other across solid-solid phase boundaries leading to energy barriers that slow the rates of hydrogen exchange. This project sought to overcome the slow rates of hydrogen exchange in boron-based hydrogen storage materials by minimizing the number of solid phases and the boron atom rearrangement over a hydrogen release and recharge cycle. Two novel approaches were explored: 1) developing matched pairs of ternary borides and mixed-metal borohydrides that could exchange hydrogen with only one hydrogenated phase (the mixed-metal borohydride) and only one dehydrogenated phase (the ternary boride); and 2) developing boranes that could release hydrogen by being lithiated using lithium hydride with no boron-boron atom rearrangement.

  11. Experiments on the stability of metal diapirs

    NASA Astrophysics Data System (ADS)

    Wacheul, J. S.; Le Bars, M.; Aurnou, J. M.; Monteux, J.

    2013-12-01

    In the late stages of their accretions, telluric planets had most likely had a magma ocean because of numerous heat sources such as the important decay of radioactive elements and giant impacts. These giant impacts involved asteroid nearly as big as the moon, which were certainly differentiated. The core of these planetary embryos ultimately merged with the planets, but the amount of heat and chemicals they exchanged with the mantle during its passing through remains a widely open question. The question of the stability of an immiscible iron diapir falling through a magma ocean is essential for our understanding of these events. Thus, we have conducted the first experiments on an analogue system that involves liquid metal; we used liquid gallium as the melted iron and glycerol as the magma ocean. This set up allowed us to reach Reynolds numbers closer to the geophysical problem than other previous studies and accurate viscosity ratios. Using video analysis, we reconstruct the spectra of droplet sizes and velocities, from which we calculate a typical length of equilibration as a function of the diapir's radius. Our preliminary results are in agreement with the scenario of the iron rain concerning the droplet sizes, with a significant influence of the viscosity ratio on the maximal size of the droplets. However, the speed of these droplets seems to be controlled by the inertia of the whole flow in a sense that the relevant concept for the mixing between metal and silicate is turbulent mixing between miscible fluids. The influence of coalescence between droplets on this mixing, involving a significant part of the flow according to our experiment, is still to be quantified.

  12. Metal stabilization of collagen and de novo designed mimetic peptides

    PubMed Central

    Parmar, Avanish S.; Xu, Fei; Pike, Douglas H.; Belure, Sandeep V.; Hasan, Nida F.; Drzewiecki, Kathryn E.; Shreiber, David I.; Nanda, Vikas

    2017-01-01

    We explore the design of metal binding sites to modulate triple-helix stability of collagen and collagen-mimetic peptides. Globular proteins commonly utilize metals to connect tertiary structural elements that are well separated in sequence, constraining structure and enhancing stability. It is more challenging to engineer structural metals into fibrous protein scaffolds, which lack the extensive tertiary contacts seen in globular proteins. In the collagen triple helix, the structural adjacency of the carboxy-termini of the three chains makes this region an attractive target for introducing metal binding sites. We engineered His3 sites based on structural modeling constraints into a series of designed homotrimeric and heterotrimeric peptides, assessing the capacity of metal binding to improve stability and in the case of heterotrimers, affect specificity of assembly. Notable enhancements in stability for both homo and heteromeric systems were observed upon addition of zinc(II) and several other metal ions only when all three histidine ligands were present. Metal binding affinities were consistent with the expected Irving-Williams series for imidazole. Unlike other metals tested, copper(II) also bound to peptides lacking histidine ligands. Acetylation of the peptide N-termini prevented copper binding, indicating proline backbone amide metal-coordination at this site. Copper similarly stabilized animal extracted Type I collagen in a metal specific fashion, highlighting the potential importance of metal homeostasis within the extracellular matrix. PMID:26225466

  13. Metal Stabilization of Collagen and de Novo Designed Mimetic Peptides.

    PubMed

    Parmar, Avanish S; Xu, Fei; Pike, Douglas H; Belure, Sandeep V; Hasan, Nida F; Drzewiecki, Kathryn E; Shreiber, David I; Nanda, Vikas

    2015-08-18

    We explore the design of metal binding sites to modulate triple-helix stability of collagen and collagen-mimetic peptides. Globular proteins commonly utilize metals to connect tertiary structural elements that are well separated in sequence, constraining structure and enhancing stability. It is more challenging to engineer structural metals into fibrous protein scaffolds, which lack the extensive tertiary contacts seen in globular proteins. In the collagen triple helix, the structural adjacency of the carboxy-termini of the three chains makes this region an attractive target for introducing metal binding sites. We engineered His3 sites based on structural modeling constraints into a series of designed homotrimeric and heterotrimeric peptides, assessing the capacity of metal binding to improve stability and in the case of heterotrimers, affect specificity of assembly. Notable enhancements in stability for both homo- and heteromeric systems were observed upon addition of zinc(II) and several other metal ions only when all three histidine ligands were present. Metal binding affinities were consistent with the expected Irving-Williams series for imidazole. Unlike other metals tested, copper(II) also bound to peptides lacking histidine ligands. Acetylation of the peptide N-termini prevented copper binding, indicating proline backbone amide metal-coordination at this site. Copper similarly stabilized animal extracted Type I collagen in a metal-specific fashion, highlighting the potential importance of metal homeostasis within the extracellular matrix.

  14. Stabilizing Crystal Oscillators With Melting Metals

    NASA Technical Reports Server (NTRS)

    Stephens, J. B.; Miller, C. G.

    1984-01-01

    Heat of fusion provides extended period of constant temperature and frequency. Crystal surrounded by metal in spherical container. As outside temperature rises to melting point of metal, metal starts to liquefy; but temperature stays at melting point until no solid metal remains. Potential terrestrial applications include low-power environmental telemetering transmitters and instrumentation transmitters for industrial processes.

  15. Effect of the boride-nitride hardening on the structure and properties of chromium steel deposited with a flux-cored wire

    NASA Astrophysics Data System (ADS)

    Eremin, E. N.; Losev, A. S.; Borodikhin, S. A.; Ivlev, K. Ye.

    2017-08-01

    Reliability and durability of pipeline valves are largely determined by the resistance of weld sealing surfaces of its shut-off valve, which in its turn depends on the weld metal properties. To improve the durability of valves a new composition of a high chromium flux-cored wire with a boride compounds complex (BN, TiB2, ZrB2) producing weld composite metal is developed. It is stated that the formation of the martensitic matrix with a reduced structural fragments average size due to appearance of dispersed boride-nitride phases in this metal has resulted in high coating hardness and wear resistance.

  16. Mechanism of boriding from pastes in a glow discharge

    SciTech Connect

    Isakov, S.A.; Al'tshuler, S.A.

    1987-09-01

    The authors investigate the boridation of steel 45 from the standpoint of the glow-discharge dissociation of a borax paste and the plasma arc spraying of the resulting boron into the steel. The effects of process parameters on the impregnation of boron into the steel and its phase behavior in the boridation process are discussed.

  17. Structure stability and spectroscopy of metal clusters. Progress report

    SciTech Connect

    Not Available

    1993-06-01

    Theory based on self-consistent field-linear combinations of atomic orbitals-molecular orbital theory was applied to clusters. Four areas were covered: electronic structure, equilibrium geometries, and stability of charged clusters, interaction of metal clusters with H and halogen atoms, thermal stability of isolated clusters, and stability and optical properties of hetero-atomic clusters. (DLC)

  18. Thermodynamic stability of ligand-protected metal nanoclusters

    NASA Astrophysics Data System (ADS)

    Taylor, Michael G.; Mpourmpakis, Giannis

    2017-07-01

    Despite the great advances in synthesis and structural determination of atomically precise, thiolate-protected metal nanoclusters, our understanding of the driving forces for their colloidal stabilization is very limited. Currently there is a lack of models able to describe the thermodynamic stability of these `magic-number' colloidal nanoclusters as a function of their atomic-level structural characteristics. Herein, we introduce the thermodynamic stability theory, derived from first principles, which is able to address stability of thiolate-protected metal nanoclusters as a function of the number of metal core atoms and thiolates on the nanocluster shell. Surprisingly, we reveal a fine energy balance between the core cohesive energy and the shell-to-core binding energy that appears to drive nanocluster stabilization. Our theory applies to both charged and neutral systems and captures a large number of experimental observations. Importantly, it opens new avenues for accelerating the discovery of stable, atomically precise, colloidal metal nanoclusters.

  19. Thermodynamic stability of ligand-protected metal nanoclusters

    PubMed Central

    Taylor, Michael G.; Mpourmpakis, Giannis

    2017-01-01

    Despite the great advances in synthesis and structural determination of atomically precise, thiolate-protected metal nanoclusters, our understanding of the driving forces for their colloidal stabilization is very limited. Currently there is a lack of models able to describe the thermodynamic stability of these ‘magic-number’ colloidal nanoclusters as a function of their atomic-level structural characteristics. Herein, we introduce the thermodynamic stability theory, derived from first principles, which is able to address stability of thiolate-protected metal nanoclusters as a function of the number of metal core atoms and thiolates on the nanocluster shell. Surprisingly, we reveal a fine energy balance between the core cohesive energy and the shell-to-core binding energy that appears to drive nanocluster stabilization. Our theory applies to both charged and neutral systems and captures a large number of experimental observations. Importantly, it opens new avenues for accelerating the discovery of stable, atomically precise, colloidal metal nanoclusters. PMID:28685777

  20. Microstructure and properties of laser-borided 41Cr4 steel

    NASA Astrophysics Data System (ADS)

    Kulka, M.; Makuch, N.; Pertek, A.

    2013-02-01

    Laser-boriding, instead of diffusion-boriding, was applied to formation of boride layers on 41Cr4 steel. The microstructure and properties of these layers were compared to those obtained after typical diffusion-boriding. Three zones characterized the microstructure of laser-borided layer: laser-borided zone, hardened medium-carbon zone (heat affected zone) and medium-carbon substrate without heat treatment. The through-hardened laser-borided steel was also analyzed. In this case two zones characterized the microstructure: laser-borided zone and hardened medium-carbon substrate. The microstructure of laser-borided zone consisted of eutectic mixture of borides and martensite. This phase composition (especially martensite presence) was the reason for microhardness decrease at the surface in comparison with diffusion-borided steel. However, the use of laser-boriding causes the decrease in microhardness gradient between the surface and the substrate in comparison with typical diffusion-boriding process. The value of mass wear intensity factor of the hardened laser-borided layer was comparable to that obtained in case of diffusion-boriding and through-hardening. The use of laser-borided layers instead of typical diffusion-borided layers may be advantageous under conditions of high abrasive wear of mating parts. For the experimental condition used, the laser-boriding process presented worst results concerning the fatigue strength. The cracks formed on the surface during laser re-melting were the reason for relatively quick first fatigue crack. In case of elements, which require high fatigue strength, the use of modified laser processing parameters would be necessary. The better results should be obtained by increasing of tracks overlapping. Although the cohesion of laser-borided layer was sufficient, the diffusion-borided layer showed a better cohesion.

  1. Boriding of high carbon high chromium cold work tool steel

    NASA Astrophysics Data System (ADS)

    Muhammad, W.

    2014-06-01

    High-carbon high-chromium cold work tool steels are widely used for blanking and cold forming of punches and dies. It is always advantageous to obtain an increased wear resistant surface to improve life and performance of these steels. In this connection boriding of a high-carbon high-chromium cold work die steel, D3, was conducted in a mixture of 30% B4C, 70% borax at 950 °C for two, four and six hours. Case depth of the borided layer obtained was between 40 to 80 μm. After boriding, the surface hardness achieved was between 1430 to 1544 HV depending upon the process time. X-ray diffraction studies confirmed the formation of a duplex compound layer consisting of FeB and Fe2B. It is generally considered that FeB is undesirable because of its inherent brittleness. Post boriding treatment (homogenization) transformed the compound layer into single-phase layer of Fe2B, while surface hardness decreased to 1345-1430 HV. Pin-on-disc wer test showed that wear resistance of the borided samples was superior as compared to non-borided material and increased with boriding time.

  2. Influence of Re Concentration on the Mechanical Properties of Tungsten Borides from First-Principles Calculations

    NASA Astrophysics Data System (ADS)

    Pan, Yong; Lin, Yuanhua

    2017-10-01

    Tungsten borides are promising high-temperature materials. However, the structure and hardening mechanisms of tungsten boride are still great challenges. To solve the problems, we apply the first-principles method to study the structure of WB3 and explore the influence of alloying element Re on the mechanical properties of WB3. The calculated Vickers hardness of WB3 is 39.1 GPa. We further find that a low concentration of Re can improve the hardness of WB3, which is in good agreement with the experimental result. However, the hardness and elastic properties of WB3 decrease gradually with increasing Re concentration. The calculated results show that the structure and hardness of WB3 are attributed to the B-B hexagonal prism. A high concentration of Re weakens the charge interaction between the B-B atoms, and reduces the mechanical properties of WB3. Therefore, we can adjust the alloy concentration to improve the Vickers hardness of transition metal borides.

  3. Influence of Re Concentration on the Mechanical Properties of Tungsten Borides from First-Principles Calculations

    NASA Astrophysics Data System (ADS)

    Pan, Yong; Lin, Yuanhua

    2017-08-01

    Tungsten borides are promising high-temperature materials. However, the structure and hardening mechanisms of tungsten boride are still great challenges. To solve the problems, we apply the first-principles method to study the structure of WB3 and explore the influence of alloying element Re on the mechanical properties of WB3. The calculated Vickers hardness of WB3 is 39.1 GPa. We further find that a low concentration of Re can improve the hardness of WB3, which is in good agreement with the experimental result. However, the hardness and elastic properties of WB3 decrease gradually with increasing Re concentration. The calculated results show that the structure and hardness of WB3 are attributed to the B-B hexagonal prism. A high concentration of Re weakens the charge interaction between the B-B atoms, and reduces the mechanical properties of WB3. Therefore, we can adjust the alloy concentration to improve the Vickers hardness of transition metal borides.

  4. Synthesis and properties of nanoscale titanium boride

    NASA Astrophysics Data System (ADS)

    Efimova, K. A.; Galevskiy, G. V.; Rudneva, V. V.

    2015-09-01

    This work reports the scientific and technological grounds for plasma synthesis of titanium diboride, including thermodynamic and kinetic conditions of boride formation when titanium and titanium dioxide are interacting with products resulting from boron gasification in the nitrogen - hydrogen plasma flow, and two variations of its behavior using the powder mixtures: titanium - boron and titanium dioxide - boron. To study these technology variations, the mathematical models were derived, describing the relation between element contents in the synthesized products of titanium and free boron and basic parameters. The probable mechanism proposed for forming titanium diboride according to a "vapour - melt - crystal" pattern was examined, covering condensation of titanium vapour in the form of aerosol, boriding of nanoscale melt droplets by boron hydrides and crystallization of titanium - boron melt. The comprehensive physical - chemical certification of titanium diboride was carried out, including the study of its crystal structure, phase and chemical composition, dispersion, morphology and particle oxidation. Technological application prospects for use of titanium diboride nanoscale powder as constituent element in the wettable coating for carbon cathodes having excellent physical and mechanical performance and protective properties.

  5. Method of making an icosahedral boride structure

    DOEpatents

    Hersee, Stephen D.; Wang, Ronghua; Zubia, David; Aselage, Terrance L.; Emin, David

    2005-01-11

    A method for fabricating thin films of an icosahedral boride on a silicon carbide (SiC) substrate is provided. Preferably the icosahedral boride layer is comprised of either boron phosphide (B.sub.12 P.sub.2) or boron arsenide (B.sub.12 As.sub.2). The provided method achieves improved film crystallinity and lowered impurity concentrations. In one aspect, an epitaxially grown layer of B.sub.12 P.sub.2 with a base layer or substrate of SiC is provided. In another aspect, an epitaxially grown layer of B.sub.12 As.sub.2 with a base layer or substrate of SiC is provided. In yet another aspect, thin films of B.sub.12 P.sub.2 or B.sub.12 As.sub.2 are formed on SiC using CVD or other vapor deposition means. If CVD techniques are employed, preferably the deposition temperature is above 1050.degree. C., more preferably in the range of 1100.degree. C. to 1400.degree. C., and still more preferably approximately 1150.degree. C.

  6. Plasma metallurgical production of nanocrystalline borides and carbides

    NASA Astrophysics Data System (ADS)

    Galevsky, G. V.; Rudneva, V. V.; Cherepanov, A. N.; Galevsky, S. G.; Efimova, K. A.

    2016-09-01

    he experience in production and study of properties of nanocrystalline borides and chromium carbides, titanium, silicon was summarized. The design and features of the vertical three-jet once-through reactor with power 150 kW, used in the plasma metallurgical production, was described. The technological, thermotechnical and resource characteristics of the reactor were identified. The parameters of borides and carbides synthesis, their main characteristics in the nanodispersed state and equipment-technological scheme of production were provided. Evaluation of engineering-and-economical performance of the laboratory and industrial levels of borides and carbides production and the state corresponding to the segment of the world market was carried out.

  7. Synthesis of metallic nanoshells on porphyrin-stabilized emulsions

    DOEpatents

    Wang, Haorong; Song, Yujiang; Shelnutt, John A.; Medforth, Craig J.

    2011-12-13

    Metal nanostructures formed by photocatalytic interfacial synthesis using a porphyrin-stabilized emulsion template and the method for making the nanostructures. Catalyst-seeded emulsion droplets are employed as templates for hollow-nanoshell growth. The hollow metal nanospheres may be formed with or without inclusions of other materials.

  8. Pack-boriding of Fe-Mn binary alloys: Characterization and kinetics of the boride layers

    SciTech Connect

    Bektes, M.; Calik, A.; Ucar, N.; Keddam, M.

    2010-02-15

    In this work, the boronizing of Fe-Mn binary alloys at 0.42, 0.76 and 0.94 wt.% Mn was carried out in a solid medium using the powder pack method. In this method, commercial Ekabor-II boron source and activator (ferro-silicon) were thoroughly mixed to form the boriding medium. The samples were boronized in an electrical resistance furnace for exposure times of 2, 4, 6 and 8 h at 1173 K under atmospheric pressure and a series of boronized samples in the temperature range 1073-1373 K for 3 h. After the furnace process, boronized samples were removed from the furnace and cooled in air. Afterwards, the boride layers generated by the pack-boronizing process were characterized by optical microscopy, scanning electron microscopy, XRD analysis, Vickers microhardness and tensile testing. The generated boride layers, showing a saw-tooth morphology, had a surface microhardness in the range 1400-1270 HV0.1. It was shown that the values of yield stresses and ultimate tensile stresses were increased as the Mn content increases in the boronized Fe-Mn binary alloys. In contrast, the values of elongations determined from the stress-strain curves were decreased. Furthermore, it was found that the calculated mean value of the activation energy of boron diffusion was close to 119 J/mol.

  9. Theoretical study of phase stability and elastic properties of T 0.75Y0.75B14 (T = Sc, Ti, V, Y, Zr, Nb, Si).

    PubMed

    Hunold, Oliver; Music, Denis; Schneider, Jochen M

    2016-03-16

    In this study the phase stability, elastic properties, and plastic behaviour of icosahedral transition metal borides T 0.75Y0.75B14 (T = Sc, Ti, V, Y, Zr, Nb, Si) have been investigated using density functional theory. Phase stability critically depends on the charge transferred by T and Y to the B icosahedra. For the metal sublattice occupancy investigated here, the minimum energy of formation is identified at an effective B icosahedra charge of - 1.8 ± 0.1. This charge corridor encompasses the highest phase stability among all the reported icosahedral transition metal boride systems so far. This data provides guidance for future experimental efforts: from a wear-resistance point of view, Sc0.75Y0.75B14, Ti0.75Y0.75B14, and Zr0.75Y0.75B14 exhibit a rather unique and attractive combination of large Young's modulus values ranging from 488 to 514 GPa with the highest phase stability for icosahedral transition metals borides reported so far.

  10. Certain physical properties of cobalt and nickel borides

    NASA Technical Reports Server (NTRS)

    Kostetskiy, I. I.; Lvov, S. N.

    1981-01-01

    The temperature dependence of the electrical resistivity, the thermal conductivity, and the thermal emf of cobalt and nickel borides were studied. In the case of the nickel borides the magnetic susceptibility and the Hall coefficient were determined at room temperature. The results are discussed with allowance for the current carrier concentration, the effect of various mechanisms of current-carrier scattering and the location of the Fermi level in relation to the 3d band.

  11. Stability of a pendant droplet in gas metal arc welding

    SciTech Connect

    Murray, P.E.

    1998-07-01

    The authors develop a model of metal transfer in gas metal arc welding and compute the critical mass of a pendant droplet in order to ascertain the size and frequency of droplets detaching from the consumable metal electrode. These results are used to predict the mode of metal transfer for a range of voltage and current encompassing free flight transfer, and the transition between globular and spray transfer. This model includes an efficient method to compute the stability of a pendant droplet and the location of the liquid bridge connecting the primary droplet and the residual liquid remaining after detachment of the primary droplet.

  12. Crystallochemical bases of radiation stability of non-metallic materials

    SciTech Connect

    Kosenkov, V.M.

    1993-12-31

    The problems are considered on volume changes of crystal bodies as a result of neutron irradiation due to change of crystal lattice periods. This change is negligible to metal bodies. At the same time the irradiation of non-metallic structures causes the increase of atomic volume above 10%. The effects of volume change were analyzed for non-metallic structures in materials having different crystallochemical features: strict co-ordinates, structural disorder, phase transitions. The proposed models of radiation damage allow the increased radiation stability for non-metallic materials to be recommended by using the energy-saturated structures of initial materials.

  13. 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.

  14. Microstructure, Growth Kinetics and Some Mechanical Properties of Boride Layers Produced on Pure Titanium by Molten-Salt Boriding

    NASA Astrophysics Data System (ADS)

    Ma, L. S.; Duan, Y. H.; Li, P.

    2017-08-01

    To modify the surface properties of pure titanium, boride layers had been fabricated by the boron molten-salt diffusion on pure titanium surfaces in the temperature range of 900-1100 °C for 5- to 30-h treatments. The results demonstrated that the boride layers were mainly composed of TiB whiskers and TiB2 layers without the rutile titanium oxide TiO2. Two diffusion models were introduced to model the growth kinetics of boride layers. The parabolic growth constants and the boron diffusion coefficients were obtained. The boron activation energies for TiB2 and TiB were 225.617 and 165.266 kJ mol-1, respectively. The surface microhardness of the borided titanium decreased with the increase in distance from the surface. The results of wear tests indicated that the wear properties had been improved significantly compared to the pure titanium under dry sliding conditions.

  15. Stabilizing the surface of lithium metal

    SciTech Connect

    Vaughey, J. T.; Liu, Gao; Zhang, Ji-Guang

    2014-05-01

    Lithium metal is an ideal anode for the next generation of high capacity rechargeable batteries, including Li-air, Li-S, and other Li-based batteries using intercalation compounds. To enable the broad applications for lithium anodes, more fundamental studies need to be conducted to simultaneously address the two barriers discussed above. One of the key breakthroughs in this field may come from the development of new electrolytes (and additives) which can form a stable SEI layer with enough mechanical strength and flexibility. The ideal electrolyte may consist of only two components; one component inhibits dendrite growth, while another component forms a stable SEI layer to improve Coulombic efficiency. In this review, the status of three approaches at manipulating and controlling the lithium metal – electrolyte interface were discussed. While previous studies concentrated on coatings with minimal surface connectivity, the approaches discussed, namely a coating that forms and dissipates into the electrolyte based on charge density, a coating bonded to the termination layer of lithium, and a conformal carbonate coating formed at the interface, all highlight new research directions. Although there are still many obstacles to be overcome, we are optimistic that Li metal can be used as an anode in rechargeable batteries in the foreseeable future. This will enable wide

  16. Free surface stability of liquid metal plasma facing components

    NASA Astrophysics Data System (ADS)

    Fiflis, P.; Christenson, M.; Szott, M.; Kalathiparambil, K.; Ruzic, D. N.

    2016-10-01

    An outstanding concern raised over the implementation of liquid metal plasma facing components in fusion reactors is the potential for ejection of liquid metal into the fusion plasma. The influences of Rayleigh-Taylor-like and Kelvin-Helmholtz-like instabilities were experimentally observed and quantified on the thermoelectric-driven liquid-metal plasma-facing structures (TELS) chamber at the University of Illinois at Urbana-Champaign. To probe the stability boundary, plasma currents and velocities were first characterized with a flush probe array. Subsequent observations of lithium ejection under exposure in the TELS chamber exhibited a departure from previous theory based on linear perturbation analysis. The stability boundary is mapped experimentally over the range of plasma impulses of which TELS is capable to deliver, and a new theory based on a modified set of the shallow water equations is presented which accurately predicts the stability of the lithium surface under plasma exposure.

  17. Structure and Stability of Monatomic Metallic Chains

    NASA Astrophysics Data System (ADS)

    Batra, Inder P.; Sen, Prasenjit; Ciraci, S.

    2001-03-01

    We have investigated atomic and electronic structure of Au and Al monatomic chains by using first-principle plane wave method within density-functional theory. Despite their different valencies, Au and Al form planar zigzag chains with each atom having four nearest neighbors. The zigzag structure is stable against linearization and non-planar deformations. We performed an extensive charge density analysis and finite temperature calculations to reveal the origin of the unusual atomic structure in these one dimensional metallic systems. The implications of the zigzag structure on the electronic properties and the balistic electron conduction have been examined.

  18. Quantum stability and magic lengths of metal atom wires

    NASA Astrophysics Data System (ADS)

    Cui, Ping; Choi, Jin-Ho; Lan, Haiping; Cho, Jun-Hyung; Niu, Qian; Yang, Jinlong; Zhang, Zhenyu

    2016-06-01

    Metal atom wires represent an important class of nanomaterials in the development of future electronic devices and other functional applications. Using first-principles calculations within density functional theory, we carry out a systematic study of the quantum stability of freestanding atom wires consisting of prototypical metal elements with s -, s p -, and s d -valence electrons. We explore how the quantum mechanically confined motion and local bonding of the valence electrons in these different wire systems can dictate their overall structural stability and find that the formation energy of essentially all the wires oscillates with respect to their length measured by the number n of atoms contained in the wires, establishing the existence of highly preferred (or magic) lengths. Furthermore, different wire classes exhibit distinctively different oscillatory characteristics and quantum stabilities. Alkali metal wires possessing an unpaired s valence electron per atom exhibit simple damped even-odd oscillations. In contrast, Al and Ga wires containing three s2p1 valence electrons per atom generally display much larger and undamped even-odd energy oscillations due to stronger local bonding of the p orbitals. Among the noble metals, the s -dominant Ag wires behave similarly to the linear alkali metal wires, while Au and Pt wires distinctly prefer to be structurally zigzagged due to strong relativistic effects. These findings are discussed in connection with existing experiments and should also be instrumental in future experimental realization of different metal atom wires in freestanding or supported environments with desirable functionalities.

  19. First-principles studies of phase stability and crystal structures in Li-Zn mixed-metal borohydrides

    NASA Astrophysics Data System (ADS)

    Wang, Yongli; Zhang, Yongsheng; Wolverton, C.

    2013-07-01

    We address the problem of finding mixed-metal borohydrides with favorable thermodynamics and illustrate the approach using the example of LiZn2(BH4)5. Using density functional theory (DFT), along with the grand-canonical linear programming method (GCLP), we examine the experimentally and computationally proposed crystal structures and the finite-temperature thermodynamics of dehydrogenation for the quaternary hydride LiZn2(BH4)5. We find the following: (i) For LiZn2(BH4)5, DFT calculations of the experimental crystal structures reveal that the structure from the neutron diffraction experiments of Ravnsbæk is more stable [by 24 kJ/(mol f.u.)] than that based on a previous x-ray study. (ii) Our DFT calculations show that when using the neutron-diffraction structure of LiZn2(BH4)5, the recently theoretically predicted LiZn(BH4)3 compound is unstable with respect to the decomposition into LiZn2(BH4)5+LiBH4. (iii) GCLP calculations show that even though LiZn2(BH4)5 is a combination of weakly [Zn(BH4)2] and strongly (LiBH4) bound borohydrides, its decomposition is not intermediate between the two individual borohydrides. Rather, we find that the decomposition of LiZn2(BH4)5 is divided into a weakly exothermic step [LiZn2(BH4)5→2Zn+(1)/(5)LiBH4+(2)/(5)Li2B12H12+(36)/(5)H2] and three strong endothermic steps (12LiBH4→10LiH+Li2B12H12+13H2; Zn+LiH→LiZn+(1)/(2)H2; 2Zn+Li2B12H12→2LiZn+12B+6H2). DFT-calculated ΔHZPET=0K values for the first three LiZn2(BH4)5 decomposition steps are -19, +37, +74 kJ/(mol H2), respectively. The behavior of LiZn2(BH4)5 shows that mixed-metal borohydrides formed by mixing borohydrides of high and low thermodynamics stabilities do not necessarily have an intermediate decomposition tendency. Our results suggest the correct strategy to find intermediate decomposition in mixed-metal borohydrides is to search for stable mixed-metal products such as ternary metal borides.

  20. Theoretical study of phase stability and elastic properties of T 0.75Y0.75B14 (T  =  Sc, Ti, V, Y, Zr, Nb, Si)

    NASA Astrophysics Data System (ADS)

    Hunold, Oliver; Music, Denis; Schneider, Jochen M.

    2016-03-01

    In this study the phase stability, elastic properties, and plastic behaviour of icosahedral transition metal borides T 0.75Y0.75B14 (T  =  Sc, Ti, V, Y, Zr, Nb, Si) have been investigated using density functional theory. Phase stability critically depends on the charge transferred by T and Y to the B icosahedra. For the metal sublattice occupancy investigated here, the minimum energy of formation is identified at an effective B icosahedra charge of  -1.8  ±  0.1. This charge corridor encompasses the highest phase stability among all the reported icosahedral transition metal boride systems so far. This data provides guidance for future experimental efforts: from a wear-resistance point of view, Sc0.75Y0.75B14, Ti0.75Y0.75B14, and Zr0.75Y0.75B14 exhibit a rather unique and attractive combination of large Young’s modulus values ranging from 488 to 514 GPa with the highest phase stability for icosahedral transition metals borides reported so far.

  1. Metallic radial head arthroplasty improves valgus stability of the elbow.

    PubMed

    King, G J; Zarzour, Z D; Rath, D A; Dunning, C E; Patterson, S D; Johnson, J A

    1999-11-01

    The stabilizing influence of radial head arthroplasty was studied in eight medial collateral ligament deficient anatomic specimen elbows. An elbow testing apparatus, which used computer controlled pneumatic actuators to apply tendon loading, was used to simulate active elbow flexion. The motion pathways of the elbow were measured using an electromagnetic tracking device, with the forearm in supination and pronation. As a measure of stability, the maximum varus to valgus laxity over the range of elbow flexion was determined from the difference between varus and valgus gravity loaded motion pathways. After transection of the medial collateral ligament, the radial head was excised and replaced with either a silicone or one of three metallic radial head prostheses. Medial collateral ligament transection caused a significant increase in the maximum varus to valgus laxity to 18.0 degrees +/- 3.2 degrees. After radial head excision, this laxity increased to 35.6 degrees +/- 10.3 degrees. The silicone implant conferred no increase in elbow stability, with a maximum varus to valgus laxity of 32.5 degrees +/- 15.5 degrees. All three metallic implants improved the valgus stability of the medial collateral ligament deficient elbow, providing stability similar to the intact radial head. The use of silicone arthroplasty to replace the radial head in the medial collateral ligament deficient elbow must be questioned. Metallic radial head arthroplasty provides improved valgus stability, approaching that of an intact radial head.

  2. Microstructure and properties of laser-borided Inconel 600-alloy

    NASA Astrophysics Data System (ADS)

    Kulka, M.; Dziarski, P.; Makuch, N.; Piasecki, A.; Miklaszewski, A.

    2013-11-01

    Nickel-based superalloys are used extensively for a variety of industrial applications involving high temperatures and aggressive environments. However, under conditions of appreciable mechanical wear (adhesive or abrasive), these materials have to be distinguished by suitable wear protection. The diffusion boronizing is the thermo-chemical treatment, which improves the tribological properties of nickel and its alloys. Nevertheless, the long duration of this process is necessary in order to obtain the layers of the thickness up to about 100 μm. Instead of the diffusion process, in this study the laser boriding is used for producing boride layer on Inconel 600-alloy. During the laser alloying, the external cylindrical surface of base material is coated by paste, including amorphous boron. Then the surface is re-melted by a laser beam. The high overlapping of multiple laser tracks (86%) causes the formation of uniform laser-alloyed layer in respect of the thickness. Laser re-melted zone, heat-affected zone and the substrate characterize the microstructure. In the re-melted zone, the three areas are observed: compact borides zone consisting of nickel, chromium and iron borides (close to the surface), zone of increased percentage of Ni-Cr-Fe-matrix (appearing in the greater distance from the surface) and zone of dominant Ni-Cr-Fe-matrix percentage (at the end of the layer). The hardness obtained is comparable to that-obtained in case of diffusion boriding. Simultaneously, the laser-borided layers are significantly thicker (about 346 or 467 μm depending on the laser power used). The significant increase in their abrasive wear resistance is observed. The wear intensity factors, as well as the relative mass loss of the laser-borided samples, are ten times smaller in comparison with untreated Inconel 600-alloy.

  3. Abandoned metal mine stability risk evaluation.

    PubMed

    Bétournay, Marc C

    2009-10-01

    The abandoned mine legacy is critical in many countries around the world, where mine cave-ins and surface subsidence disruptions are perpetual risks that can affect the population, infrastructure, historical legacies, land use, and the environment. This article establishes abandoned metal mine failure risk evaluation approaches and quantification techniques based on the Canadian mining experience. These utilize clear geomechanics considerations such as failure mechanisms, which are dependent on well-defined rock mass parameters. Quantified risk is computed using probability of failure (probabilistics using limit-equilibrium factors of safety or applicable numerical modeling factor of safety quantifications) times a consequence impact value. Semi-quantified risk can be based on failure-case-study-based empirical data used in calculating probability of failure, and personal experience can provide qualified hazard and impact consequence assessments. The article provides outlines for land use and selection of remediation measures based on risk.

  4. Plastic stability of metallic glass composites under tension

    NASA Astrophysics Data System (ADS)

    Wu, F. F.; Li, S. T.; Zhang, G. A.; Wu, X. F.; Lin, P.

    2013-10-01

    The plastic stability of metallic glass composites (MGCs) under tension was investigated. There exists a critical normalized strain-hardening rate determining the plastic stability of MGCs: if the normalized strain-hardening rate is smaller than the critical normalized strain-hardening rate, the plastic instability occurs, thus, leading to localized plastic strain in MGCs; otherwise the plastic stability is in charge of the plastic deformation of the MGCs, so the strain localization or necking is effectively suppressed, which results in homogeneous elongation in MGCs.

  5. New members of ternary rare-earth metal boride carbides containing finite boron-carbon chains: RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28}

    SciTech Connect

    Babizhetskyy, Volodymyr; Mattausch, Hansjuergen; Simon, Arndt; Gautier, Regis; Halet, Jean-Francois

    2011-07-15

    New ternary rare-earth metal boride carbides RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28} were synthesized by co-melting the elements. Nd{sub 25}B{sub 12}C{sub 28} is stable up to 1440 K. RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) exist above 1270 K. The crystal structures were investigated by means of single-crystal X-ray diffraction. Nd{sub 25}B{sub 12}C{sub 28}: space group P1-bar, a=8.3209(7) A, b=8.3231(6) A, c=29.888(2) A, {alpha}=83.730(9){sup o}, {beta}=83.294(9){sup o}, {gamma}=89.764(9){sup o}. Pr{sub 25}B{sub 14}C{sub 26}: space group P2{sub 1}/c, a=8.4243(5) A, b=8.4095(6) A, c=30.828(1) A, {beta}=105.879(4){sup o}, V=2100.6(2) A{sup 3}, (R1=0.048 (wR2=0.088) from 2961 reflections with I{sub o}>2{sigma}(I{sub o})); for Nd{sub 25}B{sub 14}C{sub 26} space group P2{sub 1}/c, Z=2, a=8.3404(6) A, b=8.3096(6) A, c=30.599(2) A, {beta}=106.065(1){sup o}. Their structures consist of a three-dimensional framework of rare-earth metal atoms resulting from the stacking of slightly corrugated and distorted square nets, leading to cavities filled with cumulene-like molecules [B{sub 2}C{sub 4}]{sup 6-} and [B{sub 3}C{sub 3}]{sup 7-}, nearly linear [BC{sub 2}]{sup 5-} and bent [BC{sub 2}]{sup 7-} units and isolated carbon atoms. Structural and theoretical analysis suggests the ionic formulation for RE{sub 25}B{sub 14}C{sub 26}: (RE{sup 3+}){sub 25}[B{sub 2}C{sub 4}]{sup 6-}([B{sub 3}C{sub 3}]{sup 7-}){sub 2}([BC{sub 2}]{sup 5-}){sub 4}([BC{sub 2}]{sup 7-}){sub 2}(C{sup 4-}){sub 4}.5e{sup -} and for Nd{sub 25}B{sub 12}C{sub 28}: (Nd{sup 3+}){sub 25}([B{sub 2}C{sub 4}]{sup 6-}){sub 3}([BC{sub 2}]{sup 5-}){sub 4}([BC{sub 2}]{sup 7-}){sub 2}(C{sup 4-}){sub 4}.7e{sup -}. Accordingly, extended Hueckel tight-binding calculations indicate that the compounds are metallic in character. - Graphical Abstract: New ternary rare-earth metal boride carbides RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28} were synthesized by co

  6. Metal Chelating Crosslinkers Form Nanogels with High Chelation Stability.

    PubMed

    Lux, Jacques; Chan, Minnie; Elst, Luce Vander; Schopf, Eric; Mahmoud, Enas; Laurent, Sophie; Almutairi, Adah

    2013-12-14

    We present a series of hydrogel nanoparticles (nanogels) incorporating either acyclic or cyclic metal chelates as crosslinkers. These crosslinkers are used to formulate polyacrylamide-based nanogels (diameter 50 to 85 nm) yielding contrast agents with enhanced relaxivities (up to 6-fold greater than Dotarem®), because this nanogel structure slows the chelator's tumbling frequency and allows fast water exchange. Importantly, these nanogels also stabilize Gd(3+) within the chelator thermodynamically and kinetically against metal displacement through transmetallation, which should reduce toxicity associated with release of free Gd(3+). This chelation stability suggests that the chelate crosslinker strategy may prove useful for other applications of metal-chelating nanoparticles in medicine, including other imaging modalities and radiotherapy.

  7. Point defect stability in a semicoherent metallic interface

    NASA Astrophysics Data System (ADS)

    González, C.; Iglesias, R.; Demkowicz, M. J.

    2015-02-01

    We present a comprehensive density functional theory (DFT) -based study of different aspects of one vacancy and He impurity atom behavior at semicoherent interfaces between the low-solubility transition metals Cu and Nb. Such interfaces have not been previously modeled using DFT. A thorough analysis of the stability and mobility of the two types of defects at the interfaces and neighboring internal layers has been performed and the results have been compared to the equivalent cases in the pure metallic matrices. The different behavior of fcc and bcc metals on both sides of the interface has been specifically assessed. The modeling effort undertaken is the first attempt to study the stability and defect energetics of noncoherent Cu/Nb interfaces from first principles, in order to assess their potential use in radiation-resistant materials.

  8. Metal Chelating Crosslinkers Form Nanogels with High Chelation Stability

    PubMed Central

    Elst, Luce Vander; Schopf, Eric; Mahmoud, Enas; Laurent, Sophie; Almutairi, Adah

    2013-01-01

    We present a series of hydrogel nanoparticles (nanogels) incorporating either acyclic or cyclic metal chelates as crosslinkers. These crosslinkers are used to formulate polyacrylamide-based nanogels (diameter 50 to 85 nm) yielding contrast agents with enhanced relaxivities (up to 6-fold greater than Dotarem®), because this nanogel structure slows the chelator's tumbling frequency and allows fast water exchange. Importantly, these nanogels also stabilize Gd3+ within the chelator thermodynamically and kinetically against metal displacement through transmetallation, which should reduce toxicity associated with release of free Gd3+. This chelation stability suggests that the chelate crosslinker strategy may prove useful for other applications of metal-chelating nanoparticles in medicine, including other imaging modalities and radiotherapy. PMID:24505553

  9. Stabilizing nanostructures in metals using grain and twin boundary architectures

    NASA Astrophysics Data System (ADS)

    Lu, K.

    2016-05-01

    Forming alloys with impurity elements is a routine method for modifying the properties of metals. An alternative approach involves the incorporation of interfaces into the crystalline lattice to enhance the metal's properties without changing its chemical composition. The introduction of high-density interfaces in nanostructured materials results in greatly improved strength and hardness; however, interfaces at the nanoscale show low stability. In this Review, I discuss recent developments in the stabilization of nanostructured metals by modifying the architectures of their interfaces. The amount, structure and distribution of several types of interfaces, such as high- and low-angle grain boundaries and twin boundaries, are discussed. I survey several examples of materials with nanotwinned and nanolaminated structures, as well as with gradient nanostructures, describing the techniques used to produce such samples and tracing their exceptional performances back to the nanoscale architectures of their interfaces.

  10. Mechanochemically Driven Syntheses of Boride Nanomaterials

    NASA Astrophysics Data System (ADS)

    Blair, Richard G.

    Solid state metathesis reactions have proven to be a viable route to the production of unfunctionalized nanomaterials. However, current implementations of this approach are limited to self-propagating reactions. We have been investigating mechanically driven metathesis reactions. The use of high-energy ball mills allows control of crystallite sizes without the use of a capping group. Reinforcement materials with crystallite sizes on the order of 5-30 nm can be produced in such a manner. Borides are of particular interest due to their strength, high melting point, and electrical conductivity. The ultimate goal of this work is to prepare oxide and capping group-free nanoparticles suitable for incorporation in thermoelectric, polymer, and ceramic composites. Ultimately this work will facilitate the production of improved thermoelectric materials that will provide robust, deployable, power generation modules to supplement or replace fuel cell, Stirling, and battery-derived power sources. It will also result in scalable, bulk syntheses of tough, refractory, conductive nanomaterials for polymer composites with improved electrical properties, ceramic composites with enhanced fracture toughness, and composites with enhanced neutron reflectance and/or absorbance.

  11. Novel magnesium borides and their superconductivity.

    PubMed

    Davari Esfahani, M Mahdi; Zhu, Qiang; Dong, Huafeng; Oganov, Artem R; Wang, Shengnan; Rakitin, Maksim S; Zhou, Xiang-Feng

    2017-06-07

    With the motivation of searching for new superconductors in the Mg-B system, we performed ab initio evolutionary searches for all the stable compounds in this binary system in the pressure range of 0-200 GPa. We found previously unknown, yet thermodynamically stable, compositions MgB3 and Mg3B10. Experimentally known MgB2 is stable in the entire pressure range 0-200 GPa, while MgB7 and MgB12 are stable at pressures below 90 GPa and 35 GPa, respectively. We predict a reentrant behavior for MgB4, which becomes unstable against decomposition into MgB2 and MgB7 at 4 GPa and then becomes stable above 61 GPa. We find ubiquity of phases with boron sandwich structures analogous to the AlB2-type structure. However, with the exception of MgB2, all other magnesium borides have low electron-phonon coupling constants λ of 0.32-0.39 and are predicted to have Tc below 3 K.

  12. Growth morphology and thermal stability of metal islands on graphene

    NASA Astrophysics Data System (ADS)

    Liu, Xiaojie; Hupalo, Myron; Wang, Cai-Zhuang; Lu, Wen-Cai; Thiel, Patricia A.; Ho, Kai-Ming; Tringides, Michael C.

    2012-08-01

    We performed an experiment to study the thermal stability of metal on graphene. We show that Fe, Gd, Dy, and Eu on graphene exhibit island growth morphology. The 3D islands of Fe, Gd, and Dy show a small decrease in island density and an increase in the height/width aspect ratio upon thermal annealing. By contrast, coarsening of Eu islands to a close flat film is observed after annealing to 365 K. By investigating the fundamental interactions (i.e., adsorption energies and diffusion barriers) between the metal adatoms and graphene using ab initio calculations, we predict that most of the 3d and group 10 transition metals, noble metals, as well as rare earth metals on graphene should exhibit a 3D growth mode as observed in experiment. Most of the metal nanostructures on graphene should also be stable against aggregation. The 3D morphology and strong thermal stability of Fe, Co, Ni, Pt, and Gd islands on graphene can serve as good candidates for surface-supported catalysis applications.

  13. Laser borided composite layer produced on austenitic 316L steel

    NASA Astrophysics Data System (ADS)

    Mikołajczak, Daria; Kulka, Michał; Makuch, Natalia

    2016-12-01

    Abstract Austenitic 316L steel is well-known for its good resistance to corrosion and oxidation. Therefore, this material is often used wherever corrosive media or high temperatures are to be expected. The main drawback of this material is very low hardness and low resistance to mechanical wear. In this study, the laser boriding was used in order to improve the wear behavior of this material. As a consequence, a composite surface layer was produced. The microstructure of laser-borided steel was characterized by only two zones: re-melted zone and base material. In the re-melted zone, a composite microstructure, consisting of hard ceramic phases (borides) and a soft austenitic matrix, was observed. A significant increase in hardness and wear resistance of such a layer was obtained.

  14. Scaffolds of magnetically active 3d metals in the valence electron controlled borides Ti{sub 9−x}M{sub 2+x}Ru{sub 18}B{sub 8} (M=Cr–Ni; x=0.5–1): Structutral, electronic and magnetic properties

    SciTech Connect

    Goerens, Christian; Brgoch, Jakoah; Miller, Gordon J.; Fokwa, Boniface P.T.

    2013-08-15

    Polycrystalline samples of the boride series Ti{sub 9−x}M{sub 2+x}Ru{sub 18}B{sub 8} (M=Cr, Co, Mn, Ni) including single crystals of Ti{sub 8}Co{sub 3}Ru{sub 18}B{sub 8} have been prepared by arc-melting the elements. The phases were characterized by powder X-ray diffraction (Rietveld refinement), single-crystal X-ray diffraction (for M=Co), and energy-dispersive X-ray (EDX) analysis. They are substitutional variants of the Zn{sub 11}Rh{sub 18}B{sub 8} structure type, space group P4/mbm (No. 127) and contain a “scaffold” structural unit (M-ladders interacting with M/Ti-chains) as well as isolated M/Ti-chains. According to DFT calculations, the Ru–X (X=B, Ti, Ti/M) bonding interactions are nearly constant throughout the series and responsible for the structural stability of these phases, whereas the M–M and Ru–M interactions vary significantly with varying valence electron count. Furthermore, density of states (DOS) analyses predict the phases with M=Mn and Ni to develop a total magnetic moment but not the M=Co phase. Susceptibility measurements confirm the Co phase to be paramagnetic and the Mn Phase orders ferrimagnetically below 120 K and thus develops a magnetic moment, as predicted. - Graphical abstract: The crystal structures of the new phases (M=Cr, Mn, Co, Ni) are confirmed by Rietveld refinement of powder diffraction data and single crystal X-ray diffraction (for M=Co) to contain beside the M-ladder also M/Ti-chains. Similar to the series Ti{sub 9}M{sub 2}Ru{sub 18}B{sub 8}, the crystal structure of the new phases are mainly stabilized by the heteroatomic Ru–B and Ru–Ti bonds that remain nearly constant throughout the series, whereas the M-containing bonds vary significantly with varying valence electron count. An experimental finding confirmed and even extended by COHP bonding analyses. In addition, the DOS analyses of the M-elements reveal the development of magnetic moments for the M=Mn, Ni cases but not for M=Co. Indeed, Ti{sub 8}Co

  15. Synthesis and stability of homoleptic metal(III) tetramethylaluminates.

    PubMed

    Occhipinti, Giovanni; Meermann, Christian; Dietrich, H Martin; Litlabø, Rannveig; Auras, Florian; Törnroos, Karl W; Maichle-Mössmer, Cäcilia; Jensen, Vidar R; Anwander, Reiner

    2011-04-27

    Whereas a number of homoleptic metal(III) tetramethylaluminates M(AlMe(4))(3) of the rare earth metals have proven accessible, the stability of these compounds varies strongly among the metals, with some even escaping preparation altogether. The differences in stability may seem puzzling given that this class of metals usually is considered to be relatively uniform with respect to properties. On the basis of quantum chemically obtained relative energies and atomic and molecular descriptors of homoleptic tris(tetramethylaluminate) and related compounds of rare earth metals, transition metals, p-block metals, and actinides, multivariate modeling has identified the importance of ionic metal-methylaluminate bonding and small steric repulsion between the methylaluminate ligands for obtaining stable homoleptic compounds. Low electronegativity and a sufficiently large ionic radius are thus essential properties for the central metal atom. Whereas scandium and many transition metals are too small and too electronegative for this task, all lanthanides and actinides covered in this study are predicted to give homoleptic compounds stable toward loss of trimethylaluminum, the expected main decomposition reaction. Three of the predicted lanthanide-based compounds Ln(AlMe(4))(3) (Ln = Ce, Tm, Yb) have been prepared and fully characterized in the present work, in addition to Ln(OCH(2)tBu)(3)(AlMe(3))(3) (Ln = Sc, Nd) and [Eu(AlEt(4))(2)](n). At ambient temperature, donor-free hexane solutions of Ln(AlMe(4))(3) of the Ln(3+)/Ln(2+) redox-active metal centers display enhanced reduction to [Ln(AlMe(4))(2)](n) with decreasing negative redox potential, in the order Eu ≫ Yb ≫ Sm. Whereas Eu(AlMe(4))(3) could not be identified, Yb(AlMe(4))(3) turned out to be isolable in low yield. All attempts to prepare the putative Sc(AlMe(4))(3), featuring the smallest rare earth metal center, failed.

  16. Increasing the Stability of Metal-Organic Frameworks

    DOE PAGES

    Bosch, Mathieu; Zhang, Muwei; Zhou, Hong-Cai

    2014-01-01

    Metal-organic frameworks (MOFs) are a new category of advanced porous materials undergoing study by many researchers for their vast variety of both novel structures and potentially useful properties arising from them. Their high porosities, tunable structures, and convenient process of introducing both customizable functional groups and unsaturated metal centers have afforded excellent gas sorption and separation ability, catalytic activity, luminescent properties, and more. However, the robustness and reactivity of a given framework are largely dependent on its metal-ligand interactions, where the metal-containing clusters are often vulnerable to ligand substitution by water or other nucleophiles, meaning that the frameworks may collapsemore » upon exposure even to moist air. Other frameworks may collapse upon thermal or vacuum treatment or simply over time. This instability limits the practical uses of many MOFs. In order to further enhance the stability of the framework, many different approaches, such as the utilization of high-valence metal ions or nitrogen-donor ligands, were recently investigated. This review details the efforts of both our research group and others to synthesize MOFs possessing drastically increased chemical and thermal stability, in addition to exemplary performance for catalysis, gas sorption, and separation.« less

  17. Molecular Modeling of High-Temperature Oxidation of Refractory Borides

    DTIC Science & Technology

    2008-02-01

    04-Feb 08 Final Technical 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER MOLECULAR MODELING OF HIGH-TEMPERATURE OXIDATION OF REFRACTORY BORIDES 5b. GRANT...Prescribed by ANSI Std. Z39.18 MOLECULAR MODELING OF HIGH-TEMPERATURE OXIDATION OF REFRACTORY BORIDES FA9550-05-1-0026 Final Report (11/15/2004-02/14...deficient centers, instead of molecular 02 as in the Deal-Grove model . These network defects will lead to sub-linear dependence of the oxidation rate with

  18. Metal Cations in G-Quadruplex Folding and Stability

    NASA Astrophysics Data System (ADS)

    Bhattacharyya, Debmalya; Mirihana Arachchilage, Gayan; Basu, Soumitra

    2016-09-01

    This review is focused on the structural and physico-chemical aspects of metal cation coordination to G-Quadruplexes (GQ) and their effects on GQ stability and conformation. G-Quadruplex structures are non-canonical secondary structures formed by both DNA and RNA. G-quadruplexes regulate a wide range of important biochemical processes. Besides the sequence requirements, the coordination of monovalent cations in the GQ is essential for its formation and determines the stability and polymorphism of GQ structures. The nature, location and dynamics of the cation coordination and their impact on the overall GQ stability are dependent on several factors such as the ionic radii, hydration energy and the bonding strength to the O6 of guanines. The intracellular monovalent cation concentration and the localized ion concentrations determine the formation of GQs and can potentially dictate their regulatory roles. A wide range of biochemical and biophysical studies on an array of GQ enabling sequences have generated at a minimum the knowledge base that allows us to often predict the stability of GQs in presence of the physiologically relevant metal ions, however, prediction of conformation of such GQs is still out of the realm.

  19. Metal Cations in G-Quadruplex Folding and Stability

    PubMed Central

    Bhattacharyya, Debmalya; Mirihana Arachchilage, Gayan; Basu, Soumitra

    2016-01-01

    This review is focused on the structural and physicochemical aspects of metal cation coordination to G-Quadruplexes (GQ) and their effects on GQ stability and conformation. G-quadruplex structures are non-canonical secondary structures formed by both DNA and RNA. G-quadruplexes regulate a wide range of important biochemical processes. Besides the sequence requirements, the coordination of monovalent cations in the GQ is essential for its formation and determines the stability and polymorphism of GQ structures. The nature, location, and dynamics of the cation coordination and their impact on the overall GQ stability are dependent on several factors such as the ionic radii, hydration energy, and the bonding strength to the O6 of guanines. The intracellular monovalent cation concentration and the localized ion concentrations determine the formation of GQs and can potentially dictate their regulatory roles. A wide range of biochemical and biophysical studies on an array of GQ enabling sequences have generated at a minimum the knowledge base that allows us to often predict the stability of GQs in the presence of the physiologically relevant metal ions, however, prediction of conformation of such GQs is still out of the realm. PMID:27668212

  20. Chemical, thermal and mechanical stabilities of metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Howarth, Ashlee J.; Liu, Yangyang; Li, Peng; Li, Zhanyong; Wang, Timothy C.; Hupp, Joseph T.; Farha, Omar K.

    2016-03-01

    The construction of thousands of well-defined, porous, metal-organic framework (MOF) structures, spanning a broad range of topologies and an even broader range of pore sizes and chemical functionalities, has fuelled the exploration of many applications. Accompanying this applied focus has been a recognition of the need to engender MOFs with mechanical, thermal and/or chemical stability. Chemical stability in acidic, basic and neutral aqueous solutions is important. Advances over recent years have made it possible to design MOFs that possess different combinations of mechanical, thermal and chemical stability. Here, we review these advances and the associated design principles and synthesis strategies. We focus on how these advances may render MOFs effective as heterogeneous catalysts, both in chemically harsh condensed phases and in thermally challenging conditions relevant to gas-phase reactions. Finally, we briefly discuss future directions of study for the production of highly stable MOFs.

  1. Formation and Characterization of Hydrogen Boride Sheets Derived from MgB2 by Cation Exchange.

    PubMed

    Nishino, Hiroaki; Fujita, Takeshi; Cuong, Nguyen Thanh; Tominaka, Satoshi; Miyauchi, Masahiro; Iimura, Soshi; Hirata, Akihiko; Umezawa, Naoto; Okada, Susumu; Nishibori, Eiji; Fujino, Asahi; Fujimori, Tomohiro; Ito, Shin-Ichi; Nakamura, Junji; Hosono, Hideo; Kondo, Takahiro

    2017-10-04

    Two-dimensional (2D) materials are promising for applications in a wide range of fields because of their unique properties. Hydrogen boride sheets, a new 2D material recently predicted from theory, exhibit intriguing electronic and mechanical properties as well as hydrogen storage capacity. Here, we report the experimental realization of 2D hydrogen boride sheets with an empirical formula of H1B1, produced by exfoliation and complete ion-exchange between protons and magnesium cations in magnesium diboride (MgB2) with an average yield of 42.3% at room temperature. The sheets feature an sp(2)-bonded boron planar structure without any long-range order. A hexagonal boron network with bridge hydrogens is suggested as the possible local structure, where the absence of long-range order was ascribed to the presence of three different anisotropic domains originating from the 2-fold symmetry of the hydrogen positions against the 6-fold symmetry of the boron networks, based on X-ray diffraction, X-ray atomic pair distribution functions, electron diffraction, transmission electron microscopy, photo absorption, core-level binding energy data, infrared absorption, electron energy loss spectroscopy, and density functional theory calculations. The established cation-exchange method for metal diboride opens new avenues for the mass production of several types of boron-based 2D materials by countercation selection and functionalization.

  2. Subminiature eddy current transducers for studying boride coatings

    NASA Astrophysics Data System (ADS)

    Dmitriev, S. F.; Ishkov, A. V.; Malikov, V. N.; Sagalakov, A. M.

    2016-07-01

    Strengthening of parts and units of machines, increased reliability and longer service life is an important task of modern mechanical engineering. The main objects of study in the work were selected steel 65G and 50HGA, wear-resistant boride coatings ternary system Fe-B-Fe n B which were investigated by scanning electron microscopy and eddy-current nondestructive methods.

  3. Stability of Bulk Metallic Glass Structure. Final Report

    SciTech Connect

    Jain, H.; Williams, D. B.

    2003-06-01

    The fundamental origins of the stability of the (Pd-Ni){sub 80}P{sub 20} bulk metallic glasses (BMGs), a prototype for a whole class of BMG formers, were explored. While much of the properties of their BMGs have been characterized, their glass-stability have not been explained in terms of the atomic and electronic structure. The local structure around all three constituent atoms was obtained, in a complementary way, using extended X-ray absorption fine structure (EXAFS), to probe the nearest neighbor environment of the metals, and extended energy loss fine structure (EXELFS), to investigate the environment around P. The occupied electronic structure was investigated using X-ray photoelectron spectroscopy (XPS). The (Pd-Ni){sub 80}P{sub 20} BMGs receive their stability from cumulative, and interrelated, effects of both atomic and electronic origin. The stability of the (Pd-Ni){sub 80}P{sub 20} BMGs can be explained in terms of the stability of Pd{sub 60}Ni{sub 20}P{sub 20} and Pd{sub 30}Ni{sub 50}P{sub 20}, glasses at the end of BMG formation. The atomic structure in these alloys is very similar to those of the binary phosphide crystals near x=0 and x=80, which are trigonal prisms of Pd or Ni atoms surrounding P atoms. Such structures are known to exist in dense, randomly-packed systems. The structure of the best glass former in this series, Pd{sub 40}Ni{sub 40}P{sub 20} is further described by a weighted average of those of Pd{sub 30}Ni{sub 50}P{sub 20} and Pd{sub 60}Ni{sub 20}P{sub 20}. Bonding states present only in the ternary alloys were found and point to a further stabilization of the system through a negative heat of mixing between Pd and Ni atoms. The Nagel and Tauc criterion, correlating a decrease in the density of states at the Fermi level with an increase in the glass stability, was consistent with greater stability of the Pd{sub x}Ni{sub 80-x}P{sub 20} glasses with respect to the binary alloys of P. A valence electron concentration of 1.8 e/a, which

  4. Adsorption of copper ions onto microwave stabilized heavy metal sludge.

    PubMed

    Hsieh, Ching-Hong; Lo, Shang-Lien; Kuan, Wen-Hui; Chen, Ching-Lung

    2006-08-21

    Microwave stabilized heavy metal sludge was used as an adsorbent to remove the copper ions from aqueous solution. The adsorption characteristics of copper on the stabilized-sludge were studied by various models, such as Freundlich and Langmuir isotherm equation. Results show that the pH(zpc) of stabilized-sludge was at 9.2-9.5. Moreover, the adsorption of copper ions onto the stabilized-sludge surface was mainly on account of the heterogeneous surface of the stabilized-sludge. In the dynamic study, the experimental data was fitted to the intraparticle diffusion model, pseudo-first order model and pseudo-second order model. However, the experimental data was only well correlated with pseudo-second order model with the correlation coefficient>0.995. Furthermore, both Freundlich and Langmuir isotherm equations were found to represent the measured adsorption data well. From the Langmuir equation, the adsorption capacity increased from 18 to 28 mg/g as the temperature rose from 15 to 55 degrees C, since this adsorption process was an endothermic reaction. After this adsorption process, copper ions can be concentrated on and in a small bead and recovery efficiently.

  5. The Wyckoff positional order and polyhedral intergrowth in the M3B2- and M5B3-type boride precipitated in the Ni-based superalloys

    PubMed Central

    Hu, X. B.; Zhu, Y. L.; Sheng, N. C.; Ma, X. L.

    2014-01-01

    Ni-based single superalloys play a crucial role in the hottest parts of jet engines. However, due to the complex geometry and macro-segregation during the solidification process, the cast defect such as stray grains is inevitable. Therefore, the transient liquid phase (TLP) bonding which can join several small single crystalline castings together is gradually believed to be an effective method for improving the yields of production of the complex components. The melting point depressant element B is always added into the interlayer filler material. Consequently, borides including the M3B2 and M5B3 phase usually precipitate during the TLP bonding process. So a comprehensive knowledge of the fine structural characteristics of the borides is very critical for an accurate evaluation of the TLP bonding process. In this work, by means of the aberration-corrected transmission electron microscopy, we show, at an atomic scale, the Wyckoff positional order phenomenon of the metal atoms in the unit cell of M3B2- and M5B3-type boride. Meanwhile, the defect along the (001) plane of the above two types of boride are determined to be the polyhedral intergrowth with complex configurations. PMID:25482386

  6. The Wyckoff positional order and polyhedral intergrowth in the M3B2- and M5B3-type boride precipitated in the Ni-based superalloys

    NASA Astrophysics Data System (ADS)

    Hu, X. B.; Zhu, Y. L.; Sheng, N. C.; Ma, X. L.

    2014-12-01

    Ni-based single superalloys play a crucial role in the hottest parts of jet engines. However, due to the complex geometry and macro-segregation during the solidification process, the cast defect such as stray grains is inevitable. Therefore, the transient liquid phase (TLP) bonding which can join several small single crystalline castings together is gradually believed to be an effective method for improving the yields of production of the complex components. The melting point depressant element B is always added into the interlayer filler material. Consequently, borides including the M3B2 and M5B3 phase usually precipitate during the TLP bonding process. So a comprehensive knowledge of the fine structural characteristics of the borides is very critical for an accurate evaluation of the TLP bonding process. In this work, by means of the aberration-corrected transmission electron microscopy, we show, at an atomic scale, the Wyckoff positional order phenomenon of the metal atoms in the unit cell of M3B2- and M5B3-type boride. Meanwhile, the defect along the (001) plane of the above two types of boride are determined to be the polyhedral intergrowth with complex configurations.

  7. Electrochemical Corrosion Behavior of Borided CoCrMo Alloy Immersed in Hanks' Solution

    NASA Astrophysics Data System (ADS)

    Rosas-Becerra, G.; Mejía-Caballero, I.; Martínez-Trinidad, J.; Palomar-Pardavé, M.; Romero-Romo, M.; Pérez-Pasten-Borja, R.; Campos-Silva, I.

    2017-02-01

    New results about the corrosion resistance of borided CoCrMo alloy exposed to the Hanks' solution during different days were estimated by means of the electrochemical impedance spectroscopy technique. The CoB-Co2B coating was developed on the surface of the borided alloy using the powder-pack boriding process at 1223 K during 6 h of exposure. The corrosion resistance of the borided cobalt alloy was evaluated by the fitting of suitable equivalent electrical circuits using Nyquist and Bode plots to obtain the electrochemical parameters; the results were compared with the CoCrMo (non-borided) alloy. The samples (borided and non-borided) were characterized by the scanning electron microscopy and by the energy-dispersive x-ray spectrometry techniques to determine the elemental chemical composition developed on the surface of the materials. In addition, the reaction products formed on the surface of the borided CoCrMo alloy exposed to the Hanks' solution after the tenth day of immersion were analyzed by the x-ray photoelectron spectroscopy (XPS) technique. The results showed that the corrosion resistance of the borided cobalt alloy was affected (or reduced) by the presence of B2S3 and CrPO4 clusters formed on the material's surface. Finally, the electrochemical reactions developed during the immersion of the borided cobalt alloy on the tenth day of exposure were proposed according to the XPS results.

  8. Stabilization of Lithium Transition Metal Silicates in the Olivine Structure

    DOE PAGES

    Sun, Xiaoqi; Tripathi, Rajesh; Popov, Guerman; ...

    2017-07-28

    While olivine LiFePO4 shows amongst the best electrochemical properties of Li-ion positive electrodes with respect to rate behavior owing to facile Li+ migration pathways in the framework, replacing the [PO4] 3- polyanion with a silicate [SO4] 4- moitie in olivine is desirable. This would allow additional balancing alkali content and hence electron transfer, and increase the capacity. We demonstrate the first stabilization of a lithium transition-metal silicate (as a pure silicate) in the olivine structure type. Using LiInSiO4 and LiScSiO4 as the parent materials, transition metal (Mn, Fe, Co) substitutions on the In/Sc site were investigated by computational modelling viamore » atomic scale simulation. Transition metal substitution was found to be only favourable for Co, a finding confirmed by the successful solid state synthesis of olivine LixInyCo2-x-ySiO4. Finally, the stabilization of the structure was achieved by entropy provided by cation disorder.« less

  9. Stability of metal oxide nanoparticles in aqueous solutions.

    PubMed

    Tso, Chih-ping; Zhung, Cheng-min; Shih, Yang-hsin; Tseng, Young-Ming; Wu, Shian-chee; Doong, Ruey-an

    2010-01-01

    The application of nanoparticles in the processes of making commercial products has increased in recent years due to their unique physical and chemical properties. With increasing amount of commercial nanoparticles released into nature, their fate and effects on the ecosystem and human health are of growing concern. This study investigated the stability and morphology of three metal oxide nanoparticles in aqueous solutions. The commercially available nanoparticles, TiO(2), ZnO, SiO(2), aggregated quickly into micrometer-size particles in aqueous solutions, which may not threaten human health. Their changes in morphology and characteristics were further examined by dynamic light scattering (DLS) method and transmission electron microscopy (TEM). Among the several dispersion approaches, ultrasonication was found to be the most effective for disaggregating nanoparticles in water. For these three selected nanoparticles, ZnO could not remain stable in suspensions, presumably due to the dissolution of particles to form high concentration of ions, resulting in enhanced aggregation of particles. In addition, the existence of dissolved organic matters stabilized nanoparticles in lake water and wastewater for several hours in spite of the high concentration of cations in these real-water samples. The fate of metal oxide nanoparticles in natural water bodies would be determined by the type and concentration of cations and organic matters. Results obtained in this study revealed that the stability of nanoparticles changed under different aqueous conditions and so did their fate in the environment.

  10. Nanotwinned metal MEMS films with unprecedented strength and stability.

    PubMed

    Sim, Gi-Dong; Krogstad, Jessica A; Reddy, K Madhav; Xie, Kelvin Y; Valentino, Gianna M; Weihs, Timothy P; Hemker, Kevin J

    2017-06-01

    Silicon-based microelectromechanical systems (MEMS) sensors have become ubiquitous in consumer-based products, but realization of an interconnected network of MEMS devices that allows components to be remotely monitored and controlled, a concept often described as the "Internet of Things," will require a suite of MEMS materials and properties that are not currently available. We report on the synthesis of metallic nickel-molybdenum-tungsten films with direct current sputter deposition, which results in fully dense crystallographically textured films that are filled with nanotwins. These films exhibit linear elastic mechanical behavior and tensile strengths exceeding 3 GPa, which is unprecedented for materials that are compatible with wafer-level device fabrication processes. The ultrahigh strength is attributed to a combination of solid solution strengthening and the presence of dense nanotwins. These films also have excellent thermal and mechanical stability, high density, and electrical properties that are attractive for next-generation metal MEMS applications.

  11. Facile self-assembly and stabilization of metal oxide nanoparticles.

    PubMed

    Charbonneau, Cecile; Holliman, Peter J; Davies, Matthew L; Watson, Trystan M; Worsley, David A

    2015-03-15

    This paper describes a facile method of self-assembling different metal oxide nanoparticles into nanostructured materials via di-carboxylate linkers (oxalic acid) using TiO2 as an example. In this method, the di-carboxylate linkers react with surface hydroxyls on metal oxide nanoparticles forming covalent, ester-like bonds, which enable the binding of two metal oxide particles, one at either end of the linker and facilitates efficient self-assembly of one group of metal oxide nanoparticles homogeneously distributed onto the surface of another group. The oxalate linkers can then be removed by thermal decomposition. This approach is shown to be effective using differently-sized TiO2 nanoparticles, namely in-house synthesized 3-5nm anatase nanocrystals and Degussa P25 titania particles (mean 21nm particle size). Our data show that the application of a high temperature heat treatment (450°C for 30min), conventionally applied to achieve a stable porous structure by thermal decomposition of the linker molecules and by inducing inter-particle necking, damages the surface area of the nanostructured material. However, here we show that sintering at 300°C for 30min or by flash near infrared radiation sintering for 12s efficiently decomposes the oxalate linkers and stabilizes the nanostructure of the material whilst maintaining its high surface area. Copyright © 2013 Elsevier Inc. All rights reserved.

  12. Stability and robustness of metal-supported SOFCs

    NASA Astrophysics Data System (ADS)

    Tucker, Michael C.; Lau, Grace Y.; Jacobson, Craig P.; DeJonghe, Lutgard C.; Visco, Steven J.

    Tubular metal-supported SOFCs with YSZ electrolyte and electrodes comprising porous YSZ backbone and infiltrated Ni and LSM catalysts are operated at 700 °C. Tolerance to five complete anode redox cycles and five very rapid thermal cycles is demonstrated. The power output of a cell with as-infiltrated Ni anode degrades rapidly over 15 h operation. This degradation can be attributed primarily to coarsening of the fine infiltrated Ni particles. A cell in which the infiltrated Ni anode is precoarsened at 800 °C before operation at 700 °C shows dramatically improved stability. Stable operation over 350 h is demonstrated.

  13. New YMo{sub 3}B{sub 7} boride and its structure

    SciTech Connect

    Mikhalenko, S.I.; Kuz`ma, Yu.B.; Babizhetskii, V.S.

    1995-05-01

    The crystal structure of YMo{sub 3}B{sub 7} boride is determined (a CAD-4 diffractometer, MoK{sub {alpha}} radiation, R = 0.019 for 668 reflections). The crystals are orthorhombic: a = 11.012(1) {Angstrom}, b = 3.1013(3) {Angstrom}, c = 12.864(1) {Angstrom}; Z = 4; {rho}{sub calc} = 6.839(2) g/cm{sup 3}; and sp. gr. Pnma. The structure belongs to a new type: metal atoms form trigonal prisms, within which boron atoms occur. Four columns of alternating empty orthorhombic [EMo{sub 4}Y] pyramids and [EMo{sub 2}Y{sub 2}] tetrahedra run in the b direction. The boron atoms form ribbons of six-membered rings. The ribbons are tilted to the ab plane. 8 refs., 3 figs.

  14. Super-hard coating creation by laser boriding technique

    NASA Astrophysics Data System (ADS)

    Monisha, K.; Kumar, S. Arun; Gunaseelan, M.; Senthilselvan, J.

    2017-05-01

    Laser surface boriding was carried out using boropak and TiB+amorphous boron coated Cp-Ti alloy with high power diode laser (HPDL). The effect of boron agents and laser processing parameters on the microstructure, crystallographic phase formations and hardness are investigated by optical microscopy, scanning electron microscopy, XRD and hardness testing. Super-hard coating with hardness in the range of 1000 to 3000 HV0.2 was created by laser alloying the boropak and TiB+amorphous boron coated Cp-Ti. It is due to the formation of TiB2, TiB and Ti3B4 composite layers. Laser boriding has resulted in 2500 µm thick coating.

  15. An Evaluation of a Borided Layer Formed on Ti-6Al-4V Alloy by Means of SMAT and Low-Temperature Boriding

    PubMed Central

    Yao, Quantong; Sun, Jian; Fu, Yuzhu; Tong, Weiping; Zhang, Hui

    2016-01-01

    In this paper, a nanocrystalline surface layer without impurities was fabricated on Ti-6Al-4V alloy by means of surface mechanical attrition treatment (SMAT). The grain size in the nanocrystalline layer is about 10 nm and grain morphology displays a random crystallographic orientation distribution. Subsequently, the low-temperature boriding behaviors (at 600 °C) of the SMAT sample, including the phase composition, microstructure, micro-hardness, and brittleness, were investigated in comparison with those of coarse-grained sample borided at 1100 °C. The results showed that the boriding kinetics could be significantly enhanced by SMAT, resulting in the formation of a nano-structured boride layers on Ti-6Al-4V alloy at lower temperature. Compared to the coarse-grained boriding sample, the SMAT boriding sample exhibits a similar hardness value, but improved surface toughness. The satisfactory surface toughness may be attributed to the boriding treatment that was carried out at lower temperature. PMID:28774115

  16. Growth and Stability of Nanocrystalline Metal Domains within Nanoporous Carbon Nanotube Aerogels

    NASA Astrophysics Data System (ADS)

    Jeong, Yeon Joo

    This thesis focuses on how to grow and stabilize nanocrystalline metal domains within nanoporous carbon nanotube aerogels. It describes the growth of isolated metal nanocrystals within carbon nanotube aerogel networks and the growth of nanocrystalline metals within 2D and 3D carbon nanotube aerogel networks. It also discusses electrochemical stability for generating electricity from fuel cells and thermal stability for reinforcing structural materials. (Abstract shortened by UMI.).

  17. Star-like copolymer stabilized noble-metal nanoparticle powders

    NASA Astrophysics Data System (ADS)

    Cao, Peng-Fei; Yan, Yun-Hui; Mangadlao, Joey Dacula; Rong, Li-Han; Advincula, Rigoberto

    2016-03-01

    The amphiphilic star-like copolymer polyethylenimine-block-poly(ε-caprolactone) (PEI-b-PCL) was utilized to transfer the pre-synthesized citrate-capped noble metal nanoparticles (NMNPs) from an aqueous layer to an organic layer without any additional reagents. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) were utilized to study the assembly of the polymers coated on the surface of the citrate-capped NMNPs. After removing the organic solvent, the polymer-coated NMNPs in powder form (PCP-NMNPs) were obtained. The excellent solubility of the PEI-b-PCL allows the PCP-NMNPs to be easily dispersed in most of the organic solvents without any significant aggregation. Moreover, the good thermal stability and long-term stability make PCP-NMNPs an excellent NMNP-containing hybrid system for different specific applications, such as surface coating, catalysis and thermoplastic processing of nanocomposite materials.The amphiphilic star-like copolymer polyethylenimine-block-poly(ε-caprolactone) (PEI-b-PCL) was utilized to transfer the pre-synthesized citrate-capped noble metal nanoparticles (NMNPs) from an aqueous layer to an organic layer without any additional reagents. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) were utilized to study the assembly of the polymers coated on the surface of the citrate-capped NMNPs. After removing the organic solvent, the polymer-coated NMNPs in powder form (PCP-NMNPs) were obtained. The excellent solubility of the PEI-b-PCL allows the PCP-NMNPs to be easily dispersed in most of the organic solvents without any significant aggregation. Moreover, the good thermal stability and long-term stability make PCP-NMNPs an excellent NMNP-containing hybrid system for different specific applications, such as surface coating, catalysis and thermoplastic processing of nanocomposite materials. Electronic supplementary information (ESI) available: Synthesis scheme and the 1H NMR spectrum of PEI

  18. Stabilization of ultrafine metal nanocatalysts on thin carbon sheets

    NASA Astrophysics Data System (ADS)

    Liu, Xiaofang; Cui, Xinrui; Liu, Yiding; Yin, Yadong

    2015-10-01

    A novel strategy was proposed to anchor ultrafine metal nanoparticles (NPs) on thin carbon sheets for highly stable and efficient heterogeneous catalysts. In this facile approach, a dense monolayer of ultrafine AuNPs was sandwiched between a silica core and a resin shell, followed by carbonization of the shell at a high temperature and then selective removal of the silica core. The shrinkage of the shells during carbonization facilitates partial embedment of the AuNPs on the carbon shell surface and provides superior stability against particle sintering during high temperature/mechanical post-treatments and catalytic reactions. It was also found that diffusion of reactants to the surface of AuNPs could be maximized by reducing the thickness of the hollow shells or simply by cracking the shells into thin carbon sheets, both significantly benefiting the catalytic efficiency. The advantages of this ultra-stable architecture together with the densely dispersed catalytic sites were demonstrated by their high stability and superior catalytic activity in reducing hydrophilic 4-nitrophenol and hydrophobic nitrobenzene.A novel strategy was proposed to anchor ultrafine metal nanoparticles (NPs) on thin carbon sheets for highly stable and efficient heterogeneous catalysts. In this facile approach, a dense monolayer of ultrafine AuNPs was sandwiched between a silica core and a resin shell, followed by carbonization of the shell at a high temperature and then selective removal of the silica core. The shrinkage of the shells during carbonization facilitates partial embedment of the AuNPs on the carbon shell surface and provides superior stability against particle sintering during high temperature/mechanical post-treatments and catalytic reactions. It was also found that diffusion of reactants to the surface of AuNPs could be maximized by reducing the thickness of the hollow shells or simply by cracking the shells into thin carbon sheets, both significantly benefiting the

  19. Electronic Principles Governing the Stability and Reactivity of Ligated Metal and Silicon Encapsulated Transition Metal Clusters

    NASA Astrophysics Data System (ADS)

    Abreu, Marissa Baddick

    A thorough understanding of the underlying electronic principles guiding the stability and reactivity of clusters has direct implications for the identification of stable clusters for incorporation into clusters-assembled materials with tunable properties. This work explores the electronic principles governing the stability and reactivity of two types of clusters: ligated metal clusters and silicon encapsulated transition metal clusters. In the first case, the reactivity of iodine-protected aluminum clusters, Al13Ix - (x=0-4) and Al14Iy- (y=0-5), with the protic species methanol was studied. The symmetrical ground states of Al13Ix- showed no reactivity with methanol but reactivity was achieved in a higher energy isomer of Al 13I2- with iodines on adjacent aluminum atoms -- complementary Lewis acid-base active sites were induced on the opposite side of the cluster capable of breaking the O-H bond in methanol. Al 14Iy- (y=2-5) react with methanol, but only at the ligated adatom site. Reaction of methanol with Al14 - and Al14I- showed that ligation of the adatom was necessary for the reaction to occur there -- revealing the concept of a ligand-activated adatom. In the second case, the study focused heavily on CrSi12, a silicon encapsulated transition metal cluster whose stability and the reason for that stability has been debated heavily in the literature. Calculations of the energetic properties of CrSi n (n=6-16) revealed both CrSi12 and CrSi14 to have enhanced stability relative to other clusters; however CrSi12 lacks all the traditional markers of a magic cluster. Molecular orbital analysis of each of these clusters showed the CNFEG model to be inadequate in describing their stability. Because the 3dz2 orbital of Cr is unfilled in CrSi12, this cluster has only 16 effective valence electrons, meaning that the 18-electron rule is not applicable. The moderate stability of CrSi 12 can be accounted for by the crystal-field splitting of the 3d orbitals, which pushes the

  20. PASSIVATION LAYER STABILITY OF A METALLIC ALLOY WASTE FORM

    SciTech Connect

    Williamson, M.; Mickalonis, J.; Fisher, D.; Sindelar, R.

    2010-08-16

    Alloy waste form development under the Waste Forms Campaign of the DOE-NE Fuel Cycle Research & Development program includes the process development and characterization of an alloy system to incorporate metal species from the waste streams generated during nuclear fuel recycling. This report describes the tests and results from the FY10 activities to further investigate an Fe-based waste form that uses 300-series stainless steel as the base alloy in an induction furnace melt process to incorporate the waste species from a closed nuclear fuel recycle separations scheme. This report is focused on the initial activities to investigate the formation of oxyhydroxide layer(s) that would be expected to develop on the Fe-based waste form as it corrodes under aqueous repository conditions. Corrosion tests were used to evaluate the stability of the layer(s) that can act as a passivation layer against further corrosion and would affect waste form durability in a disposal environment.

  1. Stability of commercial metal oxide nanoparticles in water.

    PubMed

    Zhang, Yang; Chen, Yongsheng; Westerhoff, Paul; Hristovski, Kiril; Crittenden, John C

    2008-04-01

    The fate of commercial nanoparticles in water is of significant interest to health and regulatory authorities. This research investigated the dispersion and stability of metal oxide nanoparticles in water as well as their removal by potable water treatment processes. Commercial nanoparticles were received as powder aggregates, and in water neither ultrasound nor chemical dispersants could break them up into primary nanoparticles. Lab-synthesized hematite was prepared as a primary nanoparticle (85 nm) suspension; upon drying and 1-month storage, however, hematite formed aggregates that could not be dispersed completely as primary nanoparticles in water. This observation may explain why it is difficult to disperse dry commercial nanoparticles. Except for silica, other nanoparticles rapidly aggregated in tap water due to electric double layer (EDL) compression. The stability of silica in tap water is related to its low Hamaker constant. For all these nanoparticles, at an alum dosage of 60 mg/L, coagulation followed by sedimentation could remove 20-60% of the total nanoparticle mass. Filtration using a 0.45 microm filter was required to remove more than 90% of the nanoparticle mass.

  2. Origin of Shear Stability and Compressive Ductility Enhancement of Metallic Glasses by Metal Coating

    PubMed Central

    Sun, B. A.; Chen, S. H.; Lu, Y. M.; Zhu, Z. G.; Zhao, Y. L.; Yang, Y.; Chan, K. C.; Liu, C. T.

    2016-01-01

    Metallic glasses (MGs) are notorious for the poor macroscopic ductility and to overcome the weakness various intrinsic and extrinsic strategies have been proposed in past decades. Among them, the metal coating is regarded as a flexible and facile approach, yet the physical origin is poorly understood due to the complex nature of shear banding process. Here, we studied the origin of ductile enhancement in the Cu-coating both experimentally and theoretically. By examining serrated shear events and their stability of MGs, we revealed that the thin coating layer plays a key role in stopping the final catastrophic failure of MGs by slowing down shear band dynamics and thus retarding its attainment to a critical instable state. The mechanical analysis on interplay between the coating layer and shear banding process showed the enhanced shear stability mainly comes from the lateral tension of coating layer induced by the surface shear step and the bonding between the coating layer and MGs rather than the layer thickness is found to play a key role in contributing to the shear stability. PMID:27271435

  3. Origin of Shear Stability and Compressive Ductility Enhancement of Metallic Glasses by Metal Coating

    NASA Astrophysics Data System (ADS)

    Sun, B. A.; Chen, S. H.; Lu, Y. M.; Zhu, Z. G.; Zhao, Y. L.; Yang, Y.; Chan, K. C.; Liu, C. T.

    2016-06-01

    Metallic glasses (MGs) are notorious for the poor macroscopic ductility and to overcome the weakness various intrinsic and extrinsic strategies have been proposed in past decades. Among them, the metal coating is regarded as a flexible and facile approach, yet the physical origin is poorly understood due to the complex nature of shear banding process. Here, we studied the origin of ductile enhancement in the Cu-coating both experimentally and theoretically. By examining serrated shear events and their stability of MGs, we revealed that the thin coating layer plays a key role in stopping the final catastrophic failure of MGs by slowing down shear band dynamics and thus retarding its attainment to a critical instable state. The mechanical analysis on interplay between the coating layer and shear banding process showed the enhanced shear stability mainly comes from the lateral tension of coating layer induced by the surface shear step and the bonding between the coating layer and MGs rather than the layer thickness is found to play a key role in contributing to the shear stability.

  4. Hybridization of Metal Nanoparticles with Metal-Organic Frameworks Using Protein as Amphiphilic Stabilizer.

    PubMed

    Mao, Hui; Zhang, Weina; Zhou, Weiqiang; Zou, Binghua; Zheng, Bing; Zhao, Shilin; Huo, Fengwei

    2017-07-26

    Here, a facile strategy is reported to efficiently hybridize metal nanoparticles (MNPs) with typical metal-organic frameworks (MOFs) of ZIF-8 (zeolitic imidazolate framework-8), which employs bovine serum albumin (BSA, a serum albumin protein derived from cows) as the amphiphilic stabilizer to increase the affinity of MNP toward MOFs. For instance, the as-synthesized PdNPs/ZIF-8 composites with diameter from 100 to 200 nm always maintain well-defined crystalline structure, and the PdNPs with small size of ∼2 nm are well-dispersed in the crystal of MOFs without serious aggregations due to the BSA stabilizer. In Suzuki cross-coupling reactions of aryl halide, the PdNPs/ZIF-8 as catalysts have exhibited high activity and satisfied reusability owing to the use of BSA stabilizer as well as the fixing of MOFs matrixes. In addition, the strategy also can be extended to synthesize other kinds of MNPs/MOFs hybrid composites with tunable particle size, which brings more opportunity for functional MOFs hybrid materials.

  5. Origin of Shear Stability and Compressive Ductility Enhancement of Metallic Glasses by Metal Coating.

    PubMed

    Sun, B A; Chen, S H; Lu, Y M; Zhu, Z G; Zhao, Y L; Yang, Y; Chan, K C; Liu, C T

    2016-06-08

    Metallic glasses (MGs) are notorious for the poor macroscopic ductility and to overcome the weakness various intrinsic and extrinsic strategies have been proposed in past decades. Among them, the metal coating is regarded as a flexible and facile approach, yet the physical origin is poorly understood due to the complex nature of shear banding process. Here, we studied the origin of ductile enhancement in the Cu-coating both experimentally and theoretically. By examining serrated shear events and their stability of MGs, we revealed that the thin coating layer plays a key role in stopping the final catastrophic failure of MGs by slowing down shear band dynamics and thus retarding its attainment to a critical instable state. The mechanical analysis on interplay between the coating layer and shear banding process showed the enhanced shear stability mainly comes from the lateral tension of coating layer induced by the surface shear step and the bonding between the coating layer and MGs rather than the layer thickness is found to play a key role in contributing to the shear stability.

  6. New ternary tantalum borides containing boron dumbbells: Experimental and theoretical studies of Ta2OsB2 and TaRuB

    NASA Astrophysics Data System (ADS)

    Mbarki, Mohammed; Touzani, Rachid St.; Rehorn, Christian W. G.; Gladisch, Fabian C.; Fokwa, Boniface P. T.

    2016-10-01

    The new ternary transition metal-rich borides Ta2OsB2 and TaRuB have been successfully synthesized by arc-melting the elements in a water-cooled crucible under an argon atmosphere. The crystal structures of both compounds were solved by single-crystal X-ray diffraction and their metal compositions were confirmed by EDX analysis. It was found that Ta2OsB2 and TaRuB crystallize in the tetragonal Nb2OsB2 (space group P4/mnc, no. 128) and the orthorhombic NbRuB (space group Pmma, no. 51) structure types with lattice parameters a=5.878(2) Å, c=6.857(2) Å and a=10.806(2) Å, b=3.196(1) Å, c=6.312(2) Å, respectively. Furthermore, crystallographic, electronic and bonding characteristics have been studied by density functional theory (DFT). Electronic structure relaxation has confirmed the crystallographic parameters while COHP bonding analysis indicates that B2-dummbells are the strongest bonds in both compounds. Moreover, the formation of osmium dumbbells in Ta2OsB2 through a Peierls distortion along the c-axis, is found to be the origin of superstructure formation. Magnetic susceptibility measurements reveal that the two phases are Pauli paramagnets, thus confirming the theoretical DOS prediction of metallic character. Also hints of superconductivity are found in the two phases, however lack of single phase samples has prevented confirmation. Furthermore, the thermodynamic stability of the two modifications of AMB (A=Nb, Ta; M =Ru, Os) are studied using DFT, as new possible phases containing either B4- or B2-units are predicted, the former being the most thermodynamically stable modification.

  7. Preparation of Pickering emulsions stabilized by metal organic frameworks using oscillatory woven metal micro-screen.

    PubMed

    Sabouni, R; Gomaa, H G

    2015-06-14

    Uniform Pickering emulsions stabilized by metal organic frameworks (MOFs) MIL-101 and ZIF-8 nanoparticles (NPs) were successfully prepared using an oscillatory woven metal microscreen (WMMS) emulsification system in the presence and the absence of surfactants. The effects of operating and system parameters including the frequency and amplitude of oscillation, the type of nano-particle and/or surfactant on the droplet size and coefficient of variance of the prepared emulsions are investigated. The results showed that both the hydrodynamics of the system and the hydrophobic/hydrophilic nature of the NP influenced the interfacial properties of the oil-water interface during droplet formation and after detachment, which in turn affected the final droplet size and distribution. Comparison between the measured and predicted droplet size using a simple torque balance (TB) model is discussed.

  8. Combustion synthesis of boride and other composites

    DOEpatents

    Halverson, Danny C.; Lum, Beverly Y.; Munir, Zuhair A.

    1989-01-01

    A self-sustaining combustion synthesis process for producing hard, tough, lightweight B.sub.4 C/TiB.sub.2 composites is based on the thermodynamic dependence of adiabatic temperature and product composition on the stoichiometry of the B.sub.4 C and TiB.sub.2 reactants. For lightweight products the composition must be relatively rich in the B.sub.4 C component. B.sub.4 C-rich composites are obtained by varying the initial temperature of the reactants. The product is hard, porous material whose toughness can be enhanced by filling the pores with aluminum or other metal phases using a liquid metal infiltration process. The process can be extended to the formation of other composites having a low exothermic component.

  9. Combustion synthesis of boride and other composites

    DOEpatents

    Halverson, D.C.; Lum, B.Y.; Munir, Z.A.

    1988-07-28

    A self-sustaining combustion synthesis process for producing hard, tough, lightweight B/sub 4/C/TiB/sub 2/ composites is described. It is based on the thermodynamic dependence of adiabatic temperature and product composition on the stoichiometry of the B/sub 4/C and TiB/sub 2/ reactants. For lightweight products the composition must be relatively rich in the B/sub 4/C component. B/sub 4/C-rich composites are obtained by varying the initial temperature of the reactants. The product is hard, porous material whose toughness can be enhanced by filling the pores with aluminum or other metal phases using a liquid metal infiltration process. The process can be extended to the formation of other composites having a low exothermic component. 9 figs., 4 tabs.

  10. Preliminary Evaluation of Animal Bone Char as Potential Metal Stabilization Agent in Metal Contaminated Soil.

    PubMed

    Gruden, Evelin; Bukovec, Peter; Zupančič, Marija

    2017-09-01

    The aim of this study was to evaluate the potential effect of animal bone char (ABC) addition on metal mobility in mine tailings. The mobility of metals after addition of ABC to tailings at four different application rates (0.6 g, 1.2 g, 1.8 g and 3.6 g ABC per 100 g of tailings) was evaluated by Toxicity Characteristic Leaching Procedure (TCLP) one step extraction. The obtained results indicated that the mobility of Pb, Cr and Cd gradually decreased with increasing quantity of added ABC. According to the TCLP, mobile concentrations of Pb in tailings exceeded threshold values for almost eight times. After ABC addition, Pb TCLP-extractable concentrations decreased from 39 mg L-1 in tailings to lower than the TCLP limit values of 5 mg L-1 at all ABC application rates, except in mixtures with the lowest addition of ABC. We concluded that ABC could be a successful metal stabilization agent for multi-metal contaminated soil, although attention should be paid at highly As contaminated soil.

  11. An Assessment of Binary Metallic Glasses: Correlations Between Structure, Glass Forming Ability and Stability (Preprint)

    DTIC Science & Technology

    2009-04-01

    through 3.5) and physical properties of the constituent elements (Sections 3.6 and 3.7) on the thermal stability and thickness of binary metallic glasses...containing alkali metals , inert gas and halogen elements were not found in this assessment. Most metallic elements have been used to produce binary metallic ... properties such as partial pair distribution functions recommend binary metallic glasses for more extensive characterization. There are surprisingly few

  12. Accelerated kinetics and mechanism of growth of boride layers on titanium under isothermal and cyclic diffusion

    NASA Astrophysics Data System (ADS)

    Sarma, Biplab

    2011-12-01

    The tendency of titanium (Ti) and its alloys to wear, gall and seize during high contact stresses between sliding surfaces severely limits their applications in bearings, gears etc. One way to mitigate these problems is to modify their surfaces by applying hard and wear resistant surface coatings. Boriding, which involves solid state diffusion of boron (B) into Ti, thereby forming hard surface layers consisting of TiB2 and TiB compounds has been shown to produce extremely high wear resistant surfaces in Ti and its alloys. The growth kinetics of these layers are, however, limited by the low diffusivities of B in the high melting TiB2 and TiB compounds. On the basis of the fact that HCP metals such as Ti show enhanced (anomalous) self-diffusion near the phase transition temperature, the first hypothesis of this work has been that the diffusivity enhancement should cause rapid ingress of B atoms, thereby accelerating the growth of the hard boride layers. Isothermal boriding experiments were performed close to phase transition temperature (890, 910, and 915°C) for time periods ranging from 3 to 24 hours. It was found that indeed a much deeper growth of TiB into the Ti substrate (˜75 mum) occurred at temperatures very close to the transition temperature (910°C), compared to that obtained at 1050°C. A diffusion model based on error-function solutions of Fick's second law was developed to quantitatively illustrate the combined effects of the normal B diffusion in the TiB phase and the anomalous B diffusion in Ti phase in accelerating TiB layer growth. Furthermore, isothermal boriding experiments close to transition temperature (900°C) for a period of 71 hours resulted in coating thickness well above 100 mum, while at 1050°C, the layer growth saturated after about 24 hours of treatment time. In the second part of this work, a novel approach named "cyclic-phase-changediffusion, (CPCD)," to create deeper TiB2 and TiB coating layers on CP-Ti by cyclic thermal processing

  13. Characterization and diffusion model for the titanium boride layers formed on the Ti6Al4V alloy by plasma paste boriding

    NASA Astrophysics Data System (ADS)

    Keddam, Mourad; Taktak, Sukru

    2017-03-01

    The present study is focused on the estimation of activation energy of boron in the plasma paste borided Ti6Al4V alloy, which is extensively used in technological applications, using an analytical diffusion model. Titanium boride layers were successfully produced by plasma paste boriding method on the Ti6Al4V alloy in the temperature range of 973-1073 K for a treatment time ranging from 3 to 7 h. The presence of both TiB2 top-layer and TiB whiskers sub-layer was confirmed by the XRD analysis and SEM observations. The surface hardness of the borided alloy was evaluated using Micro-Knoop indenter. The formation rates of the TiB2 and TiB layers were found to have a parabolic character at all applied process temperatures. A diffusion model was suggested to estimate the boron diffusivities in TiB2 and TiB layers under certain assumptions, by considering the effect of boride incubation times. Basing on own experimental data on boriding kinetics, the activation energies of boron in TiB2 and TiB phases were estimated as 136.24 ± 0.5 and 63.76 ± 0.5 kJ mol-1, respectively. Finally, the obtained values of boron activation energies for Ti6Al4V alloy were compared with the data available in the literature.

  14. Stabilization of heavy metals in contaminated sediments using organic chelating agents.

    PubMed

    Xu, Ying; Fang, Sheng-Rong

    2015-01-01

    A stabilization treatment for heavy metals in sediments was developed using the heavy metal chelators ammonium dipropyl dithiophosphate (ADD) and potassium diisopropyl dithiophosphate (PDD). The results indicate that 7% ADD and 7% PDD achieved Pb and Cu stabilization rates of up to 99%, Cd stabilization rates of 78% and 95%, and Zn stabilization rates of 21 and 51%, respectively. At pH levels ranging from 2 to 12, the amount of heavy metals in leachate from the stabilized product using the chelating agents were significantly less than those using Na2S and Na3PO4. After treatment, the chelating agents were mainly bound to the exchangeable fraction of heavy metals in the sediment and formed stable bonds with organic matter, thus significantly reducing the biological risks of heavy metals in sediment.

  15. PREFACE: The 16th International Symposium on Boron, Borides and Related Materials (ISBB 2008)

    NASA Astrophysics Data System (ADS)

    Tanaka, Takaho

    2009-07-01

    This volume of Journal of Physics: Conference Series contains invited and contributed peer-reviewed papers that were presented at the 16th International Symposium on Boron, Borides and Related Materials (ISBB 2008), which was held on 7-12 September 2008, at Kunibiki Messe, Matsue, Japan. This triennial symposium has a half-century long history starting from the 1st meeting in 1959 at Asbury Park, New Jersey. We were very pleased to organize ISBB 2008, which gathered chemists, physicists, materials scientists as well as diamond and high-pressure researchers. This meeting had a strong background in the boron-related Japanese research history, which includes the discovery of superconductivity in MgB2 and development of Nd-Fe-B hard magnets and of YB66 soft X-ray monochromator. The scope of ISBB 2008 spans both basic and applied interdisciplinary research that is centered on boron, borides and related materials, and the collection of articles defines the state of the art in research on these materials. The topics are centered on: 1. Preparation of new materials (single crystals, thin films, nanostructures, ceramics, etc) under normal or extreme conditions. 2. Crystal structure and chemical bonding (new crystal structures, nonstoichiometry, defects, clusters, quantum-chemical calculations). 3. Physical and chemical properties (band structure, phonon spectra, superconductivity; optical, electrical, magnetic, emissive, mechanical properties; phase diagrams, thermodynamics, catalytic activity, etc) in a wide range of temperatures and pressures. 4. Applications and prospects (thermoelectric converters, composites, ceramics, coatings, etc) There were a few discoveries of new materials, such as nanomaterials, and developments in applications. Many contributions were related to 4f heavy Fermion systems of rare-earth borides. Exotic mechanisms of magnetism and Kondo effects have been discussed, which may indicate another direction of development of boride. Two special sessions

  16. Water-in-Supercritical CO2 Microemulsion Stabilized by a Metal Complex.

    PubMed

    Luo, Tian; Zhang, Jianling; Tan, Xiuniang; Liu, Chengcheng; Wu, Tianbin; Li, Wei; Sang, Xinxin; Han, Buxing; Li, Zhihong; Mo, Guang; Xing, Xueqing; Wu, Zhonghua

    2016-10-17

    Herein we propose for the first time the utilization of a metal complex for forming water-in-supercritical CO2 (scCO2 ) microemulsions. The water solubility in the metal-complex-stabilized microemulsion is significantly improved compared with the conventional water-in-scCO2 microemulsions stabilized by hydrocarbons. Such a microemulsion provides a promising route for the in situ CO2 reduction catalyzed by a metal complex at the water/scCO2 interface.

  17. Effect of Annealing on the Passive Film Stability and Corrosion Resistance of New Families of Iron-Based Amorphous Metals

    DTIC Science & Technology

    2011-06-01

    in the expected carbides or borides . Although these phases are potentially present, they do not exist in any large quantity. SAM4X7 has similar...score for titanium mixed with iron and chromium. Once again, titanium carbide and titanium boride did not appear in any large quantity. Because

  18. Morphological stability during solidification of silicon incorporating metallic impurities

    NASA Astrophysics Data System (ADS)

    Warrender, Jeffrey M.; Mathews, Jay; Recht, Daniel; Smith, Matthew; Gradečak, Silvija; Aziz, Michael J.

    2014-04-01

    We study the stability of a planar solidification front during pulsed laser melting-induced rapid solidification of silicon containing high concentrations of ion-implanted metallic impurities. We calculate the critical impurity concentration for destabilizing plane-front solidification, and introduce the "amplification coefficient," which is an empirical parameter describing the degree of amplification that must occur between the time the planar liquid-solid interface first becomes unstable, and the time of formation of morphological features of interface breakdown that is later observed in the microstructure. By connecting our calculations to experimental observations from the literature, we determine this parameter for Au, Co, Cr, Fe, Ga, In, and Zn in (100) Si and Ti in (111) Si, and find that it increases with impurity diffusive speed vD approximately as vD0.56. We present an approximate but simple method of estimating the maximum impurity concentration that may be incorporated in a surface layer of a given thickness without the appearance of cellular breakdown.

  19. Characterisation of titanium-titanium boride composites processed by powder metallurgy techniques

    SciTech Connect

    Selva Kumar, M.; Chandrasekar, P.; Chandramohan, P.; Mohanraj, M.

    2012-11-15

    In this work, a detailed characterisation of titanium-titanium boride composites processed by three powder metallurgy techniques, namely, hot isostatic pressing, spark plasma sintering and vacuum sintering, was conducted. Two composites with different volume percents of titanium boride reinforcement were used for the investigation. One was titanium with 20% titanium boride, and the other was titanium with 40% titanium boride (by volume). Characterisation was performed using X-ray diffraction, electron probe micro analysis - energy dispersive spectroscopy and wavelength dispersive spectroscopy, image analysis and scanning electron microscopy. The characterisation results confirm the completion of the titanium boride reaction. The results reveal the presence of titanium boride reinforcement in different morphologies such as needle-shaped whiskers, short agglomerated whiskers and fine plates. The paper also discusses how mechanical properties such as microhardness, elastic modulus and Poisson's ratio are influenced by the processing techniques as well as the volume fraction of the titanium boride reinforcement. - Highlights: Black-Right-Pointing-Pointer Ti-TiB composites were processed by HIP, SPS and vacuum sintering. Black-Right-Pointing-Pointer The completion of Ti-TiB{sub 2} reaction was confirmed by XRD, SEM and EPMA studies. Black-Right-Pointing-Pointer Hardness and elastic properties of Ti-TiB composites were discussed. Black-Right-Pointing-Pointer Processing techniques were compared with respect to their microstructure.

  20. Microstructural characterization and some mechanical properties of gas-borided Inconel 600-alloy

    NASA Astrophysics Data System (ADS)

    Makuch, N.; Kulka, M.

    2014-09-01

    The excellent resistance of Ni-based alloys to corrosion and oxidation is well-known. Boriding can be applied to these alloys in order to obtain suitable wear protection. In this paper, two-stage gas boronizing in N2-H2-BCl3 atmosphere is proposed for the producing the boride layer on Inconel®600-alloy. This process consists in two stages alternately repeated: saturation by boron and diffusion annealing. Such a gas boriding is applied in order to accelerate the saturation by boron and its diffusion. It turns out to be more effective because of eliminating the excess of boron, diffusing into the substrate, during the second stage. Microstructure and some mechanical properties of the produced layer are presented. Microstructural characterization is studied with using an optical microscope, scanning electron microscope, energy-dispersive x-ray microanalysis and x-ray diffraction. The diffusion zone consists of the mixture of nickel and chromium borides, occurring in the compact boride zone and in the area located beneath, at grain boundaries. The improved hardness and wear resistance characterize the layer. The formed boride layer is significantly thicker than those-obtained by the pack-boronizing or paste process at comparable temperature and time. Simultaneously, the measured depth of layer is slightly smaller than that-reported for electrolytic boriding.

  1. Magnetohydrodynamic stability in the electromagnetic levitation of horizontal molten-metal sheets

    NASA Astrophysics Data System (ADS)

    Hull, John R.; Wiencek, Tom; Rote, Donald M.

    1989-06-01

    High-frequency electromagnetic (EM) fields are investigated for the levitation of thin horizontal sheets of liquid metal. A magnetic configuration is analyzed in which inductance stabilization provides global stability and magnetic flux compression provides local stability. Stability analysis indicates that frequencies greater than about 24 kHz are desirable to stably levitate 6 mm thick steel. For stability in systems without active feedback, a conducting screen is required below the metal, with a gap between the screen and the molten metal of no more than twice the metal thickness. Experiments in which 10 kHz EM fields were used to statically levitate sheets of molten tin indicate that dominant magnetohydrodynamic instabilities are of the Rayleigh-Taylor type and correspond to theory.

  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. Stabilized metal nanoparticles from organometallic precursors for low temperature fuel cells.

    PubMed

    Ramirez-Meneses, E; Dominguez-Crespo, M A; Torres-Huerta, A M

    2013-01-01

    In this work, a review of articles and patents related to the utilization of colloidal metal nanoparticles produced by the decomposition of organometallic precursors as supported electrocatalysts in different electrochemical reactions including hydrogen evolution reaction (HER), oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) is discussed. In the case of stabilized metal nanoparticles, the kind of functional group contained in the stabilizer as well as the metal/stabilizer ratio, to evaluate the effect of particle size on the electrochemical performance, were also debated. Potential applications and perspectives of these electrocatalysts in proton exchange membrane fuel cells (PEMFC) are contended with reference to the role played by the coordination compounds and costs.

  4. Thermal and mechanical stability of nanograined FCC metals

    NASA Astrophysics Data System (ADS)

    Hattar, Khalid Mikhiel

    The mechanisms governing and factors controlling the thermal and mechanical stability of nanograined free-standing face-centered cubic thin films were investigated through in situ transmission electron microscopy annealing and straining experiments. A variety of sample preparation techniques were developed to investigate the active mechanisms. The results obtained from the select face-centered cubic metals studied were used to develop a general understanding of face-centered cubic metals with microstructure limited to the nanometer scale. The films were analyzed, both prior to and following the in situ transmission electron microscopy experiments, via a range of analytical techniques in order to characterize chemical and microstructural details. The mechanisms observed were compared to the pertinent theories and models. In situ transmission electron microscopy heating and annealing experiments were performed on free-standing pulsed-laser deposited Au, Cu, and Ni thin films. The grain growth of pulsed-laser deposited Ni films was studied and the growth rate was found to be a function of time, temperature, film thickness, and surface abnormalities. The grain growth was classified as abnormal in nature resulting in a bimodal grain size distribution. Abnormal grain growth was found to increase with an increase in film thickness. This increase was attributed to the presence of a higher density of preferred nanograins for abnormal grain growth in thicker films, although the mechanisms that induce the rapid growth were not determined. A higher percentage of abnormal large grains were found along ridges templated from the substrate, and in regions with extensive electron beam exposure. Post-annealing analysis of pulsed-laser deposited Ni films revealed an unexpected myriad of microstructural defects including dislocations, twins, stacking faults, dislocation loops, and stacking-fault tetrahedra, as well as a metastable hexagonal closed-packed phase. The production of these

  5. Stabilizing metal components in electrodes of electrochemical cells

    DOEpatents

    Spengler, Charles J.; Ruka, Roswell J.

    1989-01-01

    Disclosed is a method of reducing the removal or transfer into a gas phase of a current carrying metal in an apparatus, such as an electrochemical cell 2 having a porous fuel electrode 6 containing metal particles 11, where the metal is subject to removal or transfer into a gaseous phase, the method characterized in that (1) a metal organic compound that decomposes to form an electronically conducting oxide coating when heated is applied to the metal and porous electrode, and (2) the compound on the metal is then heated to a temperature sufficient to decompose the compound into an oxide coating 13 by increasing the temperature at a rate that is longer than 1 hour between room temperature and 600.degree. C., resulting in at least one continuous layer 13, 14 of the oxide coating on the metal.

  6. Joining of zirconium boride based refractory ceramics to Ti6Al4V

    NASA Astrophysics Data System (ADS)

    Muolo, Maria Luigia; Ferrera, Elena; Morbelli, Luisa; Zanotti, Claudio; Passerone, Alberto

    2003-09-01

    The exploitation of the peculiar characteristics of ceramic refractory materials in extreme conditions (as for Thermal Protection Systems - TPS) often depends to a great extent on the ability to join different ceramics one to the other and to special metallic alloys. Joints may be achieved in a number of ways, but principally are made by either solid phase or liquid phase transformations (brazing). Brazed joints are difficult to realise in the presence of ceramic materials, due to the fact that they are not wet, in general, by liquid metals. This paper presents experimental results on the wettability characteristics of zirconium boride based materials (with Si3N4, Ni etc.) by an AgZr alloy, the microstructures and thermal tests of brazed joints with the special alloy Ti6Al4V. The wetting data will be examined in terms of interfacial characteristics and in terms of the kinetics of spreading. Thermal tests and models will be devoted to evaluate and measure the thermal insulation capacity of the ceramic layers in order to determine the optimal thickness as a function of the foreseen outer surface temperature.

  7. Catalytic properties of carboxylic acid functionalized-polymer microsphere-stabilized gold metallic colloids.

    PubMed

    Liu, Wei; Yang, Xinlin; Huang, Wenqiang

    2006-12-01

    Polymer-microsphere-stabilized gold metallic colloids have been prepared by a novel strategy of simple and convenient reduction of the metallic salt through the stabilization of the active carboxylic acid group on the gel and surface layer of the microsphere. The nature of the interaction between the carboxylic acid and Au nanoparticles was studied in detail by XPS. Preliminary results indicate that polymer-microsphere-stabilized gold colloids are active catalysts for the reduction of 4-nitrophenol to 4-aminophenol with sodium borohydride as reductant. The catalytic properties of the stabilized catalyst for recycling were also investigated.

  8. Electroactive compositions with poly(arylene oxide) and stabilized lithium metal particles

    DOEpatents

    Zhang, Zhengcheng; Yuan, Shengwen; Amine, Khalil

    2015-05-12

    An electroactive composition includes an anodic material; a poly(arylene oxide); and stabilized lithium metal particles; where the stabilized lithium metal particles have a size less than about 200 .mu.m in diameter, are coated with a lithium salt, are present in an amount of about 0.1 wt % to about 5 wt %, and are dispersed throughout the composition. Lithium secondary batteries including the electroactive composition along with methods of making the electroactive composition are also discussed.

  9. STABILITY IN BCC TRANSITION METALS: MADELUNG AND BAND-ENERGY EFFECTS DUE TO ALLOYING

    SciTech Connect

    Landa, A; Soderlind, P; Ruban, A; Peil, O; Vitos, L

    2009-08-28

    The phase stability of the bcc Group VB (V, Nb, and Ta) transition metals is explored by first-principles electronic-structure calculations. Alloying with a small amount of a neighboring metal can either stabilize or destabilize the bcc phase. This counterintuitive behavior is explained by competing mechanisms that dominate depending on particular dopand. We show that band-structure effects dictate stability when a particular Group VB metal is alloyed with its nearest neighbors within the same d-transition series. In this case, the neighbor with less (to the left) and more (to the right) d electrons, destabilize and stabilize bcc, respectively. When alloying with neighbors of different d-transition series, electrostatic Madelung energy dominates over the band energy and always stabilizes the bcc phase.

  10. Stability in bcc transition metals: Madelung and band-energy effects due to alloying.

    PubMed

    Landa, A; Söderlind, P; Ruban, A V; Peil, O E; Vitos, L

    2009-12-04

    The phase stability of group VB (V, Nb, and Ta) transition metals is explored by first-principles electronic-structure calculations. Alloying with a small amount of a neighboring metal can either stabilize or destabilize the body-centered-cubic phase relative to low-symmetry rhombohedral phases. 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. In this case, the neighbor with less (to the left) and more (to the right) d electrons destabilize and stabilize bcc, respectively. When alloying with neighbors of higher d-transition series, electrostatic Madelung energy dominates and stabilizes the body-centered-cubic phase. This surprising prediction invalidates current understanding of simple d-electron bonding that dictates high-symmetry cubic and hexagonal phases.

  11. Stabilization of heavy metals on spent fluid catalytic cracking catalyst using marine clay.

    PubMed

    Sun, D D; Tay, J H; Qian, C E; Lai, D

    2001-01-01

    Spent fluid catalytic cracking catalyst is a hazardous solid waste generated by petroleum refineries containing vanadium and nickel. The marine clay was used as a matrix to stabilize vanadium and nickel and produce bricks which were then fired at various temperatures. TCLP leaching tests indicated that stabilizing brick had low metal leaching, with a maximum of 6.4 mg/l for vanadium and 19.8 microg/l for nickel. Compressive strength of stabilizing brick was found to range between 20 N/mm2 and 47 N/mm2. It is believed that stabilization and encapsulation mechanisms are responsible for the stabilization of vanadium and nickel. Encapsulation is a process whereby the marine clay matrix forms a physical barrier around the heavy metals which are thus prevented from leaching out into the environment. Incorporation involves the formation of bonds between the marine clay matrix and the heavy metals which thus become incorporated in the clay microstructure.

  12. Inhibition of the bioavailability of heavy metals in sewage sludge biochar by adding two stabilizers.

    PubMed

    Huang, Zhujian; Lu, Qin; Wang, Jun; Chen, Xian; Mao, Xiaoyun; He, Zhenli

    2017-01-01

    Agricultural application of sewage sludge (SS) after carbonization is a plausible way for disposal. Despite its benefits of improving soil fertility and C sequestration, heavy metals contained in sewage sludge biochars (SSB) are still a concern. In this study, two types of heavy metal stabilizers were chosen: fulvic acid (FA) and phosphogypsum (with CaSO4, CS, as the main component). The two stabilizers were incorporated into SS prior to 350°C carbonization for 1 h at the rates of 1%, 2%, or 4%. The obtained SSBs were then analyzed by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). Total and available concentrations of four heavy metals, i.e., Zn, Pb, Cd, and Ni, in the SSBs were determined. In addition, a series of pot soil culture experiments was conducted to investigate the effects of stabilizers incorporation into SSB on heavy metal bioavailability and the uptake by plants (corn as an indicator) and plant biomass yield, with SS and SSB (no stabilizers) as controls. The results showed that incorporation of both FA and CS increased functional groups such as carboxyl, phenol, hydroxyl, amine and quinine groups in the SSBs. The percentage of heavy metals in sulfuric and oxidizable state and residual state of SSBs were significantly increased after carbonization, and hence the mobility of the heavy metals in SSBs was decreased. The introduction of the stabilizers (i.e., FA or CS) significantly lowered the total and available concentrations of Zn, Pb, Cd, and Ni. The reduction in available heavy metal concentration increased with incorporation rate of the stabilizers from 1% to 4%. In the treatments with FA or CS incorporated SSB, less heavy metals were taken up by plants and more plant biomass yields were obtained. The mitigating effects were more pronounced at higher rates of FA or CS stabilizer. These findings provide a way to lower bioavailability of heavy metals in SS or SSB for land application or horticulture as a

  13. Microstructure and properties of laser-borided composite layers formed on commercially pure titanium

    NASA Astrophysics Data System (ADS)

    Kulka, M.; Makuch, N.; Dziarski, P.; Piasecki, A.; Miklaszewski, A.

    2014-03-01

    Laser-boriding was proposed in order to produce composite boride layers on commercially pure titanium. Three zones were observed in the microstructure: laser-borided re-melted zone (TiB, TiB2 and Tiα'-phase), heat affected zone (Tiα'-phase) and the substrate without heat treatment (Tiα-phase). The stick-like titanium borides occurred in the re-melted zone. In some areas, the tubular nature of titanium borides was visible. Among the sticks of titanium borides the needles of Tiα'-phase appeared. The high overlapping of multiple laser tracks (86%) caused the formation of uniform laser-alloyed layer in respect of the thickness. The microcracks and pores were not detected in the laser-borided composite layer. The high hardness of the re-melted zone (1250-1650 HV) was obtained. The hardness gradually decreased up to 250-300 HV in heat affected zone and up to about 200 HV in the substrate. In case of higher laser beam power used (1.95 kW), the re-melted zone was thicker and more homogeneous in respect of the microstructure and hardness. The craters obtained at the surface after the Rockwell C indentation test evidently revealed ideal cohesion of the laser-borided layer (HF1 standard). The significant increase in wear resistance of laser-borided composite layers was observed in comparison with commercially pure titanium. The lower mass wear intensity factors were obtained for laser-alloyed layers. The measurements of relative mass loss were also used in order to evaluate wear behavior of the investigated materials. The tests of laser-borided layers showed the catastrophic wear of the counter-specimens. The separated particles of counter-sample caused the accelerated wear of the laser-alloyed specimen. The longer duration of the tests, carried out without the change in a counter-specimen, caused the adhesion of counter-sample particles on the laser-borided specimen. The increased contact surface was the reason for the higher temperature and created the favourable

  14. An alternative method of gas boriding applied to the formation of borocarburized layer

    SciTech Connect

    Kulka, M. Makuch, N.; Pertek, A.; Piasecki, A.

    2012-10-15

    The borocarburized layers were produced by tandem diffusion processes: carburizing followed by boriding. An alternative method of gas boriding was proposed. Two-stage gas boronizing in N{sub 2}-H{sub 2}-BCl{sub 3} atmosphere was applied to the formation of iron borides on a carburized substrate. This process consisted in two stages, which were alternately repeated: saturation by boron and diffusion annealing. The microstructure and microhardness of produced layer were compared to those-obtained in case of continuous gas boriding in H{sub 2}-BCl{sub 3} atmosphere, earlier used. The first objective of two-stage boronizing, consisting in acceleration of boron diffusion, has been efficiently implemented. Despite the lower temperature and shorter duration of boronizing, about 1.5 times larger iron borides' zone has been formed on carburized steel. Second objective, the absolute elimination of brittle FeB phase, has failed. However, the amount of FeB phase has been considerably limited. Longer diffusion annealing should provide the boride layer with single-phase microstructure, without FeB phase. - Highlights: Black-Right-Pointing-Pointer Alternative method of gas boriding in H{sub 2}-N{sub 2}-BCl{sub 3} atmosphere was proposed. Black-Right-Pointing-Pointer The process consisted in two stages: saturation by boron and diffusion annealing. Black-Right-Pointing-Pointer These stages of short duration were alternately repeated. Black-Right-Pointing-Pointer The acceleration of boron diffusion was efficiently implemented. Black-Right-Pointing-Pointer The amount of FeB phase in the boride zone was limited.

  15. Deposition and characterization of aluminum magnesium boride thin film coatings

    NASA Astrophysics Data System (ADS)

    Tian, Yun

    Boron-rich borides are a special group of materials possessing complex structures typically comprised of B12 icosahedra. All of the boron-rich borides sharing this common structural unit exhibit a variety of exceptional physical and electrical properties. In this work, a new ternary boride compound AlMgB14, which has been extensively studied in bulk form due to its novel mechanical properties, was fabricated into thin film coatings by pulsed laser deposition (PLD) technology. The effect of processing conditions (laser operating modes, vacuum level, substrate temperature, and postannealing, etc.) on the composition, microstructure evolution, chemical bonding, and surface morphology of AlMgB14 thin film coatings has been investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), atomic force microscopy (AFM) and Fourier transform infrared (FTIR) spectrometry; the mechanical, electrical, and optical properties of AlMgB14 thin films have been characterized by nanoindentation, four-point probe, van der Pauw Hall measurement, activation energy measurement, and UV-VIS-NIR spectrophotometer. Experimental results show that AlMgB14 films deposited in the temperature range of 300 K - 873 K are amorphous. Depositions under a low vacuum level (5 x 10-5 Torr) can introduce a significant amount of C and O impurities into AlMgB14 films and lead to a complex oxide glass structure. Orthorhombic AlMgB14 phase cannot be obtained by subsequent high temperature annealing. By contrast, the orthorhombic AlMgB 14 crystal structure can be attained via high temperature-annealing of AlMgB14 films deposited under a high vacuum level (< 3 x 10-6 Torr), accompanied by strong texture formation. Low vacuum level-as deposited AlMgB14 films have low hardness (10 GPa), but high vacuum level-as deposited AlMgB14 films exhibit an extremely high hardness (45 GPa - 51 GPa), and the higher deposition temperature results in still higher hardness

  16. Stabilization and separation of heavy metals in incineration fly ash during the hydrothermal treatment process.

    PubMed

    Hu, Yuyan; Zhang, Pengfei; Li, Jianping; Chen, Dezhen

    2015-12-15

    In the paper, hydrothermal treatment (HT) of MSWI fly ashes was performed to stabilize and separate heavy metals. Influences of pre-treatment, types of ferric and/or ferrous additives, and subsequent heavy metal stabilization procedure by adding phosphate were investigated. The chemical stability of hydrothermal products was examined by solid waste extraction procedure with acetic acid buffer solution. Mineralogical investigation of selected hydrothermal product was carried out by XRD. FEGE SEM- -EDX was used to study the morphology and surface compositions of the ash particles. Experimental results revealed that HT process facilitated heavy metal exposure to leaching solution. FEGE SEM-EDX images revealed that fly ash particles were re-organized during hydrothermal process and that the minerals with special shapes and containing high levels of heavy metals were formed. A mild acid washing treatment with final pH around 6.20 could remove soluble heavy metals. Therefore, it may be a proper pre- or post-treatment method for fly ash particles for the purpose of reducing heavy metal contents. For the purpose of stabilizing heavy metals, the addition of ferric/ferrous salts in the HT process or phosphate stabilization after HT is recommended. The HT process may be applied to realize the environmentally sound management of MSWI fly ash or to recover and utilize MSWI fly ash. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Two-level systems and negative thermal expansion of lutetium borides

    NASA Astrophysics Data System (ADS)

    Novikov, V. V.; Mitroshenkov, N. V.; Kornev, B. I.; Matovnikov, A. V.

    2017-05-01

    The heat capacity Cv(T) and unit cell volume V(T) temperature dependencies of lutetium borides LuB2 and LuB4 in the region of 2-300 K were analysed in the Debye-Einstein approximation. The characteristic temperatures of the Debye and Einstein components of boride heat capacity and thermal expansion were found. The anomalous contribution to the borides' thermal characteristics was revealed. This contribution was attributed to the influence of two-level systems (TLS), formed in the subsystem of lutetium ions due to asymmetry in the way they are surrounded by the boron atoms in the boride crystal structure. The TLS influence is revealed on heat capacity temperature dependencies by the Schottky-type maxima at Tmax LuB2 =13.8 K, Tmax LuB4 =22.7 K, as well as by the negative contribution to the borides' thermal expansion. The borides' Grüneisen parameters corresponding to the heat capacity and thermal expansion TLS anomalies are negative, and amount to several 10 s of units.

  18. Heavy metal leaching from hydroxide, sulphide and silicate stabilized/solidified wastes

    SciTech Connect

    Cheeseman, C.R.; Butcher, E.J.; Sollars, C.J.; Perry, R. . Centre for Environmental Control and Waste Management)

    1993-01-01

    A synthetic, mixed-metal solution has been stabilized by treatment with sodium hydroxide, sodium sulphide, and sodium silicate, respectively. The three stabilized filter cakes have subsequently been solidified using additions of ordinary Portland cement and pulverized fuel ash (PFA) which are typically used in UK solidification operations. Both the stabilized filter cakes and the solidified wastes have been subjected to an equilibrium extraction test, a modified TCLP test, and a series of single-extraction, batch leach tests using an increasingly acidic leachant. Metal release was found to be primarily dependent on the pH of the leachate. Under mildly acidic conditions, the percentages leached from the stabilized and the stabilized/solidified wastes were comparable for most metals. A high-volume fraction of these solidified wastes is occupied by the stabilized filter cake. When they are broken up and tested in single-extraction leach tests, the primary effect of the cementitious additives is to increase the pH of the leachate so that most heavy metals remain insoluble. When tested under acidic leachate conditions, copper, lead, and mercury were found to be particularly well retained within sodium sulphide stabilized wastes. Under similar tests conditions, cadmium was leached at very low levels from the sodium silicate stabilized waste.

  19. Study on the formation of rhenium borides by density functional calculations

    NASA Astrophysics Data System (ADS)

    Agundez, R. R.; Soto, G.; Moreno, M. G.; Reyes-Serrato, A.

    2009-03-01

    The searching of hard and superhard materials is a hot topic in material science. Two known factors are fundamental to get high hardness: (1) high valence-electron density; and (2) high number of electron in covalent bonds. The 5d-transition metals comply with requirement (1); so, the task is to fulfill condition (2) without expanding its native structure. Supposedly this is possible by developing interstitial alloys with elements of moderate electronegativity, like boron and/or carbon. This idea materializes in the very hard ReB2, which scratches the surface of diamond. This work is a study in the formation of rhenium borides by density functional calculations. Here, we want to reveal the changes that would occur in the hexagonal close packed lattice of Re as B is inserted into its interstitial sites. We cover compositions in ReBx from x = 0 to x = 3 in x steps of 0.125. B is positioned in octahedral and tetrahedral interstices of Re, and for each arrangements we have calculated cell volume, cohesive energy, bulk modulus, valence electron concentration, and energy density. Supported by FONDOS CONACYT I0013, SNI-ESTUDIANTES 2008-01, SOLICITUD: 103909

  20. A general mechanism for stabilizing the small sizes of precious metal nanoparticles on oxide supports

    SciTech Connect

    Li, Wei-Zhen; Kovarik, Libor; Mei, Donghai; Engelhard, Mark H.; Gao, Feng; Liu, Jun; Wang, Yong; Peden, Charles HF

    2014-09-02

    We recently discovered that MgAl2O4 spinel {111} nano-facets optimally stabilize the small sizes of platinum nanoparticles even after severe high temperature aging treatments. Here we report the thermal stabilities of other precious metals with various physical and chemical properties on the MgAl2O4 spinel {111} facets, providing important new insights into the stabilization mechanisms. Besides Pt, Rh and Ir can also be successfully stabilized as small (1-3 nm) nanoparticles and even as single atomic species after extremely severe (800 °C, 1 week) oxidative aging. However, other metals either aggregate (Ru, Pd, Ag, and Au) or sublimate (Os) even during initial catalyst synthesis. On the basis of ab initio theoretical calculations and experimental observations, we rationalize that the exceptional stabilization originates from lattice matching, and the correspondingly strong attractive interactions at interfaces between the spinel {111} surface oxygens and epitaxial metals\\metal oxides. On this basis, design principles for catalyst support oxide materials that are capable in stabilizing precious metals are proposed.

  1. Alkali Metal Carbenoids: A Case of Higher Stability of the Heavier Congeners.

    PubMed

    Molitor, Sebastian; Gessner, Viktoria H

    2016-06-27

    As a result of the increased polarity of the metal-carbon bond when going down the group of the periodic table, the heavier alkali metal organyl compounds are generally more reactive and less stable than their lithium congeners. We now report a reverse trend for alkali metal carbenoids. Simple substitution of lithium by the heavier metals (Na, K) results in a significant stabilization of these usually highly reactive compounds. This allows their isolation and handling at room temperature and the first structure elucidation of sodium and potassium carbenoids. The control of stability was used to control reactivity and selectivity. Hence, the Na and K carbenoids act as selective carbene-transfer reagents, whereas the more labile lithium systems give rise to product mixtures. Additional fine tuning of the M-C interaction by means of crown ether addition further allows for control of the stability and reactivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Thermodynamic proton-ligand and metal-ligand stability constants of some drugs.

    PubMed

    Agrawal, Y K; Patel, D R

    1986-02-01

    The thermodynamic proton-ligand (pKa) and metal-ligand stability constants of clioquinol, clofibrate, nitrofurazone, and tetracycline with Cu2+, Zn2+, Mn2+, Mg2+, and Ca2+ have been determined at 35 degrees C in 50% ethanol-water media. An empirical pH correction for mixed-aqueous media has been applied. The metal-ligand stability constants were determined by following the Bjerrum Calvin titration technique as applied by Agrawal to mixed-aqueous solvents. The effect of the basicity of the ligand and the order of stability constants is discussed. The stability constants of the divalent metals follow the order: Cu2+ greater than Zn2+ greater than Mn2+ greater than Mg2+ greater than Ca2+ with all the drugs.

  3. Changes of toxic metals during biological stabilization and their potential ecological risk assessment.

    PubMed

    Wang, Hou-cheng; Zeng, Zheng-zhong; Zhang, He-fei; Nan, Zhong-ren

    2015-01-01

    With various disadvantages of pollution control technologies for toxic metal-contaminated soil, we mixed contaminated soil with sludge for in situ composting to stabilize toxic metals, so plants are enriched to take up the toxic metals. When simulating the above, we added toxic metal solution into sewage sludge, and then composed it with steel slag to determine inhibition of the availability of toxic metals. When toxic metals were added into sludge, the potential ecological index and geoaccumulation index of Cd became high while Zn was low. Steel slag had an inhibited availability of Cd, and when the adjunction of steel slag was 7%, the availability of Cd was lowest. Steel slag promoted the availability of Zn, and when the adjunction of steel slag was 27%, the availability of Zn was highest. Results showed that during composting, with increasing steel slag, Cd stabilizing time was reached sooner but Zn stabilizing time was slower, and the availability of all metals became lower. In the end, composting inhibited the potential ecological index of Cd, but it promoted the potential ecological index of Zn. Steel slag promoted the stability of Cd and Zn as Fe/Mn oxide-bound and residual species. Therefore, composting sludge and steel slag could be used as an effective inhibitor of Zn and Cd pollution.

  4. Thermal Stability Limits of Imidazolium Ionic Liquids Immobilized on Metal-Oxides.

    PubMed

    Babucci, Melike; Akçay, Aslı; Balci, Volkan; Uzun, Alper

    2015-08-25

    Thermal stability limits of 33 imidazolium ionic liquids (ILs) immobilized on three of the most commonly used high surface area metal-oxides, SiO2, γ-Al2O3, and MgO, were investigated. ILs were chosen from a family of 13 cations and 18 anions. Results show that the acidity of C2H of an imidazolium ring is one of the key factors controlling the thermal stability. An increase in C2H bonding strength of ILs leads to an increase in their stability limits accompanied by a decrease in interionic energy. Systematic changes in IL structure, such as changes in electronic structure and size of anion/cation, methylation on C2 site, and substitution of alkyl groups on the imidazolium ring with functional groups have significant effects on thermal stability limits. Furthermore, thermal stability limits of ILs are influenced strongly by acidic character of the metal-oxide surface. Generally, as the point of zero charge (PZC) of the metal-oxide increases from SiO2 to MgO, the interactions of IL and metal-oxide dominate over interionic interactions, and metal-oxide becomes the significant factor controlling the stability limits. However, thermal stability limits of some ILs show the opposite trend, as the chemical activities of the cation functional group or the electron donating properties of the anion alter IL/metal-oxide interactions. Results presented here can help in choosing the most suitable ILs for materials involving ILs supported on metal-oxides, such as for supported ionic liquid membranes (SILM) in separation applications or for solid catalyst with ionic liquid layer (SCILL) and supported ionic liquid phase (SILP) catalysts in catalysis.

  5. Stability constants of some metal complexes of triethylenetetraminehexa-acetic acid and complexometric titration of rare earths and other metals.

    PubMed

    Soucek, D A; Cheng, K L; Droll, H A

    1968-08-01

    The stability constants of some non-protonated 1:1 metal complexes of triethylenetetraminehexa-acetic acid are reported; log K values are Cd 19.8, Co(II) 20.4, Ni 19.9, Pb 19.5, Sm(III) 24.3, Zn 20.1.

  6. The effect of thermocycling liquid boronizing on the thickness of the boride layer and the transition zone

    SciTech Connect

    Oezsoy, A.; Yaman, Y.M. )

    1993-07-15

    Boronizing is a thermo-diffusion surface treatment, which is defined as enrichment of the surface of a workpiece with boron by means of thermo-chemical treatment. The processes are based on chemical or electrochemical reactions between the boron source and the respective base metal. Boron sources or boronizing compounds are solid, liquid or gas. Boride coatings, or the formation of boride compounds near the surface have been achieved by: (a) chemical methods; using gas boronizing agents, by immersion in molten salts, electrolysis and by pack cementation with powders; (b) physical methods; such as boron ion implantation, physical vacuum deposition, sputtering and ion plating. The methods of thermocycling treatment are used for intensification of the diffusion processes and forming more uniform microstructures and grain refinement. Krishtal and Kenis reported that the diffusion processes are accelerated with increasing grain boundary length, vacancy concentration, dislocation density inside the grains, and stress gradients in the thermocycling treatment. In practice, the type of structure favoring the intensification of diffusion processes is obtained using thermocycling treatment (TCT), either as a preliminary treatment before thermo-chemical treatment (TChT) or as a combined process before and during the thermochemical treatment. The steel is usually heated to 30-50 C above Ac[sub 1] and cooled to 50-100 C below Ar[sub 1]. Such treatment achieves an increase in the diffusion layer thickness, grain refinement and formation of a polygonal structure in the bulk of the metal. The combined use of TCT and TChT was studied during carburization of steel with a solid carburizer. It was demonstrated that, at the same duration of isothermal treatment (15 h), 5 cycles of 880-750 C, TCT produce grain size No. 5-6 in the bulk and grain size No. 9-10 in the diffusion layer, while the thickness of that layer increases 1.5 times. Improved fatigue resistance was also recorded.

  7. Method of boronizing transition metal surfaces

    DOEpatents

    Koyama, Koichiro; Shimotake, Hiroshi.

    1983-08-16

    A method is presented for preparing a boride layer on a transition metal substrate for use in corrosive environments or as a harden surface in machine applications. This method is particularly useful in treating current collectors for use within a high temperature and corrosive electrochemical cell environment. A melt of a alkali metal boride tetrafluoride salt including such as KF to lower its melting point is prepared including a dissolved boron containing material, for instance NiB, MnB[sub 2], or CrB[sub 2]. A transition metal to be coated is immersed in the melt at a temperature of no more than 700 C and a surface boride layer of that transition metal is formed within a period of about 24 hours on the substrate surface. 4 figs.

  8. Method of boronizing transition metal surfaces

    DOEpatents

    Koyama, Koichiro; Shimotake, Hiroshi

    1983-01-01

    A method is presented for preparing a boride layer on a transition metal substrate for use in corrosive environments or as a harden surface in machine applications. This method is particularly useful in treating current collectors for use within a high temperature and corrosive electrochemical cell environment. A melt of a alkali metal boride tetrafluoride salt including such as KF to lower its melting point is prepared including a dissolved boron containing material, for instance NiB, MnB.sub.2, or CrB.sub.2. A transition metal to be coated is immersed in the melt at a temperature of no more than 700.degree. C. and a surface boride layer of that transition metal is formed within a period of about 24 hours on the substrate surface.

  9. Method of boronizing transition-metal surfaces

    SciTech Connect

    Koyama, K.; Shimotake, H.

    1981-08-28

    A method is presented for preparing a boride layer on a transition metal substrate for use in corrosive environments or as a harden surface in machine applications. This method is particularly useful in treating current collectors for use within a high temperature and corrosive electrochemical cell environment. A melt of a alkali metal boride tetrafluoride salt including such as KF to lower its melting point is prepared including a dissolved boron containing material, for instance NiB, MnB/sub 2/, or CrB/sub 2/. A transition metal to be coated is immersed in the melt at a temperature of no more than 700/sup 0/C and a surface boride layer of that transition metal is formed within a period of about 24 hours on the substrate surface.

  10. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

    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.

  12. Stabilized Alkali-Metal Ultraviolet-Band-Pass Filters

    NASA Technical Reports Server (NTRS)

    Mardesich, Nick; Fraschetti, George A.; Mccann, Timothy; Mayall, Sherwood D.; Dunn, Donald E.; Trauger, John T.

    1995-01-01

    Layers of bismuth 5 to 10 angstrom thick incorporated into alkali-metal ultraviolet-band-pass optical filters by use of advanced fabrication techniques. In new filters layer of bismuth helps to reduce surface migration of sodium. Sodium layer made more stable and decreased tendency to form pinholes by migration.

  13. Stabilized Alkali-Metal Ultraviolet-Band-Pass Filters

    NASA Technical Reports Server (NTRS)

    Mardesich, Nick; Fraschetti, George A.; Mccann, Timothy; Mayall, Sherwood D.; Dunn, Donald E.; Trauger, John T.

    1995-01-01

    Layers of bismuth 5 to 10 angstrom thick incorporated into alkali-metal ultraviolet-band-pass optical filters by use of advanced fabrication techniques. In new filters layer of bismuth helps to reduce surface migration of sodium. Sodium layer made more stable and decreased tendency to form pinholes by migration.

  14. Yttrium and rare earth stabilized fast reactor metal fuel

    SciTech Connect

    Guon, J.; Grantham, L.F.; Specht, E.R.

    1992-05-12

    This patent describes an improved metal alloy reactor fuel consisting essentially of uranium, plutonium, and at least one element from the group consisting of yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.

  15. Metal-oxide-metal point contact junction detectors. [detection mechanism and mechanical stability

    NASA Technical Reports Server (NTRS)

    Baird, J.; Havemann, R. H.; Fults, R. D.

    1973-01-01

    The detection mechanism(s) and design of a mechanically stable metal-oxide-metal point contact junction detector are considered. A prototype for a mechanically stable device has been constructed and tested. A technique has been developed which accurately predicts microwave video detector and heterodyne mixer SIM (semiconductor-insulator-metal) diode performance from low dc frequency volt-ampere curves. The difference in contact potential between the two metals and geometrically induced rectification constitute the detection mechanisms.

  16. Pt-B System Revisited: Pt2B, a New Structure Type of Binary Borides. Ternary WAl12-Type Derivative Borides.

    PubMed

    Sologub, Oksana; Salamakha, Leonid; Rogl, Peter; Stöger, Berthold; Bauer, Ernst; Bernardi, Johannes; Giester, Gerald; Waas, Monika; Svagera, Robert

    2015-11-16

    On the basis of a detailed study applying X-ray single-crystal and powder diffraction, differential scanning calorimetry, and scanning electron microscopy analysis, it was possible to resolve existing uncertainties in the Pt-rich section (≥65 atom % Pt) of the binary Pt-B phase diagram above 600 °C. The formation of a unique structure has been observed for Pt2B [X-ray single-crystal data: space group C2/m, a = 1.62717(11) nm, b = 0.32788(2) nm, c = 0.44200(3) nm, β = 104.401(4)°, RF2 = 0.030]. Within the homogeneity range of "Pt3B", X-ray powder diffraction phase analysis prompted two structural modifications as a function of temperature. The crystal structure of "hT-Pt3B" complies with the hitherto reported structure of anti-MoS2 [space group P63/mmc, a = 0.279377(2) nm, c = 1.04895(1) nm, RF = 0.075, RI = 0.090]. The structure of the new "[Formula: see text]T-Pt3B" is still unknown. The formation of previously reported Pt∼4B has not been confirmed from binary samples. Exploration of the Pt-rich section of the Pt-Cu-B system at 600 °C revealed a new ternary compound, Pt12CuB6-y [X-ray single-crystal data: space group Im3̅, a = 0.75790(2) nm, y = 3, RF2 = 0.0129], which exhibits the filled WAl12-type structure accommodating boron in the interstitial trigonal-prismatic site 12e. The isotypic platinum-aluminum-boride was synthesized and studied. The solubility of copper in binary platinum borides has been found to attain ∼7 atom % Cu for Pt2B but to be insignificant for "[Formula: see text]T-Pt3B". The architecture of the new Pt2B structure combines puckered layers of boron-filled and empty [Pt6] octahedra (anti-CaCl2-type fragment) alternating along the x axis with a double layer of boron-semifilled [Pt6] trigonal prisms interbedded with a layer of empty tetrahedra and tetragonal pyramids (B-deficient α-T[Formula: see text]I fragment). Assuming boron vacancies ordering (space group R3), the Pt12CuB6-y structure exhibits serpentine-like columns of edge

  17. Process Stability of Ultrasonic-Wave-Assisted Gas Metal Arc Welding

    NASA Astrophysics Data System (ADS)

    Fan, Chenglei; Xie, Weifeng; Yang, Chunli; Lin, Sanbao; Fan, Yangyang

    2017-10-01

    As a newly developed arc welding method, ultrasonic-wave-assisted arc welding successfully introduced power ultrasound into the arc and weld pool, during which the ultrasonic acts on the top of the arc in the coaxial alignment direction. The advanced process for molten metals can be realized by using an additional ultrasonic field. Compared with the conventional gas metal arc welding (GMAW), the welding arc is compressed, the droplet size is decreased, and the droplet transfer frequency is increased significantly in ultrasonic-wave-assisted GMAW (U-GMAW). However, the stability of the metal transfer has deep influence on the welding quality equally, and the ultrasonic wave effect on the stability of the metal transfer is a phenomenon that is not completely understood. In this article, the stabilities of the short-circuiting transfer process and globular transfer process are studied systematically, and the effect of ultrasonic wave on the metal transfer is analyzed further. The transfer frequency and process stability of the U-GMAW process are much higher than those of the conventional GMAW. Analytical results show that the additional ultrasonic wave is helpful for improving welding stability.

  18. Charged and metallic molecular monolayers through surface-induced aromatic stabilization.

    PubMed

    Heimel, G; Duhm, S; Salzmann, I; Gerlach, A; Strozecka, A; Niederhausen, J; Bürker, C; Hosokai, T; Fernandez-Torrente, I; Schulze, G; Winkler, S; Wilke, A; Schlesinger, R; Frisch, J; Bröker, B; Vollmer, A; Detlefs, B; Pflaum, J; Kera, S; Franke, K J; Ueno, N; Pascual, J I; Schreiber, F; Koch, N

    2013-03-01

    Large π-conjugated molecules, when in contact with a metal surface, usually retain a finite electronic gap and, in this sense, stay semiconducting. In some cases, however, the metallic character of the underlying substrate is seen to extend onto the first molecular layer. Here, we develop a chemical rationale for this intriguing phenomenon. In many reported instances, we find that the conjugation length of the organic semiconductors increases significantly through the bonding of specific substituents to the metal surface and through the concomitant rehybridization of the entire backbone structure. The molecules at the interface are thus converted into different chemical species with a strongly reduced electronic gap. This mechanism of surface-induced aromatic stabilization helps molecules to overcome competing phenomena that tend to keep the metal Fermi level between their frontier orbitals. Our findings aid in the design of stable precursors for metallic molecular monolayers, and thus enable new routes for the chemical engineering of metal surfaces.

  19. Grain boundary stability governs hardening and softening in extremely fine nanograined metals

    NASA Astrophysics Data System (ADS)

    Hu, J.; Shi, Y. N.; Sauvage, X.; Sha, G.; Lu, K.

    2017-03-01

    Conventional metals become harder with decreasing grain sizes, following the classical Hall-Petch relationship. However, this relationship fails and softening occurs at some grain sizes in the nanometer regime for some alloys. In this study, we discovered that plastic deformation mechanism of extremely fine nanograined metals and their hardness are adjustable through tailoring grain boundary (GB) stability. The electrodeposited nanograined nickel-molybdenum (Ni-Mo) samples become softened for grain sizes below 10 nanometers because of GB-mediated processes. With GB stabilization through relaxation and Mo segregation, ultrahigh hardness is achieved in the nanograined samples with a plastic deformation mechanism dominated by generation of extended partial dislocations. Grain boundary stability provides an alternative dimension, in addition to grain size, for producing novel nanograined metals with extraordinary properties.

  20. The Growth Behavior of Titanium Boride Layers in α and β Phase Fields of Titanium

    NASA Astrophysics Data System (ADS)

    Lv, Xiaojun; Hu, Lingyun; Shuang, Yajing; Liu, Jianhua; Lai, Yanqing; Jiang, Liangxing; Li, Jie

    2016-07-01

    In this study, the commercially pure titanium was successfully electrochemical borided in a borax-based electrolyte. The process was carried out at a constant cathodic current density of 300 mA cm-2 and at temperatures of 1123 K and 1223 K (850 °C and 950 °C) for 0.5, 1, 2, 3, and 5 hours. The growth behavior of titanium boride layers in the α phase field of titanium was compared with that in the β phase field. After boriding, the presence of both the TiB2 top layer and TiB whisker sub-layer was confirmed by the X-ray diffraction (XRD) and scanning electron microscope. The relationship between the thickness of boride layers and boriding time was found to have a parabolic character in both α and β phase fields of titanium. The TiB whiskers showed ultra-fast growth rate in the β phase field. Its growth rate constant was found to be as high as 3.2002 × 10-13 m2 s-1. Besides, the chemical resistance of the TiB2 layer on the surface of titanium substrate was characterized by immersion tests in molten aluminum.

  1. Temporal stability of magic-number metal clusters: beyond the shell closing model.

    PubMed

    Desireddy, Anil; Kumar, Santosh; Guo, Jingshu; Bolan, Michael D; Griffith, Wendell P; Bigioni, Terry P

    2013-03-07

    The anomalous stability of magic-number metal clusters has been associated with closed geometric and electronic shells and the opening of HOMO-LUMO gaps. Despite this enhanced stability, magic-number clusters are known to decay and react in the condensed phase to form other products. Improving our understanding of their decay mechanisms and developing strategies to control or eliminate cluster instability is a priority, to develop a more complete theory of their stability, to avoid studying mixtures of clusters produced by the decay of purified materials, and to enable technology development. Silver clusters are sufficiently reactive to facilitate the study of the ambient temporal stability of magic-number metal clusters and to begin to understand their decay mechanisms. Here, the solution phase stability of a series of silver:glutathione (Ag:SG) clusters was studied as a function of size, pH and chemical environment. Cluster stability was found to be a non-monotonic function of size. Electrophoretic separations showed that the dominant mechanism involved the redistribution of mass toward smaller sizes, where the products were almost exclusively previously known cluster sizes. Optical absorption spectra showed that the smaller clusters evolved toward the two most stable cluster sizes. The net surface charge was found to play an important role in cluster stabilization although charge screening had no effect on stability, contrary to DLVO theory. The decay mechanism was found to involve the loss of Ag(+) ions and silver glutathionates. Clusters could be stabilized by the addition of Ag(+) ions and destabilized by either the addition of glutathione or the removal of Ag(+) ions. Clusters were also found to be most stable in near neutral pH, where they had a net negative surface charge. These results provide new mechanistic insights into the control of post-synthesis stability and chemical decay of magic-number metal clusters, which could be used to develop design

  2. The intrinsic stabilities and structures of alkali metal cationized guanine quadruplexes.

    PubMed

    Azargun, M; Jami-Alahmadi, Y; Fridgen, T D

    2017-01-04

    The structures and stabilities of self-assembled guanine quadruplexes, M(9eG)8(+) (M = Na, K, Rb, Cs; 9eG = 9-ethylguanine), have been studied in the gas phase by blackbody infrared radiative dissociation to determine the difference in the stabilizing effect of the alkali metal cations. The order of stabilities to decomposition was determined to be K(+) > Rb(+) > Cs(+) ≫ Na(+), which is consistent with the observation of K(+) being the ion of choice in guanine quadruplexes in nucleic acids. In the gas phase, the sodiated quadruplex was found to lose one 9eG at a time, whereas the quadruplexes of the heavier cations lost a neutral guanine tetrad. Vibrational spectroscopy on the gas-phase quadruplex ions was consistent with the structures in which the metal cations were sandwiched between two guanine tetrads. Electronic structure calculations are also used to compare with the observed stabilities and vibrational spectra.

  3. First-principles calculation of the structural stability of 6d transition metals

    SciTech Connect

    Oestlin, A.; Vitos, L.

    2011-09-15

    The phase stability of the 6d transition metals (elements 103-111) is investigated using first-principles electronic-structure calculations. Comparison with the lighter transition metals reveals that the structural sequence trend is broken at the end of the 6d series. To account for this anomalous behavior, the effect of relativity on the lattice stability is scrutinized, taking different approximations into consideration. It is found that the mass-velocity and Darwin terms give important contributions to the electronic structure, leading to changes in the interstitial charge density and, thus, in the structural energy difference.

  4. Preparation of silica stabilized Tobacco mosaic virus templates for the production of metal and layered nanoparticles.

    PubMed

    Royston, Elizabeth S; Brown, Adam D; Harris, Michael T; Culver, James N

    2009-04-15

    The use of biological molecules as templates for the production of metal nanoparticles and wires is often limited by the stability of the bio-template and its affinity for nucleating metal deposition. In this study, Tobacco mosaic virus (TMV) was used as a model bio-template to investigate the use of silica coatings as a means to both enhance template stability and increase its affinity for metal ions. Results indicate that the unmodified TMV particle can function as a template for the growth of thin (<1 nm) silica layers. However, this thin silica shell did not enhance the stability of the template during metal deposition. To increase silica growth on the TMV template, a pretreatment with aniline was used to produce a uniform silica attractive surface. Aniline pretreated templates yielded significant silica layers of >20 nm in thickness. These silica shells conferred a high degree of stability to the TMV particle and promoted the deposition of various metal nanoparticles through conventional silica mineralization chemistries. This process provides a simple and robust method for the layering of inorganics onto a biological template.

  5. Metal Ions-Stimulated Iron Oxidation in Hydroxylases Facilitates Stabilization of HIF-1α Protein

    PubMed Central

    Kaczmarek, Monika; Cachau, Raul E.; Topol, Igor A.; Kasprzak, Kazimierz S.; Ghio, Andy; Salnikow, Konstantin

    2009-01-01

    The exposure of cells to several metal ions stabilizes HIF-1α protein. However, the molecular mechanisms are not completely understood. They may involve inhibition of hydroxylation by either substitution of iron by metal ions or by iron oxidation in the hydroxylases. Here we provide evidence supporting the latter mechanism. We show that HIF-1α stabilization in human lung epithelial cells occurred following exposure to various metal and metalloid ions, including those that cannot substitute for iron in the hydroxylases. In each case addition of the reducing agent ascorbic acid (AA)* abolished HIF-1α protein stabilization. To better understand the role of iron oxidation in hydroxylase inhibition and to define the role of AA in the enzyme recovery we applied molecular modeling techniques. Our results indicate that the energy required for iron substitution by Ni(II) in the enzyme is high and unlikely to be achieved in a biological system. Additionally, computer modeling allowed us to identify a tridentate coordination of AA with the enzyme-bound iron, which explains the specific demand for AA as the iron reductant. Thus, the stabilization of HIF-1α by numerous metal ions that cannot substitute for iron in the enzyme, the alleviation of this effect by AA, and our computer modeling data support the hypothesis of iron oxidation in the hydroxylases following exposure to metal ions. PMID:19074761

  6. Relationships between Electronic Structure and Stability of Metallic Glasses.

    DTIC Science & Technology

    1984-06-01

    the experimental reflectance and transmittance values) for three consecutive values of the frequency LJi-l, o~i, LOi +I . If we assui.e that the A and...12. T. MATSUDA and U. MIZUTANI, in Proc. 4th Int. Conf. Rapidly Quenched Metals (Sendai, 1981) p. 1315. 13. J.J. HAUSER and J. TAUC , Phys. Rev. B...N.SAKAI, H. SEKIZAWA and T. MIZOGUCHI, J. Phys. ’ Soc. Japan 50, 828 (1981). 27. E. HAUSER, R.J. ZIRCKE, J. TAUC , J.J. HAUSER and S.R. NAGEL, Phys. Rev

  7. Inhibition of the bioavailability of heavy metals in sewage sludge biochar by adding two stabilizers

    PubMed Central

    Huang, Zhujian; Lu, Qin; Wang, Jun; Chen, Xian; He, Zhenli

    2017-01-01

    Agricultural application of sewage sludge (SS) after carbonization is a plausible way for disposal. Despite its benefits of improving soil fertility and C sequestration, heavy metals contained in sewage sludge biochars (SSB) are still a concern. In this study, two types of heavy metal stabilizers were chosen: fulvic acid (FA) and phosphogypsum (with CaSO4, CS, as the main component). The two stabilizers were incorporated into SS prior to 350°C carbonization for 1 h at the rates of 1%, 2%, or 4%. The obtained SSBs were then analyzed by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). Total and available concentrations of four heavy metals, i.e., Zn, Pb, Cd, and Ni, in the SSBs were determined. In addition, a series of pot soil culture experiments was conducted to investigate the effects of stabilizers incorporation into SSB on heavy metal bioavailability and the uptake by plants (corn as an indicator) and plant biomass yield, with SS and SSB (no stabilizers) as controls. The results showed that incorporation of both FA and CS increased functional groups such as carboxyl, phenol, hydroxyl, amine and quinine groups in the SSBs. The percentage of heavy metals in sulfuric and oxidizable state and residual state of SSBs were significantly increased after carbonization, and hence the mobility of the heavy metals in SSBs was decreased. The introduction of the stabilizers (i.e., FA or CS) significantly lowered the total and available concentrations of Zn, Pb, Cd, and Ni. The reduction in available heavy metal concentration increased with incorporation rate of the stabilizers from 1% to 4%. In the treatments with FA or CS incorporated SSB, less heavy metals were taken up by plants and more plant biomass yields were obtained. The mitigating effects were more pronounced at higher rates of FA or CS stabilizer. These findings provide a way to lower bioavailability of heavy metals in SS or SSB for land application or horticulture as a

  8. Kinetics of borided 31CrMoV9 and 34CrAlNi7 steels

    SciTech Connect

    Efe, Goezde Celebi; Ipek, Mediha; Ozbek, Ibrahim; Bindal, Cuma

    2008-01-15

    In this study, kinetics of borides formed on the surface of 31CrMoV9 and 34CrAlNi7 steels borided in solid medium consisting of Ekabor II at 850-900-950 deg. C for 2, 4, 6 and 8 h were investigated. Scanning electron microscopy and optical microscopy examinations showed that borides formed on the surface of borided steels have columnar morphology. The borides formed in the coating layer confirmed by X-ray diffraction analysis are FeB, Fe{sub 2}B, CrB, and Cr{sub 2}B. The hardnesses of boride layers are much higher than that of matrix. It was found that depending on process temperature and time the fracture toughness of boride layers ranged from 3.93 to 4.48 MPa m{sup 1/2} for 31CrMoV9 and from 3.87 to 4.40 MPa m{sup 1/2} for 34CrAlNi7 steel. Activation energy, growth rate and growth acceleration of boride layer calculated according to these kinetic studies revealed that lower activation energy results in the fast growth rate and high growth acceleration.

  9. Improving hardness and toughness of boride composites based on aluminum magnesium boride

    NASA Astrophysics Data System (ADS)

    Peters, Justin Steven

    The search for new super-hard materials has usually focused on strongly bonded, highly symmetric crystal structures similar to diamond. The two hardest single-phase materials, diamond and cubic boron nitride (cBN), are metastable, and both must be produced at high temperatures and pressures, which makes their production costly. In 2000, a superhard composite based on a low-symmetry, boron-rich compound was reported. Since then, many advances have been made in the study of this AlMgB14--TiB2 composite. The composite has been shown to exhibit hardness greater than either of its constituent phases, relying on its sub-micron microstructure to provide hardening and strengthening mechanisms. With possible hardness around 40 GPa, an AlMgB 14--60 vol% TiB2 approaches the hardness of cBN, yet is amenable to processing under ambient pressure conditions. There are interesting aspects of both the AlMgB14 and TiB 2 phases. AlMgB14 is comprised of a framework of boron, mostly in icosahedral arrangements. It is part of a family of 12 known compounds with the same boron lattice, with the metal atoms replaced by Li, Na, Y or a number of Lanthanides. Another peculiar trait of this family of compounds is that every one contains a certain amount of intrinsic vacancies on one or both of the metal sites. These vacancies are significant, ranging from 3 to 43% of sites depending on the composition. TiB2 is a popular specialty ceramic material due to its high hardness, moderate toughness, good corrosion resistance, and high thermal and electrical conductivity. The major drawback is the difficulty of densification of pure TiB2 ceramics. A combination of sintering aids, pressure, and temperatures of 1800°C are often required to achieve near full density articles. The AlMgB14--TiB2 composites can achieve 99% density from hotpressing at 1400°C. This is mostly due to the preparation of powders by a high-energy milling technique known as mechanical alloying. The resulting fine powders have

  10. Lithium boride sheet and nanotubes: structure and hydrogen storage.

    PubMed

    Zhang, Hong; Wang, Jing; Tian, Zhi-Xue; Liu, Ying

    2015-06-07

    A new class of Li-B sheets, along with the related nanotubes, with a Li2B5 primitive cell has been designed using first-principles density functional theory. The dynamical stability of the proposed structures was confirmed by calculation of the soft phonon modes, and the calculated electronic structures show that all are metallic. The application of both the sheets and nanotubes for hydrogen storage has been investigated and it has been found that both of them can adsorb two H2 molecules around each Li atom, with an average binding energy of 0.152-0.194 eV per H2, leading to a gravimetric density of 10.6 wt%.

  11. Stabilization of heavy metals in wastewater treatment sludge from power plants air heater washing.

    PubMed

    Saeedi, Mohsen; Amini, Hamid Reza

    2009-05-01

    In the present investigation, for the first time in Iran, dewatered sludge waste from the air heater washing wastewater treatment of a thermal power plant was subject to investigation with regard to cement-based stabilization in order to reduce the mobility of heavy metals. Studies of the chemical composition, mineralogy, morphology and leaching characteristics of the untreated and treated waste were conducted. The stabilization was done with two cement-based mix designs with different waste/cement ratios in different samples. In the cement stabilization process the leaching of V, Ni, Zn and Cr could be decreased from 314.1, 209.1, 24.8 and 5.5 mg L(-1), respectively, in the untreated waste to 6.02, 32.11, 3.57 and 3.68 mg L(-1) in a mixture with 20% waste/cement ratio, while during stabilization with cement + sand, the toxicity characteristic leaching procedure (TCLP) leachate contents of the mentioned metals were decreased to 4.24, 16.2, 2.51 and 2.2 mg L(-1) for the same waste/cement ratio. Stabilization with sand/cement seemed to be more efficient in reducing metal leaching from the waste. X-ray diffraction studies showed that portlandite, calcite, lime, larnite and quartz were produced during the stabilization process.

  12. 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.

  13. STABILITY EVALUATION OF METAL CASK ATTACHED TO A TRANSFER PALLET DURING LONG-PERIOD SEISMIC MOTIONS

    NASA Astrophysics Data System (ADS)

    Kawaguchi, Shohei; Shirai, Koji; Kanazawa, Kenji

    Rocking behavior of unfixed body is affected by center of mass, material coefficient of restitution and so on. 2/5 scale metal cask model considering these parameter was used for seismic test to evaluate stability of grounding metal cask attached to a transfer pallet under the influence of long-period earthquake motion. The newest knowledge from seismic test indicates seismic motion with high velocity over 100 kine not always cause the raise of response velocity of metal cask because of energy consumption by cask sliding and impact deformation of concrete. And new estimation method (called "Window energy spectrum method") of earthquake response spectrum gives suitable evaluation of response energy.

  14. Resistive sensor and electromagnetic actuator for feedback stabilization of liquid metal walls in fusion reactors

    NASA Astrophysics Data System (ADS)

    Mirhoseini, S. M. H.; Volpe, F. A.

    2016-12-01

    Liquid metal walls in fusion reactors will be subject to instabilities, turbulence, induced currents, error fields and temperature gradients that will make them locally bulge, thus entering in contact with the plasma, or deplete, hence exposing the underlying solid substrate. To prevent this, research has begun to actively stabilize static or flowing free-surface liquid metal layers by locally applying forces in feedback with thickness measurements. Here we present resistive sensors of liquid metal thickness and demonstrate \\mathbf{j}× \\mathbf{B} actuators, to locally control it.

  15. Toward interfacing organic semiconductors with ferromagnetic transition metal substrates: enhanced stability via carboxylate anchoring.

    PubMed

    Han, R; Blobner, F; Bauer, J; Duncan, D A; Barth, J V; Feulner, P; Allegretti, F

    2016-07-28

    We demonstrate that chemically well-defined aromatic self-assembled monolayers (SAMs) bonded via a carboxylate head group to surfaces of ferromagnetic (FM = Co, Ni, Fe) transition metals can be prepared at ambient temperature in ultra-high vacuum and are thermally stable up to 350-400 K (depending on the metal). The much superior stability over thiolate-bonded SAMs, which readily decompose above 200 K, and the excellent electronic communication guaranteed by the carboxylate bonding render benzoate/FM-metal interfaces promising candidates for application in spintronics.

  16. Dimensional, microstructural and compositional stability of metal fuels

    SciTech Connect

    Solomon, A.A.; Dayananda, M.A.

    1993-03-15

    The projects undertaken were to address two areas of concern for metal-fueled fast reactors: metallurgical compatibility of fuel and its fission products with the stainless steel cladding, and effects of porosity development in the fuel on fuel/cladding interactions and on sodium penetration in fuel. The following studies are reported on extensively in appendices: hot isostatic pressing of U-10Zr by coupled boundary diffusion/power law creep cavitation, liquid Na intrusion into porous U-10Zr fuel alloy by differential capillarity, interdiffusion between U-Zr fuel and selected Fe-Ni-Cr alloys, interdiffusion between U-Zr fuel vs selected cladding steels, and interdiffusion of Ce in Fe-base alloys with Ni or Cr.

  17. The effect of boriding on wear resistance of cold work tool steel

    NASA Astrophysics Data System (ADS)

    Anzawa, Y.; Koyama, S.; Shohji, I.

    2017-05-01

    Recently, boriding has attracted extensive attention as surface stiffening processing of plain steel. In this research, the influence of processing time on the formation layer of cold work tool steel (KD11MAX) by Al added fused salt bath was examined. In addition, in order to improve the abrasion resistance of KD11MAX, the effect of the treatment of boronization on the formation layer has been investigated. Boriding were performed in molten borax which contained about 10 mass% Al at processing time of 1.8 ~ 7.2 ks (processing temperature of 1303 K). As a result of the examination, the hardness of the boriding layer becomes about 1900 HV when the processing time of 3.6 ks. Also the abrasion resistance has improved remarkably. Furthermore, it was revealed that the formation layer was boronized iron from the Vickers hardness and analysis of the X-ray diffraction measurement.

  18. Nano-Disperse Borides and Carbides: Plasma Technology Production, Specific Properties, Economic Evaluation

    NASA Astrophysics Data System (ADS)

    Galevskii, G. V.; Rudneva, V. V.; Galevskii, S. G.; Tomas, K. I.; Zubkov, M. S.

    2016-04-01

    The experience of production and study on properties of nano-disperse chromium and titanium borides and carbides, and silicon carbide has been generalized. The structure and special service aspects of utilized plasma-metallurgical complex equipped with a three-jet direct-flow reactor with a capacity of 150 kW have been outlined. Processing, heat engineering and service life characteristics of the reactor are specified. The synthesis parameters of borides and carbides, as well as their basic characteristics in nano-disperse condition and their production flow diagram are outlined. Engineering and economic performance of synthesizing borides in laboratory and industrial conditions is assessed, and the respective segment of the international market as well. The work is performed at State Siberian Industrial University as a project part of the State Order of Ministry of Science and Education of the Russian Federation No. 11.1531/2014/K.

  19. Kinetics and Tribological Characterization of Pack-Borided AISI 1025 Steel

    NASA Astrophysics Data System (ADS)

    Gómez-Vargas, O. A.; Keddam, M.; Ortiz-Domínguez, M.

    2017-03-01

    In this present study, the AISI 1025 steel was pack-borided in the temperature range of 1,123-1,273 K for different treatment times ranging from 2 to 8 h. A diffusion model was suggested to estimate the boron diffusion coefficients in the Fe2B layers. As a result, the boron activation energy for the AISI 1025 steel was estimated as 174.36 kJ/mol. This value of energy was compared with the literature data. To extend the validity of the present model, other additional boriding conditions were considered. The boride layers formed on the AISI 1025 steel were characterized by the following experimental techniques: scanning electron microscopy, X-ray diffraction analysis and the Daimler-Benz Rockwell-C indentation technique. Finally, the scratch and pin-on-disc tests for wear resistance were achieved using an LG Motion Ltd and a CSM tribometer, respectively, under dry sliding conditions.

  20. Modeling of the electron-beam boriding in the system Fe-B-C-O2

    NASA Astrophysics Data System (ADS)

    Dasheev, D. E.; Smirnyagina, N. N.

    2017-05-01

    This paper reviews the conditions of iron borides formation and simulation of surface layers saturation depending on the stoichiometry of original components. Temperature fields have been investigated as well, which form certain phases in accordance with the pressure in the chamber and the power of the electron beam. A thermodynamic study of phase equilibria in Fe-B-C-O systems has been performed. This was done in order to optimize conditions for forming functional layers on the surface of iron-carbon alloys as a result of electron beam boriding in vacuum. Furthermore, strength characteristics of iron boride layers have been determined. Then these layers obtained by different methods and using various source components have been thoroughly compared with each other during the analysis.

  1. Yttrium and rare earth stabilized fast reactor metal fuel

    DOEpatents

    Guon, Jerold; Grantham, LeRoy F.; Specht, Eugene R.

    1992-01-01

    To increase the operating temperature of a reactor, the melting point and mechanical properties of the fuel must be increased. For an actinide-rich fuel, yttrium, lanthanum and/or rare earth elements can be added, as stabilizers, to uranium and plutonium and/or a mixture of other actinides to raise the melting point of the fuel and improve its mechanical properties. Since only about 1% of the actinide fuel may be yttrium, lanthanum, or a rare earth element, the neutron penalty is low, the reactor core size can be reduced, the fuel can be burned efficiently, reprocessing requirements are reduced, and the nuclear waste disposal volumes reduced. A further advantage occurs when yttrium, lanthanum, and/or other rare earth elements are exposed to radiation in a reactor, they produce only short half life radioisotopes, which reduce nuclear waste disposal problems through much shorter assured-isolation requirements.

  2. Metal (Cu, Cd and Zn) removal and stabilization during multiple soil washing by saponin.

    PubMed

    Gusiatin, Zygmunt Mariusz; Klimiuk, Ewa

    2012-01-01

    The influence of multiple saponin washing on copper, cadmium and zinc removal and stability in three types of soils (loamy sand, loam, silty clay) was investigated. Distribution of metals and their mobility measured as the ratio of exchangeable form to the sum of all fractions in soils was differential. After single washing the highest efficiency of metal removal was obtained in loamy sand (82-90%) and loam (67-88%), whereas the lowest in silty clay (39-62%). In loamy sand and loam metals had higher mobility factors (44-61% Cu, 60-76% Cd, and 68-84% Zn) compared to silty clay (9% Cu, 28% Cd and 36% Zn). Triplicate washing led to increase both efficiency of metal removal and percentage content of their stable forms. In consequence, fractional patterns for metals before and after treatment changed visibly as a result of their redistribution. Based on the redistribution index, the most stable metal (mainly in residual and organic fractions) after triplicate washing was Cu in loamy sand and loam. For silty clay contaminated with Cd, effective metal removal and its stabilization required a higher number of washings. Copyright © 2011 Elsevier Ltd. All rights reserved.

  3. Stability of Electrodeposition at Solid-Solid Interfaces and Implications for Metal Anodes

    NASA Astrophysics Data System (ADS)

    Ahmad, Zeeshan; Viswanathan, Venkatasubramanian

    2017-08-01

    We generalize the conditions for stable electrodeposition at isotropic solid-solid interfaces using a kinetic model which incorporates the effects of stresses and surface tension at the interface. We develop a stability diagram that shows two regimes of stability: a previously known pressure-driven mechanism and a new density-driven stability mechanism that is governed by the relative density of metal in the two phases. We show that inorganic solids and solid polymers generally do not lead to stable electrodeposition, and provide design guidelines for achieving stable electrodeposition.

  4. Heavy metals stabilization in medical waste incinerator fly ash using alkaline assisted supercritical water technology.

    PubMed

    Jin, Jian; Li, Xiaodong; Chi, Yong; Yan, Jianhua

    2010-12-01

    This study investigated the process of aluminosilicate formation in medical waste incinerator fly ash containing large amounts of heavy metals and treated with alkaline compounds at 375 degrees C and examined how this process affected the mobility and availability of the metals. As a consequence of the treatments, the amount of dissolved heavy metals, and thus their mobility, was greatly reduced, and the metal leaching concentration was below the legislative regulations for metal leachability. Moreover, this process did not produce a high concentration of heavy metals in the effluent. The addition of alkaline compounds such as sodium hydroxide and sodium carbonate can prevent certain heavy metal ions dissolving in water. In comparison with the alkaline-free condition, the extracted concentrations of As, Mn, Pb, Sr and Zn were decreased by about 51.08, 97.22, 58.33, 96.77 and 86.89% by the addition of sodium hydroxide and 66.18, 86.11, 58.33, 83.87 and 81.91% by the addition of sodium carbonate. A mechanism for how the formation of aluminosilicate occurred in supercritical water and affected the mobility and availability of the heavy metals is discussed. The reported results could be useful as basic knowledge for planning new technologies for the hydrothermal stabilization of heavy metals in fly ash.

  5. Synthesis and stabilization of supported metal catalysts by atomic layer deposition.

    PubMed

    Lu, Junling; Elam, Jeffrey W; Stair, Peter C

    2013-08-20

    Supported metal nanoparticles are among the most important catalysts for many practical reactions, including petroleum refining, automobile exhaust treatment, and Fischer-Tropsch synthesis. The catalytic performance strongly depends on the size, composition, and structure of the metal nanoparticles, as well as the underlying support. Scientists have used conventional synthesis methods including impregnation, ion exchange, and deposition-precipitation to control and tune these factors, to establish structure-performance relationships, and to develop better catalysts. Meanwhile, chemists have improved the stability of metal nanoparticles against sintering by the application of protective layers, such as polymers and oxides that encapsulate the metal particle. This often leads to decreased catalytic activity due to a lack of precise control over the thickness of the protective layer. A promising method of catalyst synthesis is atomic layer deposition (ALD). ALD is a variation on chemical vapor deposition in which metals, oxides, and other materials are deposited on surfaces by a sequence of self-limiting reactions. The self-limiting character of these reactions makes it possible to achieve uniform deposits on high-surface-area porous solids. Therefore, design and synthesis of advanced catalysts on the nanoscale becomes possible through precise control over the structure and composition of the underlying support, the catalytic active sites, and the protective layer. In this Account, we describe our advances in the synthesis and stabilization of supported metal catalysts by ALD. After a short introduction to the technique of ALD, we show several strategies for metal catalyst synthesis by ALD that take advantage of its self-limiting feature. Monometallic and bimetallic catalysts with precise control over the metal particle size, composition, and structure were achieved by combining ALD sequences, surface treatments, and deposition temperature control. Next, we describe

  6. Polydopamine tethered enzyme/metal-organic framework composites with high stability and reusability.

    PubMed

    Wu, Xiaoling; Yang, Cheng; Ge, Jun; Liu, Zheng

    2015-12-07

    An enzyme/metal-organic framework (MOF) composite with both highly stable and easily reusable features was prepared via tethering enzyme/MOF nanocrystals with polydopamine (PDA). The micrometer-sized PDA tethered enzyme/MOF composite can be easily repeatedly used without obvious activity loss, promising for efficient enzymatic catalysis at low cost with long-term operational stability under harsh conditions.

  7. DEMONSTRATION BULLETIN: MOLECULAR BONDING SYSTEM FOR HEAVY METALS STABILIZATION - SOLUCORP INDUSTRIES LTD.

    EPA Science Inventory

    This document presents an evaluation of the Molecular Bonding System (MBS) and its ability to chemically stabilize three metals-contaminated wstes/soils during a SITe demo. The MBS process treated approximately 500 tons each of soil/Fill, Slag, and Miscellaneous Smelter Waste wit...

  8. DEMONSTRATION BULLETIN: MOLECULAR BONDING SYSTEM FOR HEAVY METALS STABILIZATION - SOLUCORP INDUSTRIES LTD.

    EPA Science Inventory

    This document presents an evaluation of the Molecular Bonding System (MBS) and its ability to chemically stabilize three metals-contaminated wstes/soils during a SITe demo. The MBS process treated approximately 500 tons each of soil/Fill, Slag, and Miscellaneous Smelter Waste wit...

  9. Stabilization of Rocky Flats combustible residues contaminated with plutonium metal and organic solvents

    SciTech Connect

    Bowen, S.M.; Cisneros, M.R.; Jacobson, L.L.; Schroeder, N.C.; Ames, R.L.

    1998-09-30

    This report describes tests on a proposed flowsheet designed to stabilize combustible residues that were generated at the Rocky Flats Environmental Technology Site (RFETS) during the machining of plutonium metal. Combustible residues are essentially laboratory trash contaminated with halogenated organic solvents and plutonium metal. The proposed flowsheet, designed by RFETS, follows a glovebox procedure that includes (1) the sorting and shredding of materials, (2) a low temperature thermal desorption of solvents from the combustible materials, (3) an oxidation of plutonium metal with steam, and (4) packaging of the stabilized residues. The role of Los Alamos National Laboratory (LANL) in this study was to determine parameters for the low temperature thermal desorption and steam oxidation steps. Thermal desorption of carbon tetrachloride (CCl{sub 4}) was examined using a heated air stream on a Rocky Flats combustible residue surrogate contaminated with CCl{sub 4}. Three types of plutonium metal were oxidized with steam in a LANL glovebox to determine the effectiveness of this procedure for residue stabilization. The results from these LANL experiments are used to recommend parameters for the proposed RFETS stabilization flowsheet.

  10. Surface hardening of steel by boriding in a cold rf plasma

    NASA Technical Reports Server (NTRS)

    Finberg, I.; Avni, R.; Grill, A.; Spalvins, T.; Buckley, D. H.

    1985-01-01

    Scanning electron spectroscopy, X-ray diffractometry, Auger electron spectroscopy, and microhardness measurements, are used to study the surfaces of 4340-steel samples that have been borided in a cold RF plasma which had been initiated in a gas mixture of 2.7 percent diborane in Ar. As a result of the dislocation of the diborane in the plasma, boron is deposited on the surface of the steel substrate and two crystalline phases, tetragonal Fe2B and orthorhombic FeB, are formed. The formation of boride phases then increases the surface microhardness from 2650 MPa to a maximum value of 7740 MPa.

  11. Surface hardening of steel by boriding in a cold rf plasma

    NASA Technical Reports Server (NTRS)

    Finberg, I.; Avni, R.; Grill, A.; Spalvins, T.; Buckley, D. H.

    1985-01-01

    Scanning electron spectroscopy, X-ray diffractometry, Auger electron spectroscopy, and microhardness measurements, are used to study the surfaces of 4340-steel samples that have been borided in a cold RF plasma which had been initiated in a gas mixture of 2.7 percent diborane in Ar. As a result of the dislocation of the diborane in the plasma, boron is deposited on the surface of the steel substrate and two crystalline phases, tetragonal Fe2B and orthorhombic FeB, are formed. The formation of boride phases then increases the surface microhardness from 2650 MPa to a maximum value of 7740 MPa.

  12. Investigation of long term stability in metal hydrides

    NASA Technical Reports Server (NTRS)

    Marmaro, Roger W.; Lynch, Franklin E.; Chandra, Dhanesh; Lambert, Steve; Sharma, Archana

    1991-01-01

    It is apparent from the literature and the results of this study that cyclic degradation of AB(5) type metal hydrides varies widely according to the details of how the specimens are cycled. The Rapid Cycle Apparatus (RCA) used produced less degradation in 5000 to 10000 cycles than earlier work with a Slow Cycle Apparatus (SCA) produced in 1500 cycles. Evidence is presented that the 453 K (356 F) Thermal Aging (TA) time spent in the saturated condition causes hydride degradation. But increasing the cooling (saturation) period in the RCA did not greatly increase the rate of degradation. It appears that TA type degradation is secondary at low temperatures to another degradation mechanism. If rapid cycles are less damaging than slow cycles when the saturation time is equal, the rate of hydriding/dehydriding may be an important factor. The peak temperatures in the RCA were about 30 C lower than the SCA. The difference in peak cycle temperatures (125 C in the SCA, 95 C in RCA) cannot explain the differences in degradation. TA type degradation is similar to cyclic degradation in that nickel peaks and line broadening are observed in X ray diffraction patterns after either form of degradation.

  13. Effects of electron doping on the stability of the metal hydride NaH.

    PubMed

    Olea-Amezcua, M A; Rivas-Silva, J F; de la Peña-Seaman, O; Heid, R; Bohnen, K P

    2017-04-12

    Alkali and alkali-earth metal hydrides have high volumetric and gravimetric hydrogen densities, but due to their high thermodynamic stability, they possess high dehydrogenation temperatures which may be reduced by transforming these compounds into less stable states/configurations. We present a systematic computational study of the electron doping effects on the stability of the alkali metal hydride NaH substituted with Mg, using the self-consistent version of the virtual crystal approximation to model the alloy Na1-x Mg x H. The phonon dispersions were studied paying special attention to the crystal stability and the correlations with the electronic structure taking into account the zero point energy contribution. We found that substitution of Na by Mg in the hydride invokes a reduction of the frequencies, leading to dynamical instabilities for Mg content of 25%. The microscopic origin of these instabilities could be related to the formation of ellipsoidal Fermi surfaces centered at the L point due to the metallization of the hydride by the Mg substitution. Applying the quasiharmonic approximation, thermodynamic properties like heat capacities, vibrational entropies and vibrational free energies as a function of temperature at zero pressure are obtained. These properties determine an upper temperature for the thermodynamic stability of the hydride, which decreases from 600 K for NaH to 300 K at 20% Mg concentration. This significant reduction of the stability range indicates that dehydrogenation could be favoured by electron doping of NaH.

  14. Effects of electron doping on the stability of the metal hydride NaH

    NASA Astrophysics Data System (ADS)

    Olea-Amezcua, M. A.; Rivas-Silva, J. F.; de la Peña-Seaman, O.; Heid, R.; Bohnen, K. P.

    2017-04-01

    Alkali and alkali-earth metal hydrides have high volumetric and gravimetric hydrogen densities, but due to their high thermodynamic stability, they possess high dehydrogenation temperatures which may be reduced by transforming these compounds into less stable states/configurations. We present a systematic computational study of the electron doping effects on the stability of the alkali metal hydride NaH substituted with Mg, using the self-consistent version of the virtual crystal approximation to model the alloy Na1-x Mg x H. The phonon dispersions were studied paying special attention to the crystal stability and the correlations with the electronic structure taking into account the zero point energy contribution. We found that substitution of Na by Mg in the hydride invokes a reduction of the frequencies, leading to dynamical instabilities for Mg content of 25%. The microscopic origin of these instabilities could be related to the formation of ellipsoidal Fermi surfaces centered at the L point due to the metallization of the hydride by the Mg substitution. Applying the quasiharmonic approximation, thermodynamic properties like heat capacities, vibrational entropies and vibrational free energies as a function of temperature at zero pressure are obtained. These properties determine an upper temperature for the thermodynamic stability of the hydride, which decreases from 600 K for NaH to 300 K at 20% Mg concentration. This significant reduction of the stability range indicates that dehydrogenation could be favoured by electron doping of NaH.

  15. Engineering Interface Structures and Thermal Stabilities via SPD Processing in Bulk Nanostructured Metals

    PubMed Central

    Zheng, Shijian; Carpenter, John S.; McCabe, Rodney J.; Beyerlein, Irene J.; Mara, Nathan A.

    2014-01-01

    Nanostructured metals achieve extraordinary strength but suffer from low thermal stability, both a consequence of a high fraction of interfaces. Overcoming this tradeoff relies on making the interfaces themselves thermally stable. Here we show that the atomic structures of bi-metal interfaces in macroscale nanomaterials suitable for engineering structures can be significantly altered via changing the severe plastic deformation (SPD) processing pathway. Two types of interfaces are formed, both exhibiting a regular atomic structure and providing for excellent thermal stability, up to more than half the melting temperature of one of the constituents. Most importantly, the thermal stability of one is found to be significantly better than the other, indicating the exciting potential to control and optimize macroscale robustness via atomic-scale bimetal interface tuning. Taken together, these results demonstrate an innovative way to engineer pristine bimetal interfaces for a new class of simultaneously strong and thermally stable materials. PMID:24573355

  16. Engineering interface structures and thermal stabilities via SPD processing in bulk nanostructured metals.

    PubMed

    Zheng, Shijian; Carpenter, John S; McCabe, Rodney J; Beyerlein, Irene J; Mara, Nathan A

    2014-02-27

    Nanostructured metals achieve extraordinary strength but suffer from low thermal stability, both a consequence of a high fraction of interfaces. Overcoming this tradeoff relies on making the interfaces themselves thermally stable. Here we show that the atomic structures of bi-metal interfaces in macroscale nanomaterials suitable for engineering structures can be significantly altered via changing the severe plastic deformation (SPD) processing pathway. Two types of interfaces are formed, both exhibiting a regular atomic structure and providing for excellent thermal stability, up to more than half the melting temperature of one of the constituents. Most importantly, the thermal stability of one is found to be significantly better than the other, indicating the exciting potential to control and optimize macroscale robustness via atomic-scale bimetal interface tuning. Taken together, these results demonstrate an innovative way to engineer pristine bimetal interfaces for a new class of simultaneously strong and thermally stable materials.

  17. Engineering Interface Structures and Thermal Stabilities via SPD Processing in Bulk Nanostructured Metals

    SciTech Connect

    Zheng, Shijian; Carpenter, John S.; McCabe, Rodney J.; Beyerlein, Irene J.; Mara, Nathan A.

    2014-02-27

    Nanostructured metals achieve extraordinary strength but suffer from low thermal stability, both a consequence of a high fraction of interfaces. Overcoming this tradeoff relies on making the interfaces themselves thermally stable. In this paper, we show that the atomic structures of bi-metal interfaces in macroscale nanomaterials suitable for engineering structures can be significantly altered via changing the severe plastic deformation (SPD) processing pathway. Two types of interfaces are formed, both exhibiting a regular atomic structure and providing for excellent thermal stability, up to more than half the melting temperature of one of the constituents. Most importantly, the thermal stability of one is found to be significantly better than the other, indicating the exciting potential to control and optimize macroscale robustness via atomic-scale bimetal interface tuning. As a result, we demonstrate an innovative way to engineer pristine bimetal interfaces for a new class of simultaneously strong and thermally stable materials.

  18. Engineering Interface Structures and Thermal Stabilities via SPD Processing in Bulk Nanostructured Metals

    DOE PAGES

    Zheng, Shijian; Carpenter, John S.; McCabe, Rodney J.; ...

    2014-02-27

    Nanostructured metals achieve extraordinary strength but suffer from low thermal stability, both a consequence of a high fraction of interfaces. Overcoming this tradeoff relies on making the interfaces themselves thermally stable. In this paper, we show that the atomic structures of bi-metal interfaces in macroscale nanomaterials suitable for engineering structures can be significantly altered via changing the severe plastic deformation (SPD) processing pathway. Two types of interfaces are formed, both exhibiting a regular atomic structure and providing for excellent thermal stability, up to more than half the melting temperature of one of the constituents. Most importantly, the thermal stability ofmore » one is found to be significantly better than the other, indicating the exciting potential to control and optimize macroscale robustness via atomic-scale bimetal interface tuning. As a result, we demonstrate an innovative way to engineer pristine bimetal interfaces for a new class of simultaneously strong and thermally stable materials.« less

  19. Electronic metal-support interaction enhanced oxygen reduction activity and stability of boron carbide supported platinum

    NASA Astrophysics Data System (ADS)

    Jackson, Colleen; Smith, Graham T.; Inwood, David W.; Leach, Andrew S.; Whalley, Penny S.; Callisti, Mauro; Polcar, Tomas; Russell, Andrea E.; Levecque, Pieter; Kramer, Denis

    2017-06-01

    Catalysing the reduction of oxygen in acidic media is a standing challenge. Although activity of platinum, the most active metal, can be substantially improved by alloying, alloy stability remains a concern. Here we report that platinum nanoparticles supported on graphite-rich boron carbide show a 50-100% increase in activity in acidic media and improved cycle stability compared to commercial carbon supported platinum nanoparticles. Transmission electron microscopy and x-ray absorption fine structure analysis confirm similar platinum nanoparticle shapes, sizes, lattice parameters, and cluster packing on both supports, while x-ray photoelectron and absorption spectroscopy demonstrate a change in electronic structure. This shows that purely electronic metal-support interactions can significantly improve oxygen reduction activity without inducing shape, alloying or strain effects and without compromising stability. Optimizing the electronic interaction between the catalyst and support is, therefore, a promising approach for advanced electrocatalysts where optimizing the catalytic nanoparticles themselves is constrained by other concerns.

  20. Stability and heavy metal distribution of soil aggregates affected by application of apatite, lime, and charcoal.

    PubMed

    Cui, Hongbiao; Ma, Kaiqiang; Fan, Yuchao; Peng, Xinhua; Mao, Jingdong; Zhou, Dongmei; Zhang, Zhongbin; Zhou, Jing

    2016-06-01

    Only a few studies have been reported on the stability and heavy metal distribution of soil aggregates after soil treatments to reduce the availability of heavy metals. In this study, apatite (22.3 t ha(-1)), lime (4.45 t ha(-1)), and charcoal (66.8 t ha(-1)) were applied to a heavy metal-contaminated soil for 4 years. The stability and heavy metal distribution of soil aggregates were investigated by dry and wet sieving. No significant change in the dry mean weight diameter was observed in any treatments. Compared with the control, three-amendment treatments significantly increased the wet mean weight diameter, but only charcoal treatment significantly increased the wet aggregate stability. The soil treatments increased the content of soil organic carbon, and the fraction 0.25-2 mm contained the highest content of soil organic carbon. Amendments' application slightly increased soil total Cu and Cd, but decreased the concentrations of CaCl2 -extractable Cu and Cd except for the fraction <0.053 mm. The fractions >2 and 0.25-2 mm contained the highest concentrations of CaCl2-extractable Cu and Cd, accounted for about 74.5-86.8 % of CaCl2-extractable Cu and Cd in soil. The results indicated that amendments' application increased the wet soil aggregate stability and decreased the available Cu and Cd. The distribution of available heavy metals in wet soil aggregates was not controlled by soil aggregate stability, but possibly by soil organic carbon.

  1. Imaging metal-like monoclinic phase stabilized by surface coordination effect in vanadium dioxide nanobeam

    NASA Astrophysics Data System (ADS)

    Li, Zejun; Wu, Jiajing; Hu, Zhenpeng; Lin, Yue; Chen, Qi; Guo, Yuqiao; Liu, Yuhua; Zhao, Yingcheng; Peng, Jing; Chu, Wangsheng; Wu, Changzheng; Xie, Yi

    2017-06-01

    In correlated systems, intermediate states usually appear transiently across phase transitions even at the femtosecond scale. It therefore remains an open question how to determine these intermediate states--a critical issue for understanding the origin of their correlated behaviour. Here we report a surface coordination route to successfully stabilize and directly image an intermediate state in the metal-insulator transition of vanadium dioxide. As a prototype metal-insulator transition material, we capture an unusual metal-like monoclinic phase at room temperature that has long been predicted. Coordinate bonding of L-ascorbic acid molecules with vanadium dioxide nanobeams induces charge-carrier density reorganization and stabilizes metallic monoclinic vanadium dioxide, unravelling orbital-selective Mott correlation for gap opening of the vanadium dioxide metal-insulator transition. Our study contributes to completing phase-evolution pathways in the metal-insulator transition process, and we anticipate that coordination chemistry may be a powerful tool for engineering properties of low-dimensional correlated solids.

  2. Hydrothermal synthesis of platinum-group-metal nanoparticles by using HEPES as a reductant and stabilizer.

    PubMed

    So, Man-Ho; Ho, Chi-Ming; Chen, Rong; Che, Chi-Ming

    2010-06-01

    Platinum-group-metal (Ru, Os, Rh, Ir, Pd and Pt) nanoparticles are synthesized in an aqueous buffer solution of 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) (200 mM, pH 7.4) under hydrothermal conditions (180 degrees C). Monodispersed (monodispersity: 11-15%) metal nanoparticles were obtained with an average particle size of less than 5 nm (Ru: 1.8+/-0.2, Os: 1.6+/-0.2, Rh: 4.5+/-0.5, Ir: 2.0+/-0.3, Pd: 3.8+/-0.4, Pt: 1.9+/-0.2 nm). The size, monodispersity, and stability of the as-obtained metal nanoparticles were affected by the HEPES concentration, pH of the HEPES buffer solution, and reaction temperature. HEPES with two tertiary amines (piperazine groups) and terminal hydroxyl groups can act as a reductant and stabilizer. The HEPES molecules can bind to the surface of metal nanoparticles to prevent metal nanoparticles from aggregation. These platinum-group-metal nanoparticles could be deposited onto the surface of graphite, which catalyzed the aerobic oxidation of alcohols to aldehydes.

  3. Polyacrylamide-metal nanocomposites: one-pot synthesis, antibacterial properties, and thermal stability

    NASA Astrophysics Data System (ADS)

    Li, Cuiyan; Cai, Yanling; Zhu, Yihua; Ma, Mingguo; Zheng, Wei; Zhu, Jiefang

    2013-09-01

    The incorporation of inorganic nanoparticles into polymers is a hot research spot, since it endows the nanocomposites with new or improved properties by exploiting synergistic effects. Here we report a facile one-pot synthesis of polyacrylamide (PAM)-metal (M = Au, Ag, or Pd) nanocomposites in ethylene glycol (EG). The simultaneous polymerization of the acylamide (AM) monomer and formation of metal nanoparticles lead to a homogeneous distribution of metal nanoparticles in the PAM matrix. The sizes of Au, Ag, and Pd nanoparticles are 55.50 ± 10.6, 14.15 ± 2.57, and 7.74 ± 1.82 nm, respectively. The reaction system only includes EG, AM monomer, and corresponding metal salt. EG acts as both the solvent and the reducing reagent. Also, no initiator for AM polymerization and no surfactant for stabilization of metal nanoparticles are used. Furthermore, this simple synthetic route does not rely on any special or expensive equipment, thus can be exploited to the synthesis of similar polymer-inorganic nanocomposites. Compared to PAM, the PAM-metal nanocomposites showed enhanced thermal stability and antibacterial properties.

  4. First principles studies of the stability and Shottky barriers of metal/CdTe(111) interfaces

    NASA Astrophysics Data System (ADS)

    Dorj, Odkhuu; Miao, M. S.; Kioussis, N.; Tari, S.; Aqariden, F.; Chang, Y.; Grein, C.

    2015-03-01

    CdZnTe and CdTe based semiconductor X-Ray and Gamma-Ray detectors have been intensively studied recently due to their promising potentials for achieving high-resolution, high signal-to-noise ratios and low leakage current, all are desirable features in applications ranging from medical diagnostics to homeland security. Understanding the atomic and electronic structures of the metal/semiconductor interfaces is essential for the further improvements of performance. Using density functional calculations, we systematically studied the stability, the atomic and electronic structures of the interfaces between Cd-terminated CdTe (111) surface and the selected metals. We also calculated the Schottky barrier height (SBH) by aligning the electrostatic potentials in semiconductor and metal regions. Our calculations revealed the importance of intermixing between semiconductor and metal layers and the formation of Te-metal alloys at the interface. The obtained SBH does not depend much on the choice of metals despite the large variation of the work functions. On the other hand, the interface structure is found to have large effect to the SBH, which is attributed to the metal induced states in the gap. The position of such states is insensitive to the metal work functions, as revealed by the analysis of the electronic structures.

  5. Effects of freeze-thaw cycling on metal-phosphate formation and stability in single and multi-metal systems.

    PubMed

    Hafsteinsdóttir, Erla G; White, Duanne A; Gore, Damian B

    2013-04-01

    Freeze-thaw cycling may influence the chemistry, mineral stability and reaction rate during metal orthophosphate fixation. This study assessed the formation and stability of Cu-, Pb-, and Zn-phosphates in chemically simple laboratory systems during 240 freeze-thaw cycles (120 days) from +10 to -20 °C, using X-ray diffractometry. In single heavy metal systems, chloro- and hydroxy-pyromorphite (Pb(5)(PO(4))(3)(Cl,OH)), sodalite (Na(6)Zn(6)(PO(4))(6)·8H(2)O), chiral zincophosphate (Na(12)(Zn(12)P(12)O(48))·12H(2)O), and copper phosphate hydrate (Cu(3)(PO(4))(2)·3H(2)O) were the primary phosphate minerals that formed, and were typically stable during the experiment. Zinc and Cu-phosphate formation was reduced in multi heavy metal systems, and was substantially lower in abundance than chloropyromorphite. Successful Cu-, Pb- and Zn-phosphate formation can be expected in cold and freezing environments like the polar regions. However, field implementation of orthophosphate fixation needs to consider competing ion effects, concentration of the phosphate source, and the amount of free-water.

  6. Dynamical stability of the cubic metallic phase of AlH3 at ambient pressure

    NASA Astrophysics Data System (ADS)

    Kim, Duck Young; Scheicher, Ralph H.; Ahuja, Rajeev

    2009-03-01

    We have characterized the high-pressure cubic phase of AlH3 using density functional theory to determine mechanical as well as electronic properties and lattice dynamics from the response function method [1]. Metallization in AlH3 under pressure has been studied, which is of great interest not only from a fundamental physics point of view for the study of phenomena related to metallic hydrogen, but also, because metallic AlH3 possesses weaker Al-H bonds than other insulating phases [2]. Our phonon calculations show the softening of a particular mode with decreasing pressure, indicating the onset of a dynamical instability that continues to persist at ambient conditions. We find from analyzing the atomic and electronic interactions using theoretical calculations that finite-temperature effects lead to the desired stabilization of metallic AlH3 at ambient conditions.[0pt] [1] PRB 78, 100102(R) (2008). [0pt] [2] APL 92, 201903 (2008).

  7. Surface hardening of St41 low carbon steel by using the hot-pressing powder-pack boriding method

    NASA Astrophysics Data System (ADS)

    Sutrisno, Soegijono, Bambang

    2014-03-01

    This research describes a powder-pack boriding process by using hot-pressing technic for St41 low carbon steel which will improve the hardness on the substrate by forming boride layer solid solution. Those method can reduce the operational cost of the research if it is compared by the conventional method with the asmospheric condition both vacuum system and gas inert condition. The concept of boriding by hot-pressing technic was verified in a laboratory scale. Welldefined and reusedable technic was achieved by using the stainless steel 304 as the container and sealed with a 5 ton pressure. This container was filled boronizing powder consisting of 5%B4C, 90%SiC, and 5%KBF4 to close the St41 low carbon steel specimen inside the container. The St41 boriding specimen was treated at the temperature of 900°C for 8 hours. The boride layer on the substrate was found as FeB and Fe2B phase with the hardness about 1800 HV. This value was more than ten times if compared with the untreated specimen that only had the hardness of 123 HV. Depend on heat treatment temperature, heat treatment time, and powder-pack boriding pressure, the depth of boride layer range from 127 to 165 μm, leading to a diffusion controlled process.

  8. Computationally efficient determination of hydrogen isotope effects on the thermodynamic stability of metal hydrides

    NASA Astrophysics Data System (ADS)

    Nicholson, Kelly M.; Sholl, David S.

    2012-10-01

    Although the thermodynamics of metal hydrides at low to moderate temperatures has been successfully described with density functional theory (DFT) calculations using 0 K total energies and simple harmonic models, it is unclear if this approach is valid for hydrides that are stable at high temperatures. To aid development of computationally efficient methods, this paper uses DFT to explore the predicted stabilities of ZrH2, HfH2, TiH2, LiH, and NaH with four levels of theory. We also investigate isotope effects to understand if these should be accounted for in screening of deuterated or tritiated materials. We show that calculations that account for vibrational corrections to the crystal lattice are not necessary to get an accurate description of relative stabilities of metal hydrides. The shifts in dissociation temperatures due to isotope substitutions are <50 K for all materials, with larger shifts for lighter materials, as expected. We show that accounting for vibrational effects due to isotope substitution in metal hydrides is unnecessary to accurately predict the relative stabilities of metal hydrides at high temperatures.

  9. A new strategy to stabilize oxytocin in aqueous solutions: I. The effects of divalent metal ions and citrate buffer.

    PubMed

    Avanti, Christina; Amorij, Jean-Pierre; Setyaningsih, Dewi; Hawe, Andrea; Jiskoot, Wim; Visser, Jan; Kedrov, Alexej; Driessen, Arnold J M; Hinrichs, Wouter L J; Frijlink, Henderik W

    2011-06-01

    In the current study, the effect of metal ions in combination with buffers (citrate, acetate, pH 4.5) on the stability of aqueous solutions of oxytocin was investigated. Both monovalent metal ions (Na(+) and K(+)) and divalent metal ions (Ca(2+), Mg(2+), and Zn(2+)) were tested all as chloride salts. The effect of combinations of buffers and metal ions on the stability of aqueous oxytocin solutions was determined by RP-HPLC and HP-SEC after 4 weeks of storage at either 4°C or 55°C. Addition of sodium or potassium ions to acetate- or citrate-buffered solutions did not increase stability, nor did the addition of divalent metal ions to acetate buffer. However, the stability of aqueous oxytocin in aqueous formulations was improved in the presence of 5 and 10 mM citrate buffer in combination with at least 2 mM CaCl(2), MgCl(2), or ZnCl(2) and depended on the divalent metal ion concentration. Isothermal titration calorimetric measurements were predictive for the stabilization effects observed during the stability study. Formulations in citrate buffer that had an improved stability displayed a strong interaction between oxytocin and Ca(2+), Mg(2+), or Zn(2+), while formulations in acetate buffer did not. In conclusion, our study shows that divalent metal ions in combination with citrate buffer strongly improved the stability of oxytocin in aqueous solutions.

  10. Investigating extent of dissolved organic carbon stabilization by metal based coagulant in a wetland environment

    NASA Astrophysics Data System (ADS)

    Henneberry, Y.; Mourad, D.; Kraus, T.; Bachand, P.; Fujii, R.; Horwath, W.

    2008-12-01

    This study is part of a larger project designed to investigate the feasibility of using metal-based coagulants to remove dissolved organic carbon (DOC) from island drainage water in the San Joaquin Delta and subsequently retaining the metal-DOC precipitate (floc) in wetlands constructed at the foot of levees to promote levee stability. Dissolved organic carbon is a constituent of concern as some forms of DOC can be converted to carcinogenic compounds during drinking water treatment. The focus of this work is to assess floc stability over time and to determine whether floc can be permanently sequestered as part of wetland sediment. Drainage water collected seasonally from Twitchell Island was coagulated with ferric sulfate and polyaluminum chloride at optimal and 50%-optimal dosage levels. Floc was incubated in the laboratory under anaerobic conditions for six weeks under various conditions including different DOC concentrations, microbial inoculants, and addition of nutrients. Preliminary results indicate the floc is a stable system; little to no DOC was released from the floc into the water column under incubations with native microbial inoculate. In addition, floc incubated with previously coagulated water appeared to remove additional DOC from the water column. Future work will involve field and laboratory studies using 13C labeled plant material to examine the effects of fresh plant matter and the effects of peat soil DOC on floc stability, in order to elucidate mechanisms behind carbon stabilization by metal-based floc.

  11. Stabilization of ultrathin (hydroxy)oxide films on transition metal substrates for electrochemical energy conversion

    NASA Astrophysics Data System (ADS)

    Zeng, Zhenhua; Chang, Kee-Chul; Kubal, Joseph; Markovic, Nenad M.; Greeley, Jeffrey

    2017-06-01

    Design of cost-effective electrocatalysts with enhanced stability and activity is of paramount importance for the next generation of energy conversion systems, including fuel cells and electrolysers. However, electrocatalytic materials generally improve one of these properties at the expense of the other. Here, using density functional theory calculations and electrochemical surface science measurements, we explore atomic-level features of ultrathin (hydroxy)oxide films on transition metal substrates and demonstrate that these films exhibit both excellent stability and activity for electrocatalytic applications. The films adopt structures with stabilities that significantly exceed bulk Pourbaix limits, including stoichiometries not found in bulk and properties that are tunable by controlling voltage, film composition, and substrate identity. Using nickel (hydroxy)oxide/Pt(111) as an example, we further show how the films enhance activity for hydrogen evolution through a bifunctional effect. The results suggest design principles for this class of electrocatalysts with simultaneously enhanced stability and activity for energy conversion.

  12. [Effects of stabilization treatment on migration and transformation of heavy metals in mineral waste residues].

    PubMed

    Zhao, Shu-Hua; Chen, Zhi-Liang; Zhang, Tai-Ping; Pan, Wei-Bin; Peng, Xiao-Chun; Che, Rong; Ou, Ying-Juan; Lei, Guo-Jian; Zhou, Ding

    2014-04-01

    Different forms of heavy metals in soil will produce different environmental effects, and will directly influence the toxicity, migration and bioavailability of heavy metals. This study used lime, fly ash, dried sludge, peanut shells as stabilizers in the treatment of heavy metals in mineral waste residues. Morphological analyses of heavy metal, leaching experiments, potted plant experiments were carried out to analyze the migration and transformation of heavy metals. The results showed that after adding stabilizers, the pH of the acidic mineral waste residues increased to more than neutral, and the organic matter content increased significantly. The main existing forms of As, Pb, and Zn in the mineral waste residues were the residual. The contents of exchangeable and organic matter-bound As decreased by 65.6% and 87.7% respectively after adding fly ash, dried sludge and peanut shells. Adding lime, fly ash and peanut shells promoted the transformation of As from the Fe-Mn oxide-bound to the carbonate-bound, and adding lime and fly ash promoted the transformation of Pb and Zn from the exchangeable, Fe-Mn oxide-bound, organic matter-bound to the residual. After the early stage of the stabilization treatment, the contents of As, Pb and Zn in the leachate had varying degrees of decline, and adding peanut shells could reduce the contents of As, Pb and Zn in the leachate further. Among them, the content of As decreased most significantly after treatment with fly ash, dried sludge and peanut shells, with a decline of 57.4%. After treatment with lime, fly ash and peanut shells, the content of Zn decreased most significantly, by 24.9%. The addition of stabilizers was advantageous to the germination and growth of plants. The combination of fly ash, dried sludge and peanut shell produced the best effect, and the Vetiveria zizanioides germination rate reached 76% in the treated wasted mineral residues.

  13. Crystal structures and compressibility of novel iron borides Fe2B7 and FexB50 synthesized at high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Bykova, E.; Gou, H.; Bykov, M.; Hanfland, M.; Dubrovinsky, L.; Dubrovinskaia, N.

    2015-10-01

    We present here a detailed description of the crystal structures of novel iron borides, Fe2B7 and FexB50 with various iron content (x=1.01(1), 1.04(1), 1.32(1)), synthesized at high pressures and high temperatures. As revealed by high-pressure single-crystal X-ray diffraction, the structure of Fe2B7 possesses short incompressible B-B bonds, which make it as stiff as diamond in one crystallographic direction. The volume compressibility of Fe2B7 (the bulk modulus K0= 259(1.8) GPa, K0‧= 4 (fixed)) is even lower than that of FeB4 and comparable with that of MnB4, known for high bulk moduli among 3d metal borides. FexB50 adopts the structure of the tetragonal δ-B, in which Fe atoms occupy an interstitial position. FexB50 does not show considerable anisotropy in the elastic behavior.

  14. Niobium boride layers deposition on the surface AISI D2 steel by a duplex treatment

    SciTech Connect

    Kon, O.; Pazarlioglu, S.

    2015-03-30

    In this paper, we investigated the possibility of deposition of niobium boride layers on the surface of AISI D2 steel by a duplex treatment. At the first step of duplex treatment, boronizing was performed on AISI D2 steel samples at 1000{sup o}C for 2h and then pre-boronized samples niobized at 850°C, 900°C and 950°C using thermo-reactive deposition method for 1–4 h. The presence of the niobium boride layers such as NbB, NbB{sub 2} and Nb{sub 3}B{sub 4} and also iron boride phases such as FeB, Fe{sub 2}B were examined by X-ray diffraction analysis. Scanning electron microscope (SEM) and micro-hardness measurements were realized. Experimental studies showed that the depth of the coating layers increased with increasing temperature and times and also ranged from 0.42 µm to 2.43 µm, depending on treatment time and temperature. The hardness of the niobium boride layer was 2620±180 HV{sub 0.005}.

  15. Superabrasive boride and a method of preparing the same by mechanical alloying and hot pressing

    DOEpatents

    Cook, Bruce A.; Harringa, Joel L.; Russell, Alan M.

    2002-08-13

    A ceramic material which is an orthorhombic boride of the general formula: AlMgB.sub.14 :X, with X being a doping agent. The ceramic is a superabrasive, and in most instances provides a hardness of 40 GPa or greater.

  16. Ultra-Fast Boriding in High-Temperature Materials Processing Industries

    SciTech Connect

    2008-12-01

    This factsheet describes a research project whose main objective is to further develop, optimize, scale-up, and commercialize an ultra-fast boriding (also referred to as “boronizing”) process that can provide much higher energy efficiency, productivity, and near-zero emissions in many of the high-temperature materials processing industries.

  17. First principles studies of the stability and Shottky barriers of metal/CdTe(111) interfaces

    NASA Astrophysics Data System (ADS)

    Liu, Zhen; Miao, Masoehng; Kioussis, Nicholas; Aqariden, Fikri; Chang, Y.; Grein, Christoph

    CdZnTe and CdTe based semiconductor X-Ray and Gamma-Ray detectors have been intensively studied recently due to their promising potentials for achieving high-resolution, high signal-to-noise ratios and low leakage current, all are desirable features in applications ranging from medical diagnostics to homeland security. Using density functional calculations, we systematically studied the stability, the atomic and electronic structures of the interfaces between CdTe (111) surfaces (Cd- and Te-terminated) and the selected metals (Cu, Al Ni, Pd and Pt). We also calculated the Schottky barrier height (SBH) by aligning the electrostatic potentials in semiconductor and metal regions. Our calculations revealed significant differences between the Cd- and Te- terminated interfaces. While metals tend to deposit directly on reconstructed Te-terminated surfaces, they form a Te-metal alloy layer at the Cd-Terminated metal/CdTe interface. For both Te- and Cd- terminated interfaces, the Schottky barrier heights do not depend much on the choice of metals despite the large variation of the work functions. On the other hand, the interface structure is found to have large effect on the SBH, which is attributed to the metal induced states in the gap.

  18. Graphene-metal interaction and its effect on the interface stability under ambient conditions

    NASA Astrophysics Data System (ADS)

    Dong, Aiyi; Fu, Qiang; Wei, Mingming; Bao, Xinhe

    2017-08-01

    Interaction between graphene (Gr) and metal plays an important role in physics and chemistry of graphene/metal interfaces. In this work, well-defined interfaces between graphene and transition metals (TMs) including Fe, Co, Pt, and Au were prepared through TM intercalation on Gr/Ru(0001) surface. The Gr-metal interaction was investigated using X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy. We found that graphene interacts most strongly with Ru, Fe and Co and most weakly with Au, following the order of Ru ≈ Fe ≈ Co > Pt > Au. The Gr/Fe, Gr/Co, Gr/Pt, and Gr/Ru interfaces can be readily intercalated by oxygen when exposed to air and illuminated by an infrared lamp. In contrast, oxygen intercalation does not happen at the Gr/Au interface under the same condition. It is suggested that both Gr-metal interaction and oxygen adsorption on the underlying metal surface are critical in the oxygen intercalation and the Gr/metal interface stability.

  19. Stabilization of cationic and anionic metal species in contaminated soils using sludge-derived biochar.

    PubMed

    Fang, Shen'en; Tsang, Daniel C W; Zhou, Fengsha; Zhang, Weihua; Qiu, Rongliang

    2016-04-01

    Currently, sludge pyrolysis has been considered as a promising technology to solve disposal problem of municipal sewage sludge, recover sludge heating value, sequester carbon and replenish nutrients in farmland soils. The resultant sludge-derived biochar (SDBC) is potentially an excellent stabilizing agent for metal species. This study applied the SDBC into four soils that had been contaminated in field with cationic Pb(II) and Cd(II)/Ni(II), and anionic Cr(VI) and As(III), respectively. The performance of metal stabilization under various operational and environmental conditions was evaluated with acid batch extraction and column leaching tests. Results indicated the SDBC could effectively stabilize these metals, which was favored by elevated temperature and longer aging. Periodic temperature decrease from 45 to 4 °C resulted in the release of immobilized Cr(VI) and As(III) but not Pb(II). However, a longer aging time offset such metal remobilization. This was possibly because more Pb was strongly bound and even formed stable precipitates, as shown by XRD and sequential extraction results. With increasing time, Cr(VI) was sorbed and partly reduced to Cr(III), while immobilized As(III) was co-oxidized to As(V) as indicated by XPS spectra. Column tests revealed that adding SDBC as a separate layer was unfavorable because the concentrated Cd(II) and Ni(II) in localized positions increased the peak levels of metal release under continuous acid leaching. In contrast, uniformly mixed SDBC could effectively delay the metal breakthrough and reduce their released amounts. Yet, a long-term monitoring may be required for evaluating the potential leaching risks and bioavailability/toxicity of these immobilized and transformed species in the SDBC-amended soils.

  20. Structures and stability of metal-doped GenM (n = 9, 10) clusters

    NASA Astrophysics Data System (ADS)

    Qin, Wei; Lu, Wen-Cai; Xia, Lin-Hua; Zhao, Li-Zhen; Zang, Qing-Jun; Wang, C. Z.; Ho, K. M.

    2015-06-01

    The lowest-energy structures of neutral and cationic GenM (n = 9, 10; M = Si, Li, Mg, Al, Fe, Mn, Pb, Au, Ag, Yb, Pm and Dy) clusters were studied by genetic algorithm (GA) and first-principles calculations. The calculation results show that doping of the metal atoms and Si into Ge9 and Ge10 clusters is energetically favorable. Most of the metal-doped Ge cluster structures can be viewed as adding or substituting metal atom on the surface of the corresponding ground-state Gen clusters. However, the neutral and cationic FeGe9,10,MnGe9,10 and Ge10Al are cage-like with the metal atom encapsulated inside. Such cage-like transition metal doped Gen clusters are shown to have higher adsorption energy and thermal stability. Our calculation results suggest that Ge9,10Fe and Ge9Si would be used as building blocks in cluster-assembled nanomaterials because of their high stabilities.

  1. Immobilization of metals in contaminated soils using natural polymer-based stabilizers.

    PubMed

    Tao, Xue; Li, Aimin; Yang, Hu

    2017-03-01

    Three low-cost natural polymer materials, namely, lignin (Ln), carboxymethyl cellulose, and sodium alginate, were used for soil amendment to immobilize lead and cadmium in two contaminated soil samples collected from a mining area in Nanjing, China. The remediation effects of the aforementioned natural polymers were evaluated by toxicity characteristic leaching procedure (TCLP) and sequential extractions. The stabilizers could lower the bioavailability of Pb and Cd in the contaminated soils, and the amount of the exchangeable forms of the aforementioned two metals were reduced evidently. TCLP results showed that the leaching concentrations of Pb and Cd were decreased by 5.46%-71.1% and 4.25%-49.6%, respectively, in the treated soils. The contents of the organic forms of the two metals both increased with the increase in stabilizer dose on the basis of the redistribution of metal forms by sequential extractions. These findings were due to the fact that the abundant oxygen-containing groups on the polymeric amendments were effective in chelating and immobilizing Pb and Cd, which have been further confirmed from the metal adsorptions in aqueous solutions. Moreover, Ln achieved the greatest effect among the three polymers under study because of the former's distinct three-dimensional molecular structure, showing the preferential immobilization of Pb over Cd in soils also. Thus, the above-mentioned natural polymers hold great application potentials for reducing metal ion entry into the food chain at a field scale.

  2. Structures and stability of metal-doped GenM (n = 9, 10) clusters

    DOE PAGES

    Qin, Wei; Lu, Wen-Cai; Xia, Lin-Hua; ...

    2015-06-26

    The lowest-energy structures of neutral and cationic Ge nM (n = 9, 10; M = Si, Li, Mg, Al, Fe, Mn, Pb, Au, Ag, Yb, Pm and Dy) clusters were studied by genetic algorithm (GA) and first-principles calculations. The calculation results show that doping of the metal atoms and Si into Ge9 and Ge10 clusters is energetically favorable. Most of the metal-doped Ge cluster structures can be viewed as adding or substituting metal atom on the surface of the corresponding ground-state Gen clusters. However, the neutral and cationic FeGe9,10,MnGe9,10 and Ge10Al are cage-like with the metal atom encapsulated inside. Suchmore » cage-like transition metal doped Gen clusters are shown to have higher adsorption energy and thermal stability. Our calculation results suggest that Ge9,10Fe and Ge9Si would be used as building blocks in cluster-assembled nanomaterials because of their high stabilities.« less

  3. Processing development of 4 tantalum carbide-hafnium carbide and related carbides and borides for extreme environments

    NASA Astrophysics Data System (ADS)

    Gaballa, Osama Gaballa Bahig

    temperature, and hot-pressing pressure. Also, WC additions to Ta4HfC5 were found to improve densification and increase microhardness. The ability to process these materials at relatively low temperature would save energy and reduce cost. Boron-based hard materials are used in numerous applications such as industrial machining, armor plating, and wear-resistant coatings. It was often thought that in addition to strong bonding, super-hard materials must also possess simple crystallographic unit cells with high symmetry and a minimum number of crystal defects (e.g., diamond and cubic boron nitride (cBN)). However, one ternary boride, AlMgB14, deviates from this paradigm; AlMgB 14 has a large, orthorhombic unit cell (oI64) with multiple icosahedral boron units. TiB2 has been shown to be an effective reinforcing phase in AlMgB 14, raising hardness, wear resistance, and corrosion resistance. Thus, it was thought that adding other, similar phases (i.e., ZrB2 and HfB2) to AlMgB14 could lead to useful improvements in properties vis-à-vis pure AlMgB14. Group IV metal diborides (XB2, where X = Ti, Zr, or Hf) are hard, ultra-high temperature ceramics. These compounds have a primitive hexagonal crystal structure (hP3) with planes of graphite-like boride rings above and below planes of metal atoms. Unlike graphite, there is strong bonding between the planes, resulting in high hardness. For this study two-phase composites of 60 vol. % metal diborides with 40 vol. % AlMgB14 were produced and characterized.

  4. [Recent advance in solidification/stabilization technology for the remediation of heavy metals-contaminated soil].

    PubMed

    Hao, Han-zhou; Chen, Tong-bin; Jin, Meng-gui; Lei, Mei; Liu, Cheng-wu; Zu, Wen-pu; Huang, Li-mi

    2011-03-01

    Remediation of heavy metals-contaminated soil is still a difficulty and a hotspot of international research projects. At present, the technologies commonly adopted for the remediation of contaminated sites mainly include excavation, solidification/stabilization (S/S), soil washing, soil vapor extraction (SVE), thermal treatment, and bioremediation. Based on the S/S technical guidelines of Unite State Environmental Protection Agency (EPA) and United Kingdom Environment Agency (EA) and the domestic and foreign patents, this paper introduced the concepts of S/S and its development status at home and abroad, and discussed its future development directions. Solidification refers to a process that binds contaminated media with a reagent, changing the media's physical properties via increasing its compressive strength, decreasing its permeability, and encapsulating the contaminants to form a solid material. Stabilization refers to the process that involves a chemical reaction which reduces the leachability of a waste, chemically immobilizes the waste and reduces its solubility, making the waste become less harmful or less mobile. S/S technology includes cement solidification, lime pozzolanic solidification, plastic materials stabilization, vitrification, and regent-based stabilization. Stabilization (or immobilization) treatment processes convert contaminants to less mobile forms through chemical or thermal interactions. In stabilization technology, the aim of adding agents is to change the soil physical and chemical properties through pH control technology, redox potential technology, precipitation techniques, adsorption technology, and ion-exchange technology that change the existing forms of heavy metals in soil, and thus, reduce the heavy metals bioavailability and mobility. This review also discussed the S/S evaluation methods, highlighted the need to enhance S/S technology in the molecular bonding, soil polymers, and formulation of China's S/S technical guidelines.

  5. Final Report for "Stabilization of resistive wall modes using moving metal walls"

    SciTech Connect

    Forest, Cary B.

    2014-02-05

    The UW experiment used a linear pinch experiment to study the stabilization of MHD by moving metal walls. The methodology of the experiment had three steps. (1) Identify and understand the no-wall MHD instability limits and character, (2) identify and understand the thin-wall MHD instabilities (re- sistive wall mode), and then (3) add the spinning wall and understand its impact on stability properties. During the duration of the grant we accomplished all 3 of these goals, discovered new physics, and completed the experiment as proposed.

  6. Surge discharge capability and thermal stability of a metal oxide surge arrester

    SciTech Connect

    Kan, M.; Kojima, S.; Nishiwaki, S.; Sato, T.; Yanabu, S.

    1983-02-01

    The surge discharge capability and the thermal stability of a metal oxide surge arrester were examined experimentally. It was found that the breakdown energy is nearly the same against the switching surge and the temporary overvoltage of various peak values and time durations. Heat dissipation capability of an 84kV porcelain-type model arrester was examined and found to be less than that of a small model unit, while this relation of the value had been considered opposite in a previously published paper. From these experimental data, the limit at high operation stress was found to be determined by the thermal stability rather than by the discharge capability

  7. Inosine octamer stabilized by alkali earth metal cations - as studied by electrospray ionization mass spectrometry.

    PubMed

    Frańska, Magdalena

    2014-01-01

    By using electrospray ionization mass spectrometry, inosine was found to be able to form an octamer stabilized by alkali earth metal cation, namely Ca(2+), Sr(2+) and Ba(2+), of which the most stable is that stabilized by Ca(2+) (ion [I8+Ca](2+)). It was established that 9-methylhypoxanthine (M) did not form an analogical octamer, since ion [M8+Ca](2+) was not detected. On the other hand, 9-methylhypoxanthine can form "mixed" octamers together with inosine (ions [InMm+Ca](2+), n + m = 8, were detected).

  8. Surface energetics of alkaline-earth metal oxides: Trends in stability and adsorption of small molecules

    NASA Astrophysics Data System (ADS)

    Bajdich, Michal; Nørskov, Jens K.; Vojvodic, Aleksandra

    2015-04-01

    We present a systematic theoretical investigation of the surface properties, stability, and reactivity of rocksalt type alkaline-earth metal oxides including MgO, CaO, SrO, and BaO. The accuracy of commonly used exchange-correlation density functionals (LDA, PBE, RPBE, PBEsol, BEEF-vdW, and hybrid HSE) and random-phase approximation (RPA) is evaluated and compared to existing experimental values. Calculated surface energies of the four most stable surface facets under vacuum conditions, the (100) surface, the metal and oxygen terminated octopolar (111), and the (110) surfaces, exhibit a monotonic increase in stability from MgO to BaO. On the MgO(100) surface, adsorption of CO, NO, and CH4 is characterized by physisorption while H2O chemisorbs, which is in agreement with experimental findings. We further use the on-top metal adsorption of CO and NO molecules to map out the surface energetics of each alkaline-earth metal oxide surface. The considered functionals all qualitatively predict similar adsorption energy trends. The ordering between the adsorption energies on different surface facets can be attributed to differences in the local geometrical surface structure and the electronic structure of the metal constituent of the alkaline-earth metal oxide. The striking observation that CO adsorption strength is weaker than NO adsorption on the (100) terraces as the period of the alkaline-earth metal in the oxide increases is analyzed in detail in terms of charge redistribution within the σ and π channels of adsorbates. Finally, we also present oxygen adsorption and oxygen vacancy formation energies in these oxide systems.

  9. Polydopamine tethered enzyme/metal-organic framework composites with high stability and reusability

    NASA Astrophysics Data System (ADS)

    Wu, Xiaoling; Yang, Cheng; Ge, Jun; Liu, Zheng

    2015-11-01

    An enzyme/metal-organic framework (MOF) composite with both highly stable and easily reusable features was prepared via tethering enzyme/MOF nanocrystals with polydopamine (PDA). The micrometer-sized PDA tethered enzyme/MOF composite can be easily repeatedly used without obvious activity loss, promising for efficient enzymatic catalysis at low cost with long-term operational stability under harsh conditions.An enzyme/metal-organic framework (MOF) composite with both highly stable and easily reusable features was prepared via tethering enzyme/MOF nanocrystals with polydopamine (PDA). The micrometer-sized PDA tethered enzyme/MOF composite can be easily repeatedly used without obvious activity loss, promising for efficient enzymatic catalysis at low cost with long-term operational stability under harsh conditions. Electronic supplementary information (ESI) available: Synthesis of enzyme-MOF nanocrystals, SEM, TEM, CLSM characterization and measurements of enzymatic performances. See DOI: 10.1039/c5nr05190h

  10. Utilization of fly ash for stabilization/solidification of heavy metal contaminated soils

    SciTech Connect

    Dermatas, D.; Meng, X.

    1995-12-01

    Pozzolanic-based stabilization/solidification (S/S) is an effective, yet economic technological alternative to immobilize heavy metals in contaminated soils and sludges. Fly ash waste materials were used along with quicklime (CaO) to immobilize lead, trivalent and hexavalent chromium present in contaminated clayey sand soils. The degree of heavy metal immobilization was evaluated using the Toxicity Characteristic Leaching Procedure (TCLP) as well as controlled extraction experiments. These leaching test results along with X-ray diffraction (XRD), scanning electron microscope and energy dispersive x-ray (SEM-EDX) analyses were also implemented to elucidate the mechanisms responsible for immobilization of the heavy metals under study. Finally, the reusability of the stabilized waste forms in construction applications was also investigated by performing unconfined compressive strength and swell tests. Results suggest that the controlling mechanism for both lead and hexavalent chromium immobilization is surface adsorption, whereas for trivalent chromium it is hydroxide precipitation. Addition of fly ash to the contaminated soils effectively reduced heavy metal leachability well below the non-hazardous regulatory limits. However, quicklime addition was necessary in order to attain satisfactory immobilization levels. Overall, fly ash addition increases the immobilization pH region for all heavy metals tested, and significantly improves the stress-strain properties of the treated solids, thus allowing their reuse as readily available construction materials. The only potential problem associated with this quicklime/fly ash treatment is the excessive formation of the pozzolanic product ettringite in the presence of sulfates. Ettringite, when brought in contact with water, may cause significant swelling and subsequent deterioration of the stabilized matrix. Addition of minimum amounts of barium hydroxide was shown to effectively eliminate ettringite formation.

  11. Ionomer-Liquid Electrolyte Hybrid Ionic Conductor for High Cycling Stability of Lithium Metal Electrodes

    PubMed Central

    Song, Jongchan; Lee, Hongkyung; Choo, Min-Ju; Park, Jung-Ki; Kim, Hee-Tak

    2015-01-01

    The inhomogeneous Li electrodeposition of lithium metal electrode has been a major impediment to the realization of rechargeable lithium metal batteries. Although single ion conducting ionomers can induce more homogeneous Li electrodeposition by preventing Li+ depletion at Li surface, currently available materials do not allow room-temperature operation due to their low room temperature conductivities. In the paper, we report that a highly conductive ionomer/liquid electrolyte hybrid layer tightly laminated on Li metal electrode can realize stable Li electrodeposition at high current densities up to 10 mA cm−2 and permit room-temperature operation of corresponding Li metal batteries with low polarizations. The hybrid layer is fabricated by laminating few micron-thick Nafion layer on Li metal electrode followed by soaking 1 M LiPF6 EC/DEC (1/1) electrolyte. The Li/Li symmetric cell with the hybrid layer stably operates at a high current density of 10 mA cm−2 for more than 2000 h, which corresponds to more than five-fold enhancement compared with bare Li metal electrode. Also, the prototype Li/LiCoO2 battery with the hybrid layer offers cycling stability more than 350 cycles. These results demonstrate that the hybrid strategy successfully combines the advantages of bi-ionic liquid electrolyte (fast Li+ transport) and single ionic ionomer (prevention of Li+ depletion). PMID:26411701

  12. Hydrothermal sulfidation and floatation treatment of heavy-metal-containing sludge for recovery and stabilization.

    PubMed

    Liang, Yan-Jie; Chai, Li-Yuan; Min, Xiao-Bo; Tang, Chong-Jian; Zhang, Hai-Jing; Ke, Yong; Xie, Xian-De

    2012-05-30

    This study focuses on the application of hydrothermal sulfidation and floatation to treat the heavy-metal-containing sludge for recovery and stabilization. After the hydrothermal sulfidation, the sulfidation percentage of zinc and lead reach up to 85.0% and 75.4%, respectively. 33.3% of Zn, 58.9% of Pb and 68.8% of Cu can be recovered from the sludge by floatation. The lower recovery of ZnS attributes to its surface and structural characteristics. To compare these characteristics, three types of synthetic metal sulfide (ZnS, PbS and CuS) were prepared and examined with XRD, SEM and TEM. The poor floatability of the finely dispersed, round shape of ZnS can be improved by crystal modification in hydrothermal condition. With increasing the temperature and reaction time, the grain size of the ZnS increased from 7.95 nm to 44.28 nm and the recovery of Zn increased to from 33.3% to 72.8%. The TCLP results indicate that all the leached heavy metal concentrations of floatation tailings are under the allowable limit. No obvious increase of heavy metal concentration was observed in continuous leaching procedure. The presence of alkaline compounds after hydrothermal sulfidation might act as mineralogical scavengers of dissolved heavy metal released by sulfide oxidation to avoid the heavy metal pollution.

  13. Chemical Stabilization of 1T' Phase Transition Metal Dichalcogenides with Giant Optical Kerr Nonlinearity.

    PubMed

    Tan, Sherman J R; Abdelwahab, Ibrahim; Ding, Zijing; Zhao, Xiaoxu; Yang, Tieshan; Loke, Gabriel Z J; Lin, Han; Verzhbitskiy, Ivan; Poh, Sock Mui; Xu, Hai; Nai, Chang Tai; Zhou, Wu; Eda, Goki; Jia, Baohua; Loh, Kian Ping

    2017-02-15

    The 2H-to-1T' phase transition in transition metal dichalcogenides (TMDs) has been exploited to phase-engineer TMDs for applications in which the metallicity of the 1T' phase is beneficial. However, phase-engineered 1T'-TMDs are metastable; thus, stabilization of the 1T' phase remains an important challenge to overcome before its properties can be exploited. Herein, we performed a systematic study of the 2H-to-1T' phase evolution by lithiation in ultrahigh vacuum. We discovered that by hydrogenating the intercalated Li to form lithium hydride (LiH), unprecedented long-term (>3 months) air stability of the 1T' phase can be achieved. Most importantly, this passivation method has wide applicability for other alkali metals and TMDs. Density functional theory calculations reveal that LiH is a good electron donor and stabilizes the 1T' phase against 2H conversion, aided by the formation of a greatly enhanced interlayer dipole-dipole interaction. Nonlinear optical studies reveal that air-stable 1T'-TMDs exhibit much stronger optical Kerr nonlinearity and higher optical transparency than the 2H phase, which is promising for nonlinear photonic applications.

  14. Alkali Metal Chlorine and Bromine Carbenoids: Their Thermal Stability and Structural Properties.

    PubMed

    Molitor, Sebastian; Gessner, Viktoria H

    2017-09-07

    The synthesis and structures of a series of M/X carbenoids of the type [Ph2 P(S)]2 CMX with M=Li, Na, and K and X=Cl and Br are reported, amongst the first isolated Na/Br and K/Br carbenoids. NMR spectroscopic as well as crystallographic studies showed distinct differences between the lithium carbenoids and their heavier congeners. In the solid state, all carbenoids showed no direct metal-carbon interaction, but an interaction between the metal and the halogen atom. This contact is only very weak in the case of the Li/Br carbenoid, but much more pronounced in the corresponding potassium and sodium compounds. Nevertheless, these interactions did not significantly influence the stability of the carbenoids by weakening the C-X bond and facilitating the MX elimination. As such all compounds were found to be stable up to approximately 60 °C in solution. Hence, M-X interactions-albeit being an essential feature for the structure formation of carbenoids-are not the only criterion determining the stability of such compounds. In the present systems, the stabilization by the thiophosphinoyl moieties is more important than the metal/halogen combination. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Feasibility of biochar manufactured from organic wastes on the stabilization of heavy metals in a metal smelter contaminated soil.

    PubMed

    Abdelhafez, Ahmed A; Li, Jianhua; Abbas, Mohamed H H

    2014-12-01

    The main objectives of the current study were to evaluate the potential effects of biochar derived from sugar cane bagasse (SC-BC) and orange peel (OP-BC) on improving the physicochemical properties of a metal smelter contaminated soil, and determining its potentiality for stabilizing Pb and As in soil. To achieve these goals, biochar was produced in a small-scale biochar producing plant, and an incubation experiment was conducted using a silt loam metal-contaminated soil treated with different application rates of biochar (0-10% w/w). The obtained results showed that, the addition of SC-BC and OP-BC increased significantly the soil aggregate stability, water-holding capacity, cation exchange capacity, organic matter and N-status in soil. SC-BC considerably decreased the solubility of Pb to values lower than the toxic regulatory level of the toxicity characteristics leaching procedure extraction (5 mg L(-1)). The rise in soil pH caused by biochar application, and the increase of soil organic matter transformed the labile Pb into less available fractions i.e. "Fe-Mn oxides" and "organic" bound fractions. On the other hand, As was desorbed from Fe-Mn oxides, which resulted in greater mobility of As in the treated soil. We concluded that SC-BC and OP-BC could be used successfully for remediating soils highly contaminated with Pb. However, considerable attention should be paid when using it in soil contaminated with As.

  16. Temporal stability of magic-number metal clusters: beyond the shell closing model

    NASA Astrophysics Data System (ADS)

    Desireddy, Anil; Kumar, Santosh; Guo, Jingshu; Bolan, Michael D.; Griffith, Wendell P.; Bigioni, Terry P.

    2013-02-01

    The anomalous stability of magic-number metal clusters has been associated with closed geometric and electronic shells and the opening of HOMO-LUMO gaps. Despite this enhanced stability, magic-number clusters are known to decay and react in the condensed phase to form other products. Improving our understanding of their decay mechanisms and developing strategies to control or eliminate cluster instability is a priority, to develop a more complete theory of their stability, to avoid studying mixtures of clusters produced by the decay of purified materials, and to enable technology development. Silver clusters are sufficiently reactive to facilitate the study of the ambient temporal stability of magic-number metal clusters and to begin to understand their decay mechanisms. Here, the solution phase stability of a series of silver:glutathione (Ag:SG) clusters was studied as a function of size, pH and chemical environment. Cluster stability was found to be a non-monotonic function of size. Electrophoretic separations showed that the dominant mechanism involved the redistribution of mass toward smaller sizes, where the products were almost exclusively previously known cluster sizes. Optical absorption spectra showed that the smaller clusters evolved toward the two most stable cluster sizes. The net surface charge was found to play an important role in cluster stabilization although charge screening had no effect on stability, contrary to DLVO theory. The decay mechanism was found to involve the loss of Ag+ ions and silver glutathionates. Clusters could be stabilized by the addition of Ag+ ions and destabilized by either the addition of glutathione or the removal of Ag+ ions. Clusters were also found to be most stable in near neutral pH, where they had a net negative surface charge. These results provide new mechanistic insights into the control of post-synthesis stability and chemical decay of magic-number metal clusters, which could be used to develop design principles

  17. Stability of high temperature chemical vapor deposited silicon based structures on metals for solar conversion.

    PubMed

    Gelard, Isabelle; Chichignoud, Guy; Blanquet, Elisabeth; Xuan, Hoan Nguyen; Cruz, Ruben; Jimenez, Carmen; Sarigiannidou, Eirini; Zaidat, Kader

    2011-09-01

    Highly crystallized silicon layers were grown on metal sheets at high temperature (950 degrees C) by thermal CVD from silane. An intermediate buffer layer was mandatory to prevent interdiffusion and silicide formation but also to compensate lattice parameters and thermal expansion coefficients mismatches between metal and silicon and ideally transfer some crystalline properties (grain size, texture) from the substrate to the silicon layer. After a thermodynamic study, aluminum nitride or titanium nitride diffusion barrier layers were selected and processed by CVD. The structure and the interfaces stabilities of these silicon/nitride/metal stacks were studied by field effect gun scanning and transmission electron microscopy, X-ray diffraction, Raman and energy dispersive X-ray spectroscopy. As a result, TiN deposited by CVD appears to be an efficient material as a buffer layer between steel and silicon.

  18. Increased stability in laser metal wire deposition through feedback from optical measurements

    NASA Astrophysics Data System (ADS)

    Heralić, Almir; Christiansson, Anna-Karin; Ottosson, Mattias; Lennartson, Bengt

    2010-04-01

    Robotized laser metal-wire deposition is a fairly new technique being developed at University West in cooperation with Swedish industry for solid freeform fabrication of fully densed metal structures. It is developed around a standard welding cell and uses robotized fiber laser welding and wire filler material together with a layered manufacturing method to create metal structures. In this work a monitoring system, comprising two cameras and a projected laser line, is developed for on-line control of the deposition process. The controller is a combination of a PI-controller for the bead width and a feed-forward compensator for the bead height. It is evaluated through deposition of single-bead walls, and the results show that the process stability is improved when the proposed controller is used.

  19. Stability of ciprofloxacin and norfloxacin in the presence and absence of metal ions in acidic solution.

    PubMed

    Hubicka, Urszula; Krzek, Jan; Walczak, Maria

    2010-01-01

    A thin-layer chromatographic-densitometric method was used to determine the stability of ciprofloxacin and norfloxacin in the presence and absence of metal ions in acidic solutions at 22 degrees C, 50 degrees C and 90 degrees C. The degradation of ciprofloxacin and norfloxacin followed first order reaction kinetics in presence of metal ions. The extent of this degradation however depended on the type of metal ion and temperature. Product structures of ciprofloxacin (1-cyclopropyl-6-fluoro-7-(piperazin-1-yl)quinolin-4(1H)-one) and norfloxacin (1-ethyl-6-fluoro-7-(piperazin-1-yl)quinolin-4(1H)-one) were determined by analysis of UV spectra and using LC-MS method.

  20. Stability diagrams for fourfold coordination of polyvalent metal ions in molten mixtures of halide salts

    SciTech Connect

    Akdeniz, Z. Istanbul Univ. . Dept. of Physics); Tosi, M.P. . Dipt. di Fisica Teorica Argonne National Lab., IL )

    1988-11-01

    The stability of local fourfold coordination for divalent and trivalent metal ions in liquid mixtures of polyvalent metal halides and alkali halides is classified by means of structural coordinates obtained from properties of the elements. In parallel with earlier classifications of compound crystal structures and molecular shapes, the elemental properties are taken from first-principles calculations of valence electron orbitals in atoms, in the form of (i) the nodal radii of Andreoni, Baldereschi and Guizzetti or (ii) the pseudopotential radii or Zunger and Cohen. As a third alternative a classification based on Pettifor's phenomenological chemical scale of the elements is also considered. The alternative structural classification schemes that are developed from these elemental properties are generally successfully in distinguishing molten mixtures in which the available experimental evidence indicates long-lived fourfold coordination of polyvalent metal ions. In addition, Pettifor's chemical scale scheme is useful in sorting out finer details of local coordination in the liquid state. 3 figs., 71 refs.

  1. Heavy metal stabilization in contaminated soil by treatment with calcined cockle shell.

    PubMed

    Islam, Mohammad Nazrul; Taki, Golam; Nguyen, Xuan Phuc; Jo, Young-Tae; Kim, Jun; Park, Jeong-Hun

    2017-01-17

    In several previous studies, the efficacy of various liming waste materials on the immobilization of heavy metals has been tested and it was found that soils contaminated with heavy metals can be stabilized using this technique. Since lime (CaO) has been identified as the main phase of calcined cockle shell (CCS), it was hypothesized that CCS could be used as a soil amendment to immobilize heavy metals in soil. However, to date, no studies have been conducted using CCS. In this study, the effectiveness of CCS powder on the immobilization of Cd, Pb, and Zn in mine tailing soil was evaluated. After 28 days of incubation, the treated soil samples were exposed to weathering (four cycles of freezing-thawing and four cycles of wetting-drying) for 8 days before being subjected to a leaching test. The results of this study revealed that the soil pH increased from 7.5 to 12.2 with the addition of 5% CCS. A similar soil pH was obtained when the soil was amended with 5% pure CaO. By leaching with 0.1 M HCl, extracted Cd, Pb, and Zn were reduced by up to 85, 85, and 91%, respectively. Therefore, CCS is suggested as a low-cost lime-based soil amendment for stabilizing heavy metals in abandoned mining sites.

  2. Stabilization of heavy metals in lightweight aggregate made from sewage sludge and river sediment.

    PubMed

    Xu, Guoren; Liu, Mingwei; Li, Guibai

    2013-09-15

    The primary goal of this research is to investigate the stabilization of heavy metals in lightweight aggregate (LWA) made from sewage sludge and river sediment. The effects of the sintering temperature, the (Fe₂O₃+CaO+MgO)/(SiO₂+Al₂O₃) ratio (K ratio), SiO₂/Al₂O₃ and Fe₂O₃/CaO/MgO (at fixed K ratio), pH, and oxidative conditions on the stabilization of heavy metals were studied. Sintering at temperatures above 1100 °C effectively binds Cd, Cr, Cu and Pb in the LWA, because the stable forms of the heavy metals are strongly bound to the aluminosilicate or silicate frameworks. Minimum leachabilities of Cd, Cr, Cu and Pb were obtained at K ratios between 0.175 and 0.2. When the LWA was subjected to rigorous leaching conditions, the heavy metals remained in the solid even when the LWA bulk structure was broken. LWA made with sewage sludge and river sediment can therefore be used as an environmentally safe material for civil engineering and other construction applications.

  3. Color stability, water sorption and cytotoxicity of thermoplastic acrylic resin for non metal clasp denture.

    PubMed

    Jang, Dae-Eun; Lee, Ji-Young; Jang, Hyun-Seon; Lee, Jang-Jae; Son, Mee-Kyoung

    2015-08-01

    The aim of this study was to compare the color stability, water sorption and cytotoxicity of thermoplastic acrylic resin for the non-metal clasp dentures to those of thermoplastic polyamide and conventional heat-polymerized denture base resins. Three types of denture base resin, which are conventional heat-polymerized acrylic resin (Paladent 20), thermoplastic polyamide resin (Bio Tone), thermoplastic acrylic resin (Acrytone) were used as materials for this study. One hundred five specimens were fabricated. For the color stability test, specimens were immersed in the coffee and green tee for 1 and 8 weeks. Color change was measured by spectrometer. Water sorption was tested after 1 and 8 weeks immersion in the water. For the test of cytotoxicity, cell viability assay was measured and cell attachment was analyzed by FE-SEM. All types of denture base resin showed color changes after 1 and 8 weeks immersion. However, there was no significant difference between denture base resins. All specimens showed significant color changes in the coffee than green tee. In water sorption test, thermoplastic acrylic resin showed lower values than conventional heat-polymerized acrylic resin and thermoplastic polyamide resin. Three types of denture base showed low cytotoxicity in cell viability assay. Thermoplastic acrylic resin showed the similar cell attachment but more stable attachment than conventional heat-polymerized acrylic resin. Thermoplastic acrylic resin for the non-metal clasp denture showed acceptable color stability, water sorption and cytotoxicity. To verify the long stability in the mouth, additional in vitro studies are needed.

  4. Thermal stability increase in metallic nanoparticles-loaded cellulose nanocrystal nanocomposites.

    PubMed

    Goikuria, U; Larrañaga, A; Vilas, J L; Lizundia, E

    2017-09-01

    Due to the potential of CNC-based flexible materials for novel industrial applications, the aim of this work is to improve the thermal stability of cellulose nanocrystals (CNC) films through a straightforward and scalable method. Based of nanocomposite approach, five different metallic nanoparticles (ZnO, SiO2, TiO2, Al2O3 and Fe2O3) have been co-assembled in water with CNCs to obtain free-standing nanocomposite films. Thermogravimetric analysis (TGA) reveals an increased thermal stability upon nanoparticle. This increase in the thermal stability reaches a maximum of 75°C for the nanocomposites having 10wt% of Fe2O3 and ZnO. The activation energies of thermodegradation process (Ea) determined according to Kissinger and Ozawa-Flynn-Wall methods further confirm the delayed degradation of CNC nanocomposites upon heating. Finally, the changes induced in the crystalline structure during thermodegradation were followed by wide angle X-ray diffraction (WAXD). It is also observed that thermal degradation proceeds at higher temperatures for nanocomposites having metallic nanoparticles. Overall, experimental findings here showed make nanocomposite approach a simple low-cost environmentally-friendly strategy to overcome the relatively poor thermal stability of CNCs when extracted via sulfuric acid assisted hydrolysis of cellulose. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Evaluation of the tool life and fracture toughness of cutting tools boronized by the paste boriding process

    NASA Astrophysics Data System (ADS)

    Campos, I.; Farah, M.; López, N.; Bermúdez, G.; Rodríguez, G.; VillaVelázquez, C.

    2008-03-01

    The present study evaluates the tool life and the fracture toughness of AISI M2 steel cutting tools boronized by the paste boriding process. The treatment was done in selective form on the tool tips of the steels. The temperatures were set at 1173 and 1273 K with 4 h of exposure time and modifying the boron carbide paste thicknesses in 3 and 4 mm. Microindentation fracture toughness method was used on the borided tool at the temperature of 1273 K and a 4 mm paste thickness, with a 100 g load at different distances from the surface. Also, the borided cutting tools were worn by the turning process that implied the machining of AISI 1018 steel increasing the nominal cutting speed, of 55 m/min, in 10 and 25% and maintaining the feed and the depth cut constants. The tool life was evaluated by the Taylor's equation that shows the dependence of the experimental parameters of the boriding process.

  6. Stabilization of heavy metals in MSWI fly ash using silica fume

    SciTech Connect

    Li, Xinying; Chen, Quanyuan; Zhou, Yasu; Tyrer, Mark; Yu, Yang

    2014-12-15

    Highlights: • The stabilization of heavy metals in MSWI fly ash was investigated. • The addition of silica fume effectively reduced the leaching of Pb and Cd. • The relation of solid phase transformation and leaching behavior of heavy metals was discussed. - Abstract: The objective of this work was to investigate the feasibility and effectiveness of silica fume on stabilizing heavy metals in municipal solid waste incineration (MSWI) fly ash. In addition to compressive strength measurements, hydrated pastes were characterized by X-ray diffraction (XRD), thermal-analyses (DTA/TG), and MAS NMR ({sup 27}Al and {sup 29}Si) techniques. It was found that silica fume additions could effectively reduce the leaching of toxic heavy metals. At the addition of 20% silica fume, leaching concentrations for Cu, Pb and Zn of the hydrated paste cured for 7 days decreased from 0.32 mg/L to 0.05 mg/L, 40.99 mg/L to 4.40 mg/L, and 6.96 mg/L to 0.21 mg/L compared with the MSWI fly ash. After curing for 135 days, Cd and Pb in the leachates were not detected, while Cu and Zn concentrations decreased to 0.02 mg/L and 0.03 mg/L. The speciation of Pb and Cd by the modified version of the European Community Bureau of Reference (BCR) extractions showed that these metals converted into more stable state in hydrated pastes of MSWI fly ash in the presence of silica fume. Although exchangeable and weak-acid soluble fractions of Cu and Zn increased with hydration time, silica fume addition of 10% can satisfy the requirement of detoxification for heavy metals investigated in terms of the identification standard of hazardous waste of China.

  7. Theoretical confirmation of Ga-stabilized anti-ferromagnetism in plutonium metal

    NASA Astrophysics Data System (ADS)

    Söderlind, Per; Landa, Alex

    2014-05-01

    Density functional theory (DFT) for plutonium metal is shown to be consistent with recent magnetic measurements that suggest anti-ferromagnetism in Pu-Ga alloys at low temperatures. The theoretical model predicts a stabilization of the face-centered-cubic (fcc, δ) form of plutonium in an anti-ferromagnetic configuration when alloyed with gallium. The ordered magnetic phase occurs because Ga removes the mechanical instability that exists for unalloyed δ-Pu. The cause of the Ga-induced stabilization is a combination of a lowering of the band (kinetic) and electrostatic (Coulomb) energies for the cubic relative to the tetragonal phase. Similarly, gallium plays an important role in stabilizing anti-ferromagnetism in the tetragonal P4/mmm Pu3Ga compound.

  8. Stability evaluation of short-circuiting gas metal arc welding based on ensemble empirical mode decomposition

    NASA Astrophysics Data System (ADS)

    Huang, Yong; Wang, Kehong; Zhou, Zhilan; Zhou, Xiaoxiao; Fang, Jimi

    2017-03-01

    The arc of gas metal arc welding (GMAW) contains abundant information about its stability and droplet transition, which can be effectively characterized by extracting the arc electrical signals. In this study, ensemble empirical mode decomposition (EEMD) was used to evaluate the stability of electrical current signals. The welding electrical signals were first decomposed by EEMD, and then transformed to a Hilbert–Huang spectrum and a marginal spectrum. The marginal spectrum is an approximate distribution of amplitude with frequency of signals, and can be described by a marginal index. Analysis of various welding process parameters showed that the marginal index of current signals increased when the welding process was more stable, and vice versa. Thus EEMD combined with the marginal index can effectively uncover the stability and droplet transition of GMAW.

  9. A structural model for surface-enhanced stabilization in some metallic glass formers

    NASA Astrophysics Data System (ADS)

    Levchenko, Elena V.; Evteev, Alexander V.; Yavari, Alain R.; Louzguine-Luzgin, Dmitri V.; Belova, Irina V.; Murch, Graeme E.

    2013-01-01

    A structural model for surface-enhanced stabilization in some metallic glass formers is proposed. In this model, the alloy surface structure is represented by five-layer Kagomé-net-based lateral ordering. Such surface structure has intrinsic abilities to stabilize icosahedral-like short-range order in the bulk, acting as 'a cloak of liquidity'. In particular, recent experimental observations of surface-induced lateral ordering and a very high glass forming ability of the liquid alloy Au49Ag5.5Pd2.3Cu26.9Si16.3 can be united using this structural model. This model may be useful for the interpretation of surface structure of other liquid alloys with a high glass forming ability. In addition, it suggests the possibility of guiding the design of the surface coating of solid containers for the stabilization of undercooled liquids.

  10. A kinetic model for estimating the boron activation energies in the FeB and Fe2B layers during the gas-boriding of Armco iron: Effect of boride incubation times

    NASA Astrophysics Data System (ADS)

    Keddam, M.; Kulka, M.; Makuch, N.; Pertek, A.; Małdziński, L.

    2014-04-01

    The present work deals with a simulation of the growth kinetics of boride layers grown on Armco iron substrate. The formed boride layers (FeB + Fe2B) are obtained by the gas-boriding in the temperature range of 1073-1273 K during a time duration ranging from 80 to 240 min. The used approach solves the mass balance equations at the two growing fronts: (FeB/Fe2B) and (Fe2B/Fe) under certain assumptions. To consider the effect of the incubation times for the borides formation, the temperature-dependent function Φ(T) was incorporated in the model. The following input data: (the boriding temperature, the treatment time, the upper and lower values of boron concentrations in FeB and Fe2B and the experimental parabolic growth constants) are needed to determine the boron activation energies in the FeB and Fe2B layers. The obtained values of boron activation energies were then compared with the values available in the literature. Finally, a good agreement was obtained between the simulated values of boride layers thicknesses and the experimental ones in the temperature range of 1073-1273 K.

  11. Enhancement stabilization of heavy metals (Zn, Pb, Cr and Cu) during vermifiltration of liquid-state sludge.

    PubMed

    Yang, Jian; Zhao, Chunhui; Xing, Meiyan; Lin, Yanan

    2013-10-01

    This paper illustrated the potential effect of earthworms on heavy metal stabilization after vermifiltration of liquid-state sludge. Significant enhancement of organics degradation in sludge caused an increase of heavy metal concentrations in VF effluent sludge. However, the analysis of heavy metal chemical speciation indicated earthworms made unstable fractions of heavy metals transformed into stable fractions. Further investigation using principal component analysis revealed that transformations of heavy metal fractions were mainly due to the changes in sludge physico-chemical properties of pH, soluble chemical oxygen demand and available phosphorus. The bioassay of earthworms indicated that only zinc was accumulated by earthworms because the unstable fraction was its main chemical speciation. Furthermore, risk analysis demonstrated that earthworm activities weakened heavy metal risk due to the formation of stable fractions although their total concentrations increased. These results indicated that earthworms in vermifilter had a positive role in stabilizing heavy metals in sewage sludge. Copyright © 2013 Elsevier Ltd. All rights reserved.

  12. [Surgical stabilization of multiple rib fractures successfully achieved with the use of long metalic plates].

    PubMed

    Tanaka, A; Sato, T; Osawa, H; Koyanagi, T; Maekawa, K; Watanabe, N; Nakase, A; Sakata, J; Kamada, K

    1998-05-01

    Surgical stabilization of multiple rib fractures in 5 male patients was successfully achieved with the use of orthopedic A-O metalic plates, which are called reconstruction plates. In each patient, we prevented deformity of the rib cage and flail chest which frequently occurs after multiple rib fractures. Three of these patients received emergency operations because of severe hemopneumothorax and flail chest due to crushing injuries to the chest. They were treated by the standard thoracotomy, hemostasis of intrapleural bleeding, and stabilization of fractured ribs with reconstruction plates, in addition two of the patients underwent a single lobectomy to control the pulmonary hemorrhage. Another two patients were treated with mechanical ventilation and closed-tube thoracotomy following the chest trauma because their thoracic bleeding from drainage tubes was tolerable. But flail chest and respiratory insufficiency did not improve, in spite of positive controlled ventilation as a mode of internal pneumatic stabilization. Then surgical stabilization of the fractured ribs with these plates was carried out ten to twelve days after the accidents in each case. All patients tolerated the surgical procedures well and were successfully removed from the respirator, demonstrating complete stability of the chest wall. The long metal reconstruction plates with many perforations were very useful for the external fixation of segmentary fractured ribs as an external brace. This was because they were long enough to cover the whole length of the fractured ribs and moderately soft enough to be appropriately bent or twisted by hand at the time of operation. Moreover a number of holes in it allowed the suture to pass through the plate and rib, avoiding displacement of the prosthesis. This is the first report which describes the usefulness of orthopedic reconstruction plates for the stabilization of multiple rib fractures.

  13. Protective metal matrix coating with nanocomponents

    NASA Astrophysics Data System (ADS)

    Galevsky, G. V.; Rudneva, V. V.; Cherepanov, A. N.; Galevsky, S. G.; Efimova, K. A.

    2016-09-01

    Experience of nanocrystalline chromium, titanium, silicon carbides and borides components application as nickel, zinc, chromium based electrodeposited composite coating is generalized. Electrodepositing conditions are determined. Structure and physicochemical properties of coatings, namely micro-hardness, adhesion to steel base, inherent stresses, heat resistance, corrosion currents, en-during quality, and their change during isothermal annealing are studied. As is shown, nanocomponents act as metal matrix modifier. Technological and economic feasibility study to evaluate expediency of replacing high priced nano-diamonds with nanocrystalline borides and carbides is undertaken.

  14. Improving the Adhesion Resistance of the Boride Coatings to AISI 316L Steel Substrate by Diffusion Annealing

    NASA Astrophysics Data System (ADS)

    Campos-Silva, I.; Bernabé-Molina, S.; Bravo-Bárcenas, D.; Martínez-Trinidad, J.; Rodríguez-Castro, G.; Meneses-Amador, A.

    2016-09-01

    In this study, new results about the practical adhesion resistance of boride coating/substrate system formed at the surface of AISI 316 L steel and improved by means of a diffusion annealing process are presented. First, the boriding of AISI 316 L steel was performed by the powder-pack method at 1173 K with different exposure times (4-8 h). The diffusion annealing process was conducted on the borided steels at 1273 K with 2 h of exposure using a diluent atmosphere of boron powder mixture. The mechanical behavior of the boride coating/substrate system developed by both treatments was established using Vickers and Berkovich tests along the depth of the boride coatings, respectively. Finally, for the entire set of experimental conditions, the scratch tests were performed with a continuously increasing normal force, in which the practical adhesion resistance of the boride coating/substrate system was represented by the critical load. The failure mechanisms developed over the surface of the scratch tracks were analyzed; the FeB-Fe2B/substrate system exhibited an adhesive mode, while the Fe2B/substrate system obtained by the diffusion annealing process showed predominantly a cohesive failure mode.

  15. Synthesis, morphological control, dispersion stabilization and in situ self-assembly of noble metal nanostructures using multidentate resorcinarene surfactants

    NASA Astrophysics Data System (ADS)

    Han, Sangbum

    In this dissertation, a detailed investigation on the influence of various macrocyclic resorcinarene surfactants in determining the morphology, stabilization and self-assembly of mono- and bi- metallic nanoparticles was undertaken. (Abstract shortened by ProQuest.).

  16. Fractionation of heavy metals in sludge from anaerobic wastewater stabilization ponds in southern Spain

    SciTech Connect

    Alonso, E.

    2006-07-01

    The analysis of heavy metals is a very important task to assess the potential environmental and health risk associated with the sludge coming from wastewater treatment plants (WWTPs). However, it is necessary to apply sequential extraction techniques to obtain suitable information about their bioavailability or toxicity. In this paper, a sequential extraction scheme according to the Standard, Measurements and Testing Programme of the European Commission was applied to sludge samples collected from ten anaerobic wastewater stabilization ponds (WSPs) located in southern Spain. Al, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Ti and Zn were determined in the sludge extracts by inductively coupled plasma atomic emission spectrometry. In relation to current international legislation for the use of sludge for agricultural purposes, none of the metal concentrations exceeded maximum permitted levels. Overall, heavy metals were mainly associated with the two less-available fractions (34% oxidizable metal and 55% residual metal). Only Mn and Zn showed the highest share of the available (exchangeable and reducible) fractions (25-48%)

  17. Research on the stability of heavy metals (Cu, Zn) in excess sludge with the pretreatment of thermal hydrolysis.

    PubMed

    Wu, Huimin; Li, Meng; Zhang, Lei; Sheng, Chao

    2016-01-01

    Thermal hydrolysis (TH) has been used to improve anaerobic digestion performance as well as the stability of heavy metals in sludge. Because the toxicity of heavy metals is closely related to both the concentration and the chemical speciation, more exhaustive studies on speciation distribution are urgently needed. This research aimed to investigate the effects of TH treatment (especially the time and temperature) on the concentration and stability of heavy metals in sludge, and to define the optimal TH conditions. The TH experiment indicated that the content of the stable form of Cu and Zn reached 83% and 47.4%, respectively, with TH at 210°C and 30 min. Compared with the raw sludge, the proportion of Cu and Zn increased by 11.88% and 7.3%, respectively. Results indicated that the heavy metals were combined with sludge in a more stable form with the pretreatment of TH, which improved the stability of heavy metals.

  18. Formation and stabilization of anionic metal complexes in concentrated aqueous quaternary ammonium salt solutions

    SciTech Connect

    Aronson, F.L.; Hwang, L.L.Y.; Ronca, N.; Solomon, N.A.; Steigman, J.

    1985-02-04

    Anionic complexes of transition metals were stabilized in aqueous solutions containing high concentrations of various short-chain quaternary ammonium salts. Compounds with longer paraffin chains were effective in much less concentrated solution. Complex ions were detected spectrophotometrically. FeCl/sub 4//sup -/, which is usually formed in concentrated HCl, was the predominant Fe(III) complex in 30 m choline chloride containing only 0.12 M HCl. A yellow transitory Tc(VII) chloro-addition intermediate, formed in the reduction of TcO/sub 4//sup -/ by concentrated HCl, was stabilized when the solution also contained 25 m choline chloride. Its spectrum, as well as the isolation of an already known Tc(VII) bipyridyl complex, is reported. Concentrated organic electrolytes also stabilized Tc(V) oxide halides against disproportionation and Tc(IV) hexahalides against hydrolysis. Halochromates of Cr(VI) were formed and stabilized in dilute acid containing quaternary ammonium salts. Their UV spectra showed the well-resolved vibronic fine structure associated with the symmetric chromium-to-oxygen charge-transfer band. It is known that these progressions are resolved in aprotic solvents, but not in aqueous acidic solution alone, and that the loss of fine structure in aqueous media is due to hydrogen bonding. The stabilization of anionic metal complexes and the resolution of vibronic structure in halochromates are probably consequences of water-structure-enforced ion paring. The present work suggests that the water molecules in immediate contact with the complex anions are more strongly hydrogen bonded to each other than to the complex. 21 references, 4 figures.

  19. Effect of Transition Metal Cations on Stability Enhancement for Molybdate-Based Hybrid Supercapacitor.

    PubMed

    Watcharatharapong, Teeraphat; Minakshi Sundaram, Manickam; Chakraborty, Sudip; Li, Dan; Shafiullah, G M; Aughterson, Robert D; Ahuja, Rajeev

    2017-05-31

    The race for better electrochemical energy storage systems has prompted examination of the stability in the molybdate framework (MMoO4; M = Mn, Co, or Ni) based on a range of transition metal cations from both computational and experimental approaches. Molybdate materials synthesized with controlled nanoscale morphologies (such as nanorods, agglomerated nanostructures, and nanoneedles for Mn, Co, and Ni elements, respectively) have been used as a cathode in hybrid energy storage systems. The computational and experimental data confirms that the MnMoO4 crystallized in β-form with α-MnMoO4 type whereas Co and Ni cations crystallized in α-form with α-CoMoO4 type structure. Among the various transition metal cations studied, hybrid device comprising NiMoO4 vs activated carbon exhibited excellent electrochemical performance having the specific capacitance 82 F g(-1) at a current density of 0.1 A g(-1) but the cycling stability needed to be significantly improved. The specific capacitance of the NiMoO4 electrode material is shown to be directly related to the surface area of the electrode/electrolyte interface, but the CoMoO4 and MnMoO4 favored a bulk formation that could be suitable for structural stability. The useful insights from the electronic structure analysis and effective mass have been provided to demonstrate the role of cations in the molybdate structure and its influence in electrochemical energy storage. With improved cycling stability, NiMoO4 can be suitable for renewable energy storage. Overall, this study will enable the development of next generation molybdate materials with multiple cation substitution resulting in better cycling stability and higher specific capacitance.

  20. Properties of particle phases for metal-matrix-composite design.

    PubMed

    Baron, C; Springer, H

    2017-06-01

    Successful metallurgical design of metal-matrix-composites relies on the knowledge of the intrinsic property profiles of the metal matrix and especially the compounds employed for particles, whiskers or fibres. In this work we compiled the key properties melting point, bulk modulus, shear modulus, Young׳s modulus, density, hardness, Poisson׳s ratio and structure/space group from the widespread literature data for the most relevant compound types, i.e. borides, carbo-borides, carbides, oxides, nitrides and intermetallic phases.

  1. Heavy metal bioleaching and sludge stabilization in a single-stage reactor using indigenous acidophilic heterotrophs.

    PubMed

    Mehrotra, Akanksha; Sreekrishnan, T R

    2017-01-10

    Simultaneous sludge digestion and metal leaching (SSDML) have been reported at mesophilic temperature. It is generally perceived that while sludge stabilization is effected by heterotrophs at neutral pH, metal bioleaching is done by acidophilic autotrophs. However, little information is available on the microbial communities involved in the process. This study carried out SSDML in a single-stage reactor using sludge indigenous microorganisms and looked at the bacterial communities responsible for the process. Volatile suspended solids were reduced by more than 40%. The concentration of zinc, copper, chromium, cadmium and nickel decreased by more than 45% in the dry sludge. Acidophilic species of Alicyclobacillus genus were the dominant heterotrophs. A few heterotrophic bacteria were detected which can oxidize iron (Alicyclobacillus ferrooxydans, Alicyclobacillus ferripilum and Ferrimicrobium acidiphilum). Acidithiobacillus ferrooxidans (autotroph) was responsible for the oxidation of both iron and sulfur which lead to a change in the pH from neutral to acidic. The presence of acidophilic heterotrophs, which can oxidize either iron or sulfur, enhanced the efficiency of SSDML process with respect to sludge stabilization and metal leaching. This study shows that it is possible to carry out the SSDML in a single-stage reactor with indigenous microorganisms.

  2. Coinage Metal Superatomic Cores: Insights into Their Intrinsic Stability and Optical Properties from Relativistic DFT Calculations.

    PubMed

    Gam, Franck; Paez-Hernandez, Dayan; Arratia-Perez, Ramiro; Liu, C W; Kahlal, Samia; Saillard, Jean-Yves; Muñoz-Castro, Alvaro

    2017-08-22

    Coinage-metal atomically precise nanoclusters are made of a well-defined metallic core embedded in a ligand-protecting outer shell. Whereas gold derivatives are particularly well documented, examples of silver nanoclusters are somewhat limited and copper species remain particularly scare. Our DFT relativistic calculations on superatomic metallic cores indicate that copper species are almost as stable as gold clusters and more stable than their silver counterparts. Thus, for silver superatomic cores, the role of the stabilizing ligands is more crucial in the stabilization of the overall structure, in comparison to copper and gold. Hence, the chemistry of the earlier counterparts of gold, especially copper, should grow quickly with at least characterizations of species related to that found in the heavier elements in the triad, which requires tackling synthetic challenges. Time-dependent (TD)-DFT calculations show that with an increase of the cluster core nuclearity, the absorption bands are redshifted, allowing us to differentiate between the clusters types. Moreover, the optical properties of the silver cores are fairly different from that of their Cu and Au relatives. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Recovery of heavy metals and stabilization of spent hydrotreating catalyst using a glass-ceramic matrix.

    PubMed

    Sun, D D; Tay, J H; Cheong, H K; Leung, D L; Qian, G

    2001-10-12

    Chemical analysis of spent Co/Mo/gamma Al(2)O(3) catalyst revealed the presence of carbon, molybdenum, sulfur, vanadium and cobalt at levels of 16.0, 10.9, 7.3, 4.6 and 4.0 wt.%, respectively. It was found that calcination at 500 degrees C provides an effective solution for the removal of carbon and sulfur and this generates the oxide form of the heavy metals. The removal of these heavy metals can be achieved through a two-stage leaching process. During the first stage, in which concentrated ammonia is used and it has been found that this process can be successful in removing as much as 83% (w/v) Mo. In a second stage, it was found that using 10% (v/v) of sulfuric acid, it was possible to account for up to 77% (w/v) Co and 4% (w/v) Mo removal. Leaching test results indicated that the vanadium present in the heated spent catalyst was almost stabilized but the molybdenum and cobalt were not. The combination of two solid wastes, ladle furnace slag (LFS) and treated residue of spent catalyst, could be used for making a high value-added anorthite glass-ceramic materials. Further leaching tests showed that ceramic glass materials provided a very effective method of Co, Mo and V heavy metals stabilization resulting in a product with a possible commercial value.

  4. Isolated metal active site concentration and stability control catalytic CO2 reduction selectivity.

    PubMed

    Matsubu, John C; Yang, Vanessa N; Christopher, Phillip

    2015-03-04

    CO2 reduction by H2 on heterogeneous catalysts is an important class of reactions that has been studied for decades. However, atomic scale details of structure-function relationships are still poorly understood. Particularly, it has been suggested that metal particle size plays a unique role in controlling the stability of CO2 hydrogenation catalysts and the distribution of active sites, which dictates reactivity and selectivity. These studies often have not considered the possible role of isolated metal active sites in the observed dependences. Here, we utilize probe molecule diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) with known site-specific extinction coefficients to quantify the fraction of Rh sites residing as atomically dispersed isolated sites (Rhiso), as well as Rh sites on the surface of Rh nanoparticles (RhNP) for a series of TiO2 supported Rh catalysts. Strong correlations were observed between the catalytic reverse water gas shift turn over frequency (TOF) and the fraction of Rhiso sites and between catalytic methanation TOF and the fraction of RhNP sites. Furthermore, it was observed that reaction condition-induced disintegration of Rh nanoparticles, forming Rhiso active sites, controls the changing reactivity with time on stream. This work demonstrates that isolated atoms and nanoparticles of the same metal on the same support can exhibit uniquely different catalytic selectivity in competing parallel reaction pathways and that disintegration of nanoparticles under reaction conditions can play a significant role in controlling stability.

  5. Characterization of the dimensional stability of advanced metallic materials using an optical test bench structure

    NASA Technical Reports Server (NTRS)

    Hsieh, Cheng; O'Donnell, Timothy P.

    1991-01-01

    The dimensional stability of low-density high specific-strength metal-matrix composites (including 30 vol pct SiC(p)/SXA 24-T6 Al, 25 vol pct SiC(p)/6061-T6 Al, 40 vol pct graphite P100 fiber/6061 Al, 50 vol pct graphite P100 fiber/6061 Al, and 40 vol pct P100 graphite fiber/AZ91D Mg composites) and an Al-Li-Mg metal alloy was evaluated using a specially designed five-strut optical test bench structure. The structure had 30 thermocouple locations, one retroreflector, one linear interferometer multilayer insulation, and various strip heaters. It was placed in a 10 exp -7 torr capability vacuum chamber with a laser head positioned at a window port, and a laser interferometer system for collecting dimensional change data. It was found that composite materials have greater 40-C temporal dimensional stability than the AL-Li-Mg alloy. Aluminum-based composites demonstrated better 40-C temporal stability than Mg-based composites.

  6. Insight from first principles into the stability and magnetism of alkali-metal superoxide nanoclusters

    NASA Astrophysics Data System (ADS)

    Arcelus, Oier; Suaud, Nicolas; Katcho, Nebil A.; Carrasco, Javier

    2017-05-01

    Alkali-metal superoxides are gaining increasing interest as 2p magnetic materials for information and energy storage. Despite significant research efforts on bulk materials, gaps in our knowledge of the electronic and magnetic properties at the nanoscale still remain. Here, we focused on the role that structural details play in determining stability, electronic structure, and magnetic couplings of (MO2)n (M = Li, Na, and K, with n = 2-8) clusters. Using first-principles density functional theory based on the Perdew-Burke-Ernzerhof and Heyd-Scuseria-Ernzerhof functionals, we examined the effect of atomic structure on the relative stability of different polymorphs within each investigated cluster size. We found that small clusters prefer to form planar-ring structures, whereas non-planar geometries become more stable when increasing the cluster size. However, the crossover point depends on the nature of the alkali metal. Our analysis revealed that electrostatic interactions govern the highly ionic M-O2 bonding and ultimately control the relative stability between 2-D and 3-D geometries. In addition, we analyzed the weak magnetic couplings between superoxide molecules in (NaO2)4 clusters comparing model Hamiltonian methods based on Wannier function projections onto πg states with wave function-based multi-reference calculations.

  7. Effects of the Electronic Doping In the Stability of the Metal Hydride NaH

    NASA Astrophysics Data System (ADS)

    Olea-Amezcua, Monica-Araceli; Rivas-Silva, Juan-Francisco; de La Peña-Seaman, Omar; Heid, Rolf; Bohnen, Klaus-Peter

    2015-03-01

    Despite metal hydrides light weight and high hydrogen volumetric densities, the Hydrogen desorption process requires excessively high temperatures due to their high stability. Attempts for improvement the hydrogenation properties have been focus on the introduction of defects, impurities and doping on the metal hydride. We present a systematic study of the electronic doping effects on the stability of a model system, NaH doped with magnesium, forming the alloying system Na1-xMgxH. We use the density functional theory (DFT) and the self-consistent version of the virtual crystal approximation (VCA) to model the doping of NaH with Mg. The evolution of the ground state structural and electronic properties is analyzed as a function of Mg-content. The full-phonon dispersion, calculated by the linear response theory (LRT) and density functional perturbation theory (DFPT), is analyzed for several Mg-concentrations, paying special attention to the crystal stability and the correlations with the electronic structure. Applying the quasiharmonic approximation (QHA), the free energy from zero-point motion is obtained, and its influence on the properties under study is analyzed. This work is partially supported by the VIEP-BUAP (OMPS-EXC14-I) and CONACYT-Mexico (No. 221807) projects.

  8. Stability of alkali-metal hydrides: effects of n-type doping

    NASA Astrophysics Data System (ADS)

    Olea Amezcua, Monica Araceli; de La Peña Seaman, Omar; Rivas Silva, Juan Francisco; Heid, Rolf; Bohnen, Klaus-Peter

    Metal hydrides could be considered ideal solid-state hydrogen storage systems, they have light weight and high hydrogen volumetric densities, but the hydrogen desorption process requires excessively high temperatures due to their high stability. Efforts have been performed to improve their dehydrogenation properties, based on the introduction of defects, impurities and doping. We present a systematic study of the n-type (electronic) doping effects on the stability of two alkali-metal hydrides: Na1-xMgxH and Li1-xBexH. These systems have been studied within the framework of density functional perturbation theory, using a mixed-basis pseudopotential method and the self-consistent version of the virtual crystal approximation to model the doping. The full-phonon dispersions are analyzed for several doping content, paying special attention to the crystal stability. It is found a doping content threshold for each system, where they are close to dynamical instabilities, which are related to charge redistribution in interstitial zones. Applying the quasiharmonic approximation, the vibrational free energy, the linear thermal expansion and heat capacities are obtained for both hydrides systems and are analyzed as a function of the doping content. This work is partially supported by the VIEP-BUAP 2016 and CONACYT-México (No.221807) projects.

  9. Low-cost industrially available molybdenum boride and carbide as "platinum-like" catalysts for the hydrogen evolution reaction in biphasic liquid systems.

    PubMed

    Scanlon, Micheál D; Bian, Xiaojun; Vrubel, Heron; Amstutz, Véronique; Schenk, Kurt; Hu, Xile; Liu, BaoHong; Girault, Hubert H

    2013-02-28

    Rarely reported low-cost molybdenum boride and carbide microparticles, both of which are available in abundant quantities due to their widespread use in industry, adsorb at aqueous acid-1,2-dichloroethane interfaces and efficiently catalyse the hydrogen evolution reaction in the presence of the organic electron donor - decamethylferrocene. Kinetic studies monitoring biphasic reactions by UV/vis spectroscopy, and further evidence provided by gas chromatography, highlight (a) their superior rates of catalysis relative to other industrially significant transition metal carbides and silicides, as well as a main group refractory compound, and (b) their highly comparable rates of catalysis to Pt microparticles of similar dimensions. Insight into the catalytic processes occurring for each adsorbed microparticle was obtained by voltammetry at the liquid-liquid interface.

  10. MINE WASTE TECHNOLOGY PROGRAM; PHOSPHATE STABILIZATION OF HEAVY METALS CONTAMINATED MINE WASTE YARD SOILS, JOPLIN, MISSOURI NPL SITE

    EPA Science Inventory

    This document summarizes the results of Mine Waste Technology Project 22-Phosphate Stabilization of Heavy Metals-Contaminated Mine Waste Yard Soils. Mining, milling, and smelting of ores near Joplin, Missouri, have resulted in heavy metal contamination of the area. The Joplin s...

  11. MINE WASTE TECHNOLOGY PROGRAM; PHOSPHATE STABILIZATION OF HEAVY METALS CONTAMINATED MINE WASTE YARD SOILS, JOPLIN, MISSOURI NPL SITE

    EPA Science Inventory

    This document summarizes the results of Mine Waste Technology Project 22-Phosphate Stabilization of Heavy Metals-Contaminated Mine Waste Yard Soils. Mining, milling, and smelting of ores near Joplin, Missouri, have resulted in heavy metal contamination of the area. The Joplin s...

  12. Effect of refining treatment on the diffusion saturation of refractory metals with boron and silicon

    SciTech Connect

    Dzyadykevich, Y.V.

    1995-06-01

    Earlier studies showed that annealing of refractory metals in a getter mixture ensures removal of interstitial impurities from the interior of the metal, thus enhancing its plasticity. Therefore, it is interesting to study the effect of this refining treatment on the formation of boride and silicide coatings on refractory metals (niobium, tantalum, molybdenum, and tungsten).

  13. Adsorption of micelle-forming surfactants from aqueous solutions on disperse titanium boride

    SciTech Connect

    Grodskii, A.S.; Komleva, E.A.; Frolov, Yu.G.

    1988-08-10

    Adsorption studies showed that nonionogenic and cationic surfactants are adsorbed on the surface of disperse titanium boride. Anionic surfactants are virtually not adsorbed due to the negative charge of the particles. It was found that in the region of low concentrations of surfactants in the solution, adsorption of Sintanols takes place in lyophobic regions and the surface of the particles becomes hydrophilic. The Sintamid molecules are adsorbed on the entire interface, including both hydrophobic and hydrophilic sections, with subsequent formation of bimolecular layers by adsorption on hydrophobic sections. Catamine-AB is adsorbed on hydrophilic sections of the surface also with the formation of bimolecular layers. Developed polymolecular layers up to 10-15 nm thick are formed on titanium boride particles from micellar solutions of nonionigenic and cationic surfactants.

  14. Boriding 5khNM hot-working dies in coatings

    SciTech Connect

    Luk'yanov, V.P.; Mitrokhovich, N.N.; Polovnikov, V.M.

    1983-03-01

    The life of the forging die determines the effectiveness of close died forging methods. Boron impregnation expands the life of the die. Tests were run on boriding pastes where boron carbide is the supplier of active boron and cryolite the binder and activator. High cryolite results in the highest boron impregnation activity but must be kept in ratio to the boron. The establishment of the chemical mechanism of the paste discovers 3-5 sodium flouride along with cryolite and boron, from which an optimum composition at 860 C for 4h. is determined. The optimum thickness of the layer should be 3-5mm, less not being thick enough, more causing runoff and oxidation. Steel impregnated with boron paste was then tested for erosion, with good results. Boriding in the coating of forging dies, now in use at the Lepse South Kama Plant, is recommended.

  15. Friction and wear of radiofrequency-sputtered borides, silicides, and carbides

    NASA Technical Reports Server (NTRS)

    Brainard, W. A.; Wheeler, D. R.

    1978-01-01

    The friction and wear properties of several refractory compound coatings were examined. These compounds were applied to 440 C bearing steel surfaces by radiofrequency (RF) sputtering. The refractory compounds were the titanium and molybdenum borides, the titanium and molybdenum silicides, and the titanium, molybdenum, and boron carbides. Friction testing was done with a pin-on-disk wear apparatus at loads from 0.1 to 5.0 newtons. Generally, the best wear properties were obtained when the coatings were bias sputtered onto 440 C disks that had been preoxidized. Adherence was improved because of the better bonding of the coatings to the iron oxide formed during preoxidation. As a class the carbides provided wear protection to the highest loads. Titanium boride coatings provided low friction and good wear properties to moderate loads.

  16. 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.

  17. High thermal stability and sluggish crystallization kinetics of high-entropy bulk metallic glasses

    NASA Astrophysics Data System (ADS)

    Yang, M.; Liu, X. J.; Ruan, H. H.; Wu, Y.; Wang, H.; Lu, Z. P.

    2016-06-01

    Metallic glasses are metastable and their thermal stability is critical for practical applications, particularly at elevated temperatures. The conventional bulk metallic glasses (BMGs), though exhibiting high glass-forming ability (GFA), crystallize quickly when being heated to a temperature higher than their glass transition temperature. This problem may potentially be alleviated due to the recent developments of high-entropy (or multi-principle-element) bulk metallic glasses (HE-BMGs). In this work, we demonstrate that typical HE-BMGs, i.e., ZrTiHfCuNiBe and ZrTiCuNiBe, have higher kinetic stability, as compared with the benchmark glass Vitreoy1 (Zr41.2Ti13.8Cu12.5Ni10Be22.5) with a similar chemical composition. The measured activation energy for glass transition and crystallization of the HE-BMGs is nearly twice that of Vitreloy 1. Moreover, the sluggish crystallization region ΔTpl-pf, defined as the temperature span between the last exothermic crystallization peak temperature Tpl and the first crystallization exothermic peak temperature Tpf, of all the HE-BMGs is much wider than that of Vitreloy 1. In addition, high-resolution transmission electron microscopy characterization of the crystallized products at different temperatures and the continuous heating transformation diagram which is proposed to estimate the lifetime at any temperature below the melting point further confirm high thermal stability of the HE-BMGs. Surprisingly, all the HE-BMGs show a small fragility value, which contradicts with their low GFA, suggesting that the underlying diffusion mechanism in the liquid and the solid of HE-BMGs is different.

  18. High thermal stability and sluggish crystallization kinetics of high-entropy bulk metallic glasses

    SciTech Connect

    Yang, M.; Liu, X. J.; Wu, Y.; Wang, H.; Lu, Z. P.; Ruan, H. H.

    2016-06-28

    Metallic glasses are metastable and their thermal stability is critical for practical applications, particularly at elevated temperatures. The conventional bulk metallic glasses (BMGs), though exhibiting high glass-forming ability (GFA), crystallize quickly when being heated to a temperature higher than their glass transition temperature. This problem may potentially be alleviated due to the recent developments of high-entropy (or multi-principle-element) bulk metallic glasses (HE-BMGs). In this work, we demonstrate that typical HE-BMGs, i.e., ZrTiHfCuNiBe and ZrTiCuNiBe, have higher kinetic stability, as compared with the benchmark glass Vitreoy1 (Zr{sub 41.2}Ti{sub 13.8}Cu{sub 12.5}Ni{sub 10}Be{sub 22.5}) with a similar chemical composition. The measured activation energy for glass transition and crystallization of the HE-BMGs is nearly twice that of Vitreloy 1. Moreover, the sluggish crystallization region ΔT{sub pl-pf}, defined as the temperature span between the last exothermic crystallization peak temperature T{sub pl} and the first crystallization exothermic peak temperature T{sub pf}, of all the HE-BMGs is much wider than that of Vitreloy 1. In addition, high-resolution transmission electron microscopy characterization of the crystallized products at different temperatures and the continuous heating transformation diagram which is proposed to estimate the lifetime at any temperature below the melting point further confirm high thermal stability of the HE-BMGs. Surprisingly, all the HE-BMGs show a small fragility value, which contradicts with their low GFA, suggesting that the underlying diffusion mechanism in the liquid and the solid of HE-BMGs is different.

  19. 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

    2017-06-01

    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.

  20. Dynamics and thermal stability of surface-confined metal-organic chains

    NASA Astrophysics Data System (ADS)

    Ecija, D.; Marschall, M.; Reichert, J.; Kasperski, A.; Nieckarz, D.; Szabelski, P.; Auwärter, W.; Barth, J. V.

    2016-01-01

    Understanding the dynamics and thermal stability of metallosupramolecular chains on surfaces is of relevance for the development of molecular connectors in nanoelectronics or other fields. Here we present a combined study using temperature-controlled STM and Monte Carlo simulations to explore the behavior of metal-organic porphyrin chains on Cu(111) based on two-fold pyridyl-Cu-pyridyl coordination motifs. We monitor their behavior in the 180-360 K range, revealing three thermal regimes: i) flexibility up to 240 K, ii) diffusion of chain fragments and partial dissociation into a fluid phase for T > 240 K, and iii) full dissolution with temperatures exceeding ~ 320 K. The experimentally estimated reaction enthalpy of the metal-organic bonding is ~ 0.6 eV. Monte Carlo simulations reproduce qualitatively our STM observations and reveal the preference for linear and extended supramolecular chains with reduced substrate temperatures.

  1. Equation of state and stability of metal crystals at high pressure by DFT calculations

    NASA Astrophysics Data System (ADS)

    Minakov, Dmitry; Levashov, Pavel

    2013-06-01

    In this work we present ab initio equation-of-state calculations for crystals of some metals. Density functional theory at finite temperature (VASP code) is used to obatin the properties of electrons; lattice is simulated in quasi-harmonic approximation at non-zero temperature of electrons. Anharmonic effects are taken into account by the thermal expansion of a crystal. All calculations were performed for aluminum, copper and gold. We compare our results with available shock-wave data in crystal phase, including isentropic expansion. The melting curves are calculated by different criteria; the effect of different temperatures of electrons and ions is taken into account. Also we determine thermodynamic and kinetic boundaries of stability of crystals. Our calculations demonstrate that ab initio approaches can be used to theoretically reconstruct thermodynamically complete EOS of metallic crystals. This work was supported by RFBR grant 12-08-31475 mol a.

  2. Improved Photo-Induced Stability in Amorphous Metal-Oxide Based TFTs for Transparent Displays.

    PubMed

    Koo, Sang-Mo; Ha, Tae-Jun

    2015-10-01

    In this paper, we investigate the origin of photo-induced instability in amorphous metal-oxide based thin-film transistors (oxide-TFTs) by exploring threshold voltage (Vth) shift in transfer characteristics. The combination of photo irradiation and prolonged gate bias stress enhanced the shift in Vth in amorphous hafnium-indium-zinc-oxide (a-HfIZO) TFTs. Such results stem from the extended trapped charges at the localized defect states related to oxygen vacancy which play a role in a screening effect on the electric field induced by gate voltage. We also demonstrate the chemically clean interface in oxide-TFTs by employing oxygen annealing which reduces the density of trap states, thereby resulting in improved photo-induced stability. We believe that this work stimulates the research society of transparent electronics by providing a promising approach to suppress photo-induced instability in metal-oxide TFTs.

  3. Stability of Weyl points in magnetic half-metallic Heusler compounds

    NASA Astrophysics Data System (ADS)

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

    2017-07-01

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

  4. Inducing half-metallicity with enhanced stability in zigzag graphene nanoribbons via fluorine passivation

    NASA Astrophysics Data System (ADS)

    Jaiswal, Neeraj K.; Tyagi, Neha; Kumar, Amit; Srivastava, Pankaj

    2017-02-01

    Half metals are the primary ingredients for the realization of novel spintronic devices. In the present work, by employing density functional theory based first-principles calculation, we predict half metallic behavior in fluorine passivated zigzag graphene nanoribbons (F-ZGNR). Four different structures have been investigated viz. one edge F passivated ZGNR (F-ZGNR-1), both edges F passivated ZGNR (F-ZGNR-2), F passivation on alternate sites in first configuration (alt-1) and F passivation on alternate sites in second configuration (alt-2). Interestingly, it is noticed that F passivation is analogous to H passivation (pristine), however, F-ZGNR are reckoned energetically more stable than pristine ones. An spin induced band gap is noticed for all F-ZGNR irrespective of their widths although its magnitude is slightly less than the pristine counterparts. With an external transverse electric field, ribbons undergo semiconducting to half metallic transformation. The observed half metallic character with enhanced stability present F-ZGNR as a better candidate than pristine ZGNR towards the realization of upcoming spintronic devices.

  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. Interfacial Stability of Li Metal-Solid Electrolyte Elucidated via in Situ Electron Microscopy.

    PubMed

    Ma, Cheng; Cheng, Yongqiang; Yin, Kuibo; Luo, Jian; Sharafi, Asma; Sakamoto, Jeff; Li, Juchuan; More, Karren L; Dudney, Nancy J; Chi, Miaofang

    2016-11-09

    Despite their different chemistries, novel energy-storage systems, e.g., Li-air, Li-S, all-solid-state Li batteries, etc., face one critical challenge of forming a conductive and stable interface between Li metal and a solid electrolyte. An accurate understanding of the formation mechanism and the exact structure and chemistry of the rarely existing benign interfaces, such as the Li-cubic-Li7-3xAlxLa3Zr2O12 (c-LLZO) interface, is crucial for enabling the use of Li metal anodes. Due to spatial confinement and structural and chemical complications, current investigations are largely limited to theoretical calculations. Here, through an in situ formation of Li-c-LLZO interfaces inside an aberration-corrected scanning transmission electron microscope, we successfully reveal the interfacial chemical and structural progression. Upon contact with Li metal, the LLZO surface is reduced, which is accompanied by the simultaneous implantation of Li(+), resulting in a tetragonal-like LLZO interphase that stabilizes at an extremely small thickness of around five unit cells. This interphase effectively prevented further interfacial reactions without compromising the ionic conductivity. Although the cubic-to-tetragonal transition is typically undesired during LLZO synthesis, the similar structural change was found to be the likely key to the observed benign interface. These insights provide a new perspective for designing Li-solid electrolyte interfaces that can enable the use of Li metal anodes in next-generation batteries.

  7. Phase stability in heavy f-electron metals from first-principles theory

    SciTech Connect

    Soderlind, P

    2005-11-17

    The structural phase stability of heavy f-electron metals is studied by means of density-functional theory (DFT). These include temperature-induced transitions in plutonium metal as well as pressure-induced transitions in the trans-plutonium metals Am, Cm, Bk, and Cf. The early actinides (Th-Np) display phases that could be rather well understood from the competition of a crystal-symmetry breaking mechanism (Peierls distortion) of the 5f states and electrostatic forces, while for the trans-plutonium metals (Am-Cf) the ground-state structures are governed by 6d bonding. We show in this paper that new physics is needed to understand the phases of the actinides in the volume range of about 15-30 {angstrom}{sup 3}. At these volumes one would expect, from theoretical arguments made in the past, to encounter highly complex crystal phases due to a Peierls distortion. Here we argue that the symmetry reduction associated with spin polarization can make higher symmetry phases competitive. Taking this into account, DFT is shown to describe the well-known phase diagram of plutonium and also the recently discovered complex and intriguing high-pressure phase diagrams of Am and Cm. The theory is further applied to investigate the behaviors of Bk and Cf under compression.

  8. Degradation mechanisms and stability forecasting and adhesion contacts of metal films with binary dielectric substrates

    SciTech Connect

    Stolyarova, S.; Nemirovsky, Y.; Simanovskis, A.

    1996-12-31

    In this paper the authors present their conception of degradation and stability on the adhesion contacts of metal films with binary nonmetallic crystals. There are numerous works devoted to the atomic scale determination of adhesion forces and development of adhesion interaction laws. But in the real life the kinetic processes, taking place on the adhesion contact, can lead to such dramatic changes in adhesion strength values that the initial adhesion characteristics do not worth much for practice. Sometimes, adhesion contact with a metal which supposed to be highly adhesive failes in a short period of aging time. What the authors have learned from their studies of the contact processes is that in many cases the aging could not be separately addressed to the individual properties of film metal or to those of the substrate material. It depends mainly on the relationships between the parameters of interacting pair. The question is: what parameters should be taken into account to explain degradation phenomena and to predict them? The purpose of the present work is to show how the relative chemical activity of film metal and substrate cation affects the contact degradation in a vacuum and in different environmental conditions.

  9. Swelled plastics in supercritical CO2 as media for stabilization of metal nanoparticles and for catalytic hydrogenation.

    PubMed

    Ohde, Hiroyuki; Ohde, Mariko; Wai, Chien M

    2004-04-21

    Swelled plastics in supercritical carbon dioxide provide unique environments for stabilizing palladium and rhodium nanoparticles and for catalytic hydrogenation. Complete hydrogenation of benzene to cyclohexane can be achieved in 10 minutes using the plastic stabilized Rh nanoparticles at 50 degrees C in supercritical CO(2). High efficiency, reusability, and rapid separation of products are some advantages of the plastic stabilized metal nanoparticles for catalytic hydrogenation in supercritical CO(2).

  10. Enzyme immobilization on a nanoadsorbent for improved stability against heavy metal poisoning.

    PubMed

    Pogorilyi, R P; Melnyk, I V; Zub, Y L; Seisenbaeva, G A; Kessler, V G

    2016-08-01

    Magnetic nanoparticles modified with siloxane layers bearing amino and thiol functions have been used for immobilization of urease either by adsorption or via surface grafting. The activity of the immobilized enzyme in the hydrolysis of urea extended to the levels typical of the native enzyme, while its long-term stability in combination with magnetic retraction opened for its repeated use in both analysis and detoxification of bio-fluids. The immobilized urease revealed strongly enhanced stability and 65% activity in the presence of 0.1mmol/l of Hg(2+) or 0.3mmol/l of Cu(2+) while the native urease did not retain any activity at all. The enzyme grafting was shown to be a potentially perspective tool in alleviation of heavy metal poisoning and to be providing an opportunity for use of the developed adsorbents as both biosensors and bio-reactants for removal of urea from biofluids.

  11. Oxidation induced amorphous stabilization of the subsurface region in Zr-Cu metallic glass

    SciTech Connect

    Lim, K. R.; Park, J. M.; Park, S. H.; Na, M. Y.; Kim, K. C.; Kim, D. H.; Kim, W. T.

    2014-01-20

    In the present study, we demonstrate that selective surface oxidation of Zr{sub 70}Cu{sub 30} metallic glass can stabilize the amorphous structure in the subsurface region of the matrix. The oxidation proceeds by selective oxidation of Zr, forming monoclinic ZrO{sub 2} layer on the surface, and the subsurface layer becomes Cu-enriched due to back diffusion of Cu atoms from the oxide layer. Interestingly, in this system, the composition change in the subsurface region leads to enhancement of glass stability, forming of a double layered surface structure consisted of inner amorphous layer and outer monoclinic ZrO{sub 2} layer even when the remaining matrix is completely crystallized.

  12. Improve the operational stability of the inverted organic solar cells using bilayer metal oxide structure.

    PubMed

    Chang, Jingjing; Lin, Zhenhua; Jiang, Changyun; Zhang, Jie; Zhu, Chunxiang; Wu, Jishan

    2014-11-12

    Operational stability is a big obstacle for the application of inverted organic solar cells (OSCs), however, less talked about in the research reports. Due to photoinduced degradation of the metal oxide interlayer, which can cause shunts generation and degeneration in ZnO interlayer, a significant degradation of open circuit voltage (Voc) and fill factor (FF) has been observed by in situ periodic measurements of the device current density-voltage (J-V) curves with light illumination. By combining TiOx and ZnO to form bilayer structures on ITO, the photovoltaic performance is improved and the photoinduced degradation is reduced. It was found that the device based on ZnO/TiOx bilayer structure achieved better operational stability as compared to that with ZnO or TiOx interlayer.

  13. Distinct surface hydration behaviors of boron-rich boride thin film coatings

    NASA Astrophysics Data System (ADS)

    Lu, Xinhong; Liu, Wei; Ouyang, Jun; Tian, Yun

    2014-08-01

    In this work, the surface boron chemical states and surface hydration behaviors of the as-deposited and annealed boron-rich boride thin film coatings, including AlMgB14, TiB2 and AlMgB14-TiB2, were systematically studied by use of X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The XPS results indicate that boron at annealed AlMgB14 film surface can be oxidized; surprisingly, such oxidation does not lead to the formation of boric acid in ambient air. Instead, boric acid can be produced at the surface of annealed TiB2 film and AlMgB14-TiB2 film. It is shown, via the water contact angle measurements, that these boride films exhibit distinct surface wettability characteristics, which are believed to result in the observed surface hydration processes. Furthermore, we found anatase TiO2 formation plays a major role in the surface wetting behaviors for these boride films.

  14. The Effects of Borides on the Mechanical Properties of TLPB Repaired Inconel 738 Superalloy

    NASA Astrophysics Data System (ADS)

    Wei, J.; Ye, Y.; Sun, Z.; Zou, G.; Bai, H.; Wu, A.; Liu, L.

    2017-10-01

    The transient liquid phase diffusion bonding (TLPB) method was used to repair an artificial crack in Inconel 738, which was notched by a femtosecond laser. Mixed ratios of BNi-1a:DF-4B were investigated at the bonding temperature of 1373 K (1100 °C) for 2 to 36 hours. The effect of borides on the mechanical properties of TLPB repaired joints was studied through analysis of the microstructure, fracture path, and morphology observations. The borides formation, morphology, distribution, and joints strength were studied in detail. The results showed that the diffusion of B can either increase or decrease the joint strength, depending on its distribution and morphology. The amount of large blocky Ni-B compounds in the precipitate zone were reduced with increasing holding time, which resulted in an increase in joint strength. Nevertheless, further increasing the holding time led to a decrease in joint strength because of the formation of continuous acicular borides in the diffusion-affected zone. The fracture modes of TLPB joints were also discussed on the basis of the microstructure and fractography.

  15. Fluorous Metal-Organic Frameworks with Enhanced Stability and High H2/CO2 Storage Capacities

    PubMed Central

    Zhang, Da-Shuai; Chang, Ze; Li, Yi-Fan; Jiang, Zhong-Yi; Xuan, Zhi-Hong; Zhang, Ying-Hui; Li, Jian-Rong; Chen, Qiang; Hu, Tong-Liang; Bu, Xian-He

    2013-01-01

    A new class of metal-organic frameworks (MOFs) has been synthesized by ligand-functionalization strategy. Systematic studies of their adsorption properties were performed at low and high pressure. Importantly, when fluorine was introduced into the framework via the functionalization, both the framework stabilities and adsorption capacities towards H2/CO2 were enhanced significantly. This consequence can be well interpreted by theoretical studies of these MOFs structures. In addition, one of these MOFs TKL-107 was used to fabricate mixed matrix membranes, which exhibit great potential for the application of CO2 separation. PMID:24264725

  16. Relaxation kinetics and mechanical stability of metallic glasses and supercooled melts

    NASA Astrophysics Data System (ADS)

    Mayr, S. G.

    2009-02-01

    Metallic glasses are characterized by a rather complex viscoelastic response and the occurrence of the glass transition, while the atomistic origins are still poorly understood. Using a realistic CuTi model glass we employ global and local elasticity tensors for a thorough analysis of relaxation kinetics and mechanical stability. We obtain strong indication that (i) α relaxation is governed by an underlying process (identified as slow β relaxation) which resembles diffusion in its temperature dependence, (ii) glasses reveal intrinsic mechanical instabilities, which are closely linked to collective shear events within shear transformation zones, and (iii) glass transition can be understood as a percolation transition of mechanically unstable regions.

  17. 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.

  18. A Versatile Al(III) -Based Metal-Organic Framework with High Physicochemical Stability.

    PubMed

    Wang, Zhuo-Wei; Chen, Min; Liu, Chun-Sen; Wang, Xi; Zhao, Hui; Du, Miao

    2015-11-23

    A unique Al(III) -based metal-organic framework (467-MOF) with two types of square channels has been designed and synthesized by using a flexible tricarboxylate ligand under solvothermal conditions. 467-MOF exhibits superior thermal and chemical stability and, moreover, shows high CO2 sorption selectivity over H2 , with a selectivity, based on the ideal adsorbed solution theory (IAST) of approximately 45 at 273 or 293 K. Furthermore, its solvent-dependent photoluminescence makes it an applicable sensor in the detection of nitrobenzene explosives through fluorescence quenching. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Stability and Electronic properties of Ultra-thin Metallic nanowires on MoS2 monolayer

    NASA Astrophysics Data System (ADS)

    Kumar, Ashok; Zhong, Xiaoliang; Gupta, Sanjeev K.; Ahluwalia, P. K.; Karna, Shashi P.; Pandey, Ravindra

    2014-03-01

    MoS2 has emerged as a promising 2D nanomaterial for several technological applications. It has recently been shown that the highly capacitive Au nanoparticles raised the effective gate voltage for the MoS2 based device by an order of magnitude (Nano Lett. 13, 4434-41, 2013). In this talk, we examine stability and electronic properties of commensurable ultra-thin noble-metal nanowires (Cu, Ag, Au, Pt) on MoS2 monolayer. Results based on density functional theory will be presented to determine the preferred configuration for nanowires on the monolayer together with the enhancement in the conductivity of the composite system considered.

  20. Stabilization and solidification of metal-laden wastes by compaction and magnesium phosphate-based binder.

    PubMed

    Rao, A J; Pagilla, K R; Wagh, A S

    2000-09-01

    Bench-scale and full-scale investigations of waste stabilization and volume reduction were conducted using spiked soil and ash wastes containing heavy metals such as Cd, Cr, Pb, Ni, and Hg. The waste streams were stabilized and solidified using chemically bonded phosphate ceramic (CBPC) binder, and then compacted by either uniaxial or harmonic press for volume reduction. The physical properties of the final waste forms were determined by measuring volume reduction, density, porosity, and compressive strength. The leachability of heavy metals in the final waste forms was determined by a toxicity characteristic leaching procedure (TCLP) test and a 90-day immersion test (ANS 16.1). The structural composition and nature of waste forms were determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. CBPC binder and compaction can achieve 80-wt% waste loading and 39-47% reduction in waste volume. Compressive strength of final waste forms ranged from 1500 to 2000 psi. TCLP testing of waste forms showed that all heavy metals except Hg passed the TCLP limits using the phosphate-based binder. When Na2S was added to the binder, the waste forms also passed TCLP limits for Hg. Long-term leachability resistance of the final waste forms was achieved for all metals in both soil and ash wastes, and the leachability index was approximately 14. XRD patterns of waste forms indicated vermiculite in the ash waste was chemically incorporated into the CBPC matrix. SEM showed that waste forms are layered when compacted by uniaxial press and are homogeneous when compacted by harmonic press.

  1. Stabilization of ultrathin (hydroxy)oxide films on transition metal substrates for electrochemical energy conversion

    DOE PAGES

    Zeng, Zhenhua; Chang, Kee-Chul; Kubal, Joseph; ...

    2017-05-08

    Design of cost-effective electrocatalysts with enhanced stability and activity is of paramount importance for the next generation of energy conversion systems, including fuel cells and electrolyzers. However, electrocatalytic materials generally improve one of these properties at the expense of the other. Here, using Density Functional Theory calculations and electrochemical surface science measurements, we explore atomic-level features of ultrathin (hydroxy)oxide films on transition metal substrates and demonstrate that these films exhibit both excellent stability and activity for electrocatalytic applications. The films adopt structures with stabilities that significantly exceed bulk Pourbaix limits, including stoichiometries not found in bulk and properties that aremore » tunable by controlling voltage, film composition, and substrate identity. Using nickel (hydroxy)oxide/Pt(111) as an example, we further show how the films enhance activity for hydrogen evolution through a bifunctional effect. Finally, the results suggest design principles for a new class of electrocatalysts with simultaneously enhanced stability and activity for energy conversion.« less

  2. Metal Hydride Nanoparticles with Ultrahigh Structural Stability and Hydrogen Storage Activity Derived from Microencapsulated Nanoconfinement.

    PubMed

    Zhang, Jiguang; Zhu, Yunfeng; Lin, Huaijun; Liu, Yana; Zhang, Yao; Li, Shenyang; Ma, Zhongliang; Li, Liquan

    2017-06-01

    Metal hydrides (MHs) have recently been designed for hydrogen sensors, switchable mirrors, rechargeable batteries, and other energy-storage and conversion-related applications. The demands of MHs, particular fast hydrogen absorption/desorption kinetics, have brought their sizes to nanoscale. However, the nanostructured MHs generally suffer from surface passivation and low aggregation-resisting structural stability upon absorption/desorption. This study reports a novel strategy named microencapsulated nanoconfinement to realize local synthesis of nano-MHs, which possess ultrahigh structural stability and superior desorption kinetics. Monodispersed Mg2 NiH4 single crystal nanoparticles (NPs) are in situ encapsulated on the surface of graphene sheets (GS) through facile gas-solid reactions. This well-defined MgO coating layer with a thickness of ≈3 nm efficiently separates the NPs from each other to prevent aggregation during hydrogen absorption/desorption cycles, leading to excellent thermal and mechanical stability. More interestingly, the MgO layer shows superior gas-selective permeability to prevent further oxidation of Mg2 NiH4 meanwhile accessible for hydrogen absorption/desorption. As a result, an extremely low activation energy (31.2 kJ mol(-1) ) for the dehydrogenation reaction is achieved. This study provides alternative insights into designing nanosized MHs with both excellent hydrogen storage activity and thermal/mechanical stability exempting surface modification by agents. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Color stability, water sorption and cytotoxicity of thermoplastic acrylic resin for non metal clasp denture

    PubMed Central

    Jang, Dae-Eun; Lee, Ji-Young; Jang, Hyun-Seon; Lee, Jang-Jae

    2015-01-01

    PURPOSE The aim of this study was to compare the color stability, water sorption and cytotoxicity of thermoplastic acrylic resin for the non-metal clasp dentures to those of thermoplastic polyamide and conventional heat-polymerized denture base resins. MATERIALS AND METHODS Three types of denture base resin, which are conventional heat-polymerized acrylic resin (Paladent 20), thermoplastic polyamide resin (Bio Tone), thermoplastic acrylic resin (Acrytone) were used as materials for this study. One hundred five specimens were fabricated. For the color stability test, specimens were immersed in the coffee and green tee for 1 and 8 weeks. Color change was measured by spectrometer. Water sorption was tested after 1 and 8 weeks immersion in the water. For the test of cytotoxicity, cell viability assay was measured and cell attachment was analyzed by FE-SEM. RESULTS All types of denture base resin showed color changes after 1 and 8 weeks immersion. However, there was no significant difference between denture base resins. All specimens showed significant color changes in the coffee than green tee. In water sorption test, thermoplastic acrylic resin showed lower values than conventional heat-polymerized acrylic resin and thermoplastic polyamide resin. Three types of denture base showed low cytotoxicity in cell viability assay. Thermoplastic acrylic resin showed the similar cell attachment but more stable attachment than conventional heat-polymerized acrylic resin. CONCLUSION Thermoplastic acrylic resin for the non-metal clasp denture showed acceptable color stability, water sorption and cytotoxicity. To verify the long stability in the mouth, additional in vitro studies are needed. PMID:26330974

  4. Development of Boride Composite Materials for Cold Cathode Devices

    DTIC Science & Technology

    1981-05-01

    22 7. Diagram of the Induction Heating Facilities .. .. .....24 8. Typical Pellet After RF Heating...technique in an RF induction furnace. Pellets of the eu- tectic composition available from the literature were melted as well as pellets of a composition...com- pounds with the metals and metal oxides . Pure boron is silvery gray in color. In order to avoid reactions with Other materials at high tempera

  5. Corrosion behavior of titanium boride composite coating fabricated on commercially pure titanium in Ringer's solution for bioimplant applications.

    PubMed

    Sivakumar, Bose; Singh, Raghuvir; Pathak, Lokesh Chandra

    2015-03-01

    The boriding of commercially pure titanium was performed at 850°C, 910°C, and 1050°C for varied soaking periods (1, 3 and 5h) to enhance the surface properties desirable for bioimplant applications. The coating developed was characterized for the evolution of phases, microstructure and morphology, microhardness, and consequent corrosion behavior in the Ringer's solution. Formation of the TiB2 layer at the outermost surface followed by the TiB whiskers across the borided CpTi is unveiled. Total thickness of the composite layer on the substrates borided at 850, 910, and 1050°C for 5h was found to be 19.1, 26.4, and 18.2μm respectively which includes <3μm thick TiB2 layer. The presence of TiB2 phase was attributed to the high hardness ~2968Hv15gf of the composite coating. The anodic polarization studies in the simulated body fluid unveiled a reduction in the pitting corrosion resistance after boriding the CpTi specimens. However, this value is >0.55VSCE (electrochemical potential in in-vivo physiological environment) and hence remains within the safe region. Both the untreated and borided CpTi specimens show two passive zones associated with different passivation current densities. Among the CpTi borided at various times and temperatures, a 3h treated shows better corrosion resistance. The corrosion of borided CpTi occurred through the dissolution of TiB2. Copyright © 2014. Published by Elsevier B.V.

  6. Metals affect the structure and activity of human plasminogen activator inhibitor-1. I. Modulation of stability and protease inhibition

    PubMed Central

    Thompson, Lawrence C; Goswami, Sumit; Ginsberg, David S; Day, Duane E; Verhamme, Ingrid M; Peterson, Cynthia B

    2011-01-01

    Human plasminogen activator inhibitor type 1 (PAI-1) is a serine protease inhibitor with a metastable active conformation. Under physiological conditions, half of the inhibitor transitions to a latent state within 1–2 h. The interaction between PAI-1 and the plasma protein vitronectin prolongs this active lifespan by ∼50%. Previously, our group demonstrated that PAI-1 binds to resins using immobilized metal affinity chromatography (Day, U.S. Pat. 7,015,021 B2, March 21, 2006). In this study, the effect of these metals on function and stability was investigated by measuring the rate of the transition from the active to latent conformation. All metals tested showed effects on stability, with the majority falling into one of two types depending on their effects. The first type of metal, which includes magnesium, calcium and manganese, invoked a slight stabilization of the active conformation of PAI-1. A second category of metals, including cobalt, nickel and copper, showed the opposite effects and a unique vitronectin-dependent modulation of PAI-1 stability. This second group of metals significantly destabilized PAI-1, although the addition of vitronectin in conjunction with these metals resulted in a marked stabilization and slower conversion to the latent conformation. In the presence of copper and vitronectin, the half-life of active PAI-1 was extended to 3 h, compared to a half-life of only ∼30 min with copper alone. Nickel had the largest effect, reducing the half-life to ∼5 min. Together, these data demonstrate a heretofore-unknown role for metals in modulating PAI-1 stability. PMID:21280127

  7. A stability concept for metal ion coordination to single-stranded nucleic acids and affinities of individual sites.

    PubMed

    Sigel, Roland K O; Sigel, Helmut

    2010-07-20

    The three-dimensional architecture and function of nucleic acids strongly depend on the presence of metal ions, among other factors. Given the negative charge of the phosphate-sugar backbone, positively charged species, mostly metal ions, are necessary for compensation. However, these ions also allow and induce folding of complicated RNA structures. Furthermore, metal ions bind to specific sites, stabilizing local motifs and positioning themselves correctly to aid (or even enable) a catalytic mechanism, as, for example, in ribozymes. Many nucleic acids thereby exhibit large differences in folding and activity depending not only on the concentration but also on the kind of metal ion involved. As a consequence, understanding the role of metal ions in nucleic acids requires knowing not only the exact positioning and coordination sphere of each specifically bound metal ion but also its intrinsic site affinity. However, the quantification of metal ion affinities toward certain sites in a single-stranded (though folded) nucleic acid is a demanding task, and few experimental data exist. In this Account, we present a new tool for estimating the binding affinity of a given metal ion, based on its ligating sites within the nucleic acid. To this end, we have summarized the available affinity constants of Mg(2+), Ca(2+), Mn(2+), Cu(2+), Zn(2+), Cd(2+), and Pb(2+) for binding to nucleobase residues, as well as to mono- and dinucleotides. We have also estimated for these ions the stability constants for coordinating the phosphodiester bridge. In this way, stability increments for each ligand site are obtained, and a clear selectivity of the ligating atoms, as well as their discrimination by different metal ions, can thus be recognized. On the basis of these data, we propose a concept that allows one to estimate the intrinsic stabilities of nucleic acid-binding pockets for these metal ions. For example, the presence of a phosphate group has a much larger influence on the overall

  8. Use of alum water treatment sludge to stabilize C and immobilize P and metals in composts.

    PubMed

    Haynes, R J; Zhou, Y-F

    2015-09-01

    Alum water treatment sludge is composed of amorphous hydroxyl-Al, which has variable charge surfaces with a large Brunauer-Emmett-Teller (BET) surface area (103 m(-2) g(-1)) capable of specific adsorption of organic matter molecules, phosphate, and heavy metals. The effects of adding dried, ground, alum water treatment sludge (10% w/w) to the feedstock for composting municipal green waste alone, green waste plus poultry manure, or green waste plus biosolids were determined. Addition of water treatment sludge reduced water soluble C, microbial biomass C, CO2 evolution, extractable P, and extractable heavy metals during composting. The decrease in CO2 evolution (i.e., C sequestration) was greatest for poultry manure and least for biosolid composts. The effects of addition of water treatment sludge to mature green waste-based poultry manure and biosolid composts were also determined in a 24-week incubation experiment. The composts were either incubated alone or after addition to a soil. Extractable P and heavy metal concentrations were decreased by additions of water treatment sludge in all treatments, and CO2 evolution was also reduced from the poultry manure compost over the first 16-18 weeks. However, for biosolid compost, addition of water treatment sludge increased microbial biomass C and CO2 evolution rate over the entire 24-week incubation period. This was attributed to the greatly reduced extractable heavy metal concentrations (As, Cr, Cu, Pb, and Zn) present following addition of water treatment sludge, and thus increased microbial activity. It was concluded that addition of water treatment sludge reduces concentrations of extractable P and heavy metals in composts and that its effect on organic matter stabilization is much greater during the composting process than for mature compost because levels of easily decomposable organic matter are initially much higher in the feedstock than those in matured composts.

  9. A facile surface chemistry route to a stabilized lithium metal anode

    NASA Astrophysics Data System (ADS)

    Liang, Xiao; Pang, Quan; Kochetkov, Ivan R.; Sempere, Marina Safont; Huang, He; Sun, Xiaoqi; Nazar, Linda F.

    2017-09-01

    Lithium metal is a highly desirable anode for lithium rechargeable batteries, having the highest theoretical specific capacity and lowest electrochemical potential of all material candidates. Its most notable problem is dendritic growth upon Li plating, which is a major safety concern and exacerbates reactivity with the electrolyte. Here we report that Li-rich composite alloy films synthesized in situ on lithium by a simple and low-cost methodology effectively prevent dendrite growth. This is attributed to the synergy of fast lithium ion migration through Li-rich ion conductive alloys coupled with an electronically insulating surface component. The protected lithium is stabilized to sustain electrodeposition over 700 cycles (1,400 h) of repeated plating/stripping at a practical current density of 2 mA cm‑2 and a 1,500 cycle-life is realized for a cell paired with a Li4Ti5O12 positive electrode. These findings open up a promising avenue to stabilize lithium metal with surface layers having targeted properties.

  10. Long-term stability of metal-supported solid oxide fuel cells employing infiltrated electrodes

    NASA Astrophysics Data System (ADS)

    Zhou, Yucun; Chen, Ting; Li, Junliang; Yuan, Chun; Xin, Xianshuang; Chen, Guoyi; Miao, Guoshuan; Zhan, Weiting; Zhan, Zhongliang; Wang, Shaorong

    2015-11-01

    Here, stability of the metal-supported solid oxide fuel cell (MS-SOFC) with Ni-Ce0.8Sm0.2O2-δ (SDC) infiltrated 430L anode and La0.6Sr0.4Fe0.9Sc0.1O3-δ (LSFSc) infiltrated scandia-stabilized zirconia (SSZ) cathode is evaluated. It is found that the degradation rate defined as the voltage loss during a fixed period is faster at higher operation temperatures and larger current densities. Scanning electron microscopy (SEM) and energy dispersive X-ray spectra (EDS) analysis indicate that the degradation is mainly caused by the morphological change of the anode while metal element diffusion between Ni catalyst and 430L substrate contributes little. A 1500 h durability test measured at 650 °C and 0.9 A cm-2 shows a degradation rate of 1.3% kh-1 and the voltage decrease is mainly found in the initial 500 h.

  11. Polyaniline and Perfluorosulfonic Acid Co-Stabilized Metal Catalysts for Oxygen Reduction Reaction.

    PubMed

    Ye, Bei; Cheng, Kun; Li, Wenqiang; Liu, Jing; Zhang, Jie; Mu, Shichun

    2017-06-06

    A proton (perfluorosulfonic acid, PFSA) and electron (polyaniline, PANI) conductor polymer costabilized Pt catalyst (Pt-PFSA/C@PANI) is synthesized to improve the long-term stability of polymer electrolyte membrane fuel cells (PEMFCs). The prepared catalyst not only displays comparable oxygen reduction reaction (ORR) activity, but significantly higher electrochemical stability than commercial porous carbon nanosphere supported Pt catalysts (Pt/C). This robust electrochemical property can be due to the result of PFSA and PANI. PANI as protector inhibits carbon nanospheres from corrosion of carbon supports in harsh chemical and electrochemical conditions. Meanwhile, PFSA wrapped Pt NPs (Pt@PFSA) can also anchor Pt NPs on C@PANI to avoid aggregation and detachment of Pt NPs, due to the increased metal-support interaction caused by the strong electrostatic attraction between PANI and PFSA with corresponding positive and negative charges. Significantly, after coating PANI on carbon supports (C@PANI), almost all micropores in the surface of carbon disappear, effectively avoiding the embedding of Pt nanopaticles into micropores. Furthermore, the triple-phase boundary toward ORR catalysis can be facilitated by PFSA as proton conductor (solid electrolyte). These are of benefit to increase utilization of Pt noble metals and ORR activity of our new catalysts.

  12. 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.

  13. Thermostable alkaline phytase from Bacillus sp. MD2: effect of divalent metals on activity and stability.

    PubMed

    Tran, Thuy Thi; Hashim, Suhaila Omar; Gaber, Yasser; Mamo, Gashaw; Mattiasson, Bo; Hatti-Kaul, Rajni

    2011-07-01

    Phytate, the major source of phosphorus in seeds, exists as a complex with different metal ions. Alkaline phytases are known to dephosphorylate phytate complexed with calcium ions in contrast to acid phytases that act only on phytic acid. A recombinant alkaline phytase from Bacillus sp. MD2 has been purified and characterized with respect to the effect of divalent metal ions on the enzyme activity and stability. The presence of Ca(2+) on both the enzyme and the substrate is required for optimal activity and stability. Replacing Ca(2+) with Ba(2+), Mn(2+), Mg(2+) and Sr(2+) in the phytase resulted in the expression of >90% of the maximal activity with calcium-phytate as the substrate, while Fe(2+) and Zn(2+) rendered the enzyme inactive. On the other hand, the calcium loaded phytase showed significant activity (60%) with sodium phytate and lower activity (17-20%) with phytate complexed with only Mg(2+), Sn(2+) and Sr(2+), respectively. On replacing Ca(2+) on both the enzyme and the substrate with other metal ions, about 20% of the maximal phytase activity was obtained only with Mg(2+) and Sr(2+), respectively. Only Ca(2+) resulted in a marked increase in the melting temperature (T(m)) of the enzyme by 12-21°C, while Ba(2+), Mn(2+), Sr(2+) or Cu(2+) resulted in a modest (2-3.5°C) increase in T(m). In the presence of 1-5mM Ca(2+), the optimum temperature of the phytase activity was increased from 40°C to 70°C, while optimum pH of the enzyme shifted by 0.4-1 pH unit towards the acidic region.

  14. Distinct reaction pathway promoted by non-divalent-metal cations in a tertiary stabilized hammerhead ribozyme

    PubMed Central

    Roychowdhury-Saha, Manami; Burke, Donald H.

    2007-01-01

    Divalent ion sensitivity of hammerhead ribozymes is significantly reduced when the RNA structure includes appropriate tertiary stabilization. Therefore, we investigated the activity of the tertiary stabilized “RzB” hammerhead ribozyme in several nondivalent ions. Ribozyme RzB is active in spermidine and Na+ alone, although the cleavage rates are reduced by more than 1,000-fold relative to the rates observed in Mg2+ and in transition metal ions. The trivalent cobalt hexammine (CoHex) ion is often used as an exchange-inert analog of hydrated magnesium ion. Trans-cleavage rates exceeded 8 min−1 in 20 mM CoHex, which promoted cleavage through outersphere interactions. The stimulation of catalysis afforded by the tertiary structural interactions within RzB does not require Mg2+, unlike other extended hammerhead ribozymes. Site-specific interaction with at least one Mg2+ ion is suggested by CoHex competition experiments. In the presence of a constant, low concentration of Mg2+, low concentrations of CoHex decreased the rate by two to three orders of magnitude relative to the rate in Mg2+ alone. Cleavage rates increased as CoHex concentrations were raised further, but the final fraction cleaved was lower than what was observed in CoHex or Mg2+ alone. These observations suggest that Mg2+ and CoHex compete for binding and that they cause misfolded structures when they are together. The results of this study support the existence of an alternate catalytic mechanism used by nondivalent ions (especially CoHex) that is distinct from the one promoted by divalent metal ions, and they imply that divalent metals influence catalysis through a specific nonstructural role. PMID:17456566

  15. Stabilization of heavy metals in soil using two organo-bentonites.

    PubMed

    Yu, Kai; Xu, Jian; Jiang, Xiaohong; Liu, Cun; McCall, Wesley; Lu, Jinlong

    2017-10-01

    Stabilization of Cu, Zn, Cd, Hg, Cr and As in soil using tetramethylammonium (TMA) and dodecyltrimethylammonium (DTMA) modified bentonites (T-Bents and D-Bents) as amendments was investigated. Toxicity characteristic leaching procedure (TCLP) was used to quantify the metal mobility after soil treatment. The structural parameters of modified bentonites, including the BET surface area, basal spacing and zeta potential were obtained as a function of the TMA and DTMA loading at 40, 80, 120, 160 and 200% of the bentonite's cation exchange capacity, respectively. The results indicated that the characteristics of the organo-bentonites fundamentally varied depending on the species and concentration of modifiers loaded on bentonite. T-Bents and D-Bents manifested distinct immobilization effectiveness towards various metals. In association with the organo-bentonite characteristics, the main interactive mechanisms for Cu, Zn and Cd proceeded via cation exchange, Hg proceeded via physical adsorption and partitioning, Cr and As proceeded via specific adsorption and electrostatic attraction, respectively. This study provided operational and mechanistic basis for optimizing the organic clay synthesis and selecting as the appropriate amendment for remediation of heavy metal contaminated soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Stabilization of metallic phase in V2O3 thin film

    NASA Astrophysics Data System (ADS)

    Majid, S. S.; Shukla, D. K.; Rahman, F.; Gautam, K.; Choudhary, R. J.; Sathe, V. G.; Phase, D. M.

    2017-04-01

    The tailoring and understanding of the metal-insulator transitions (MITs) in vanadium sesquioxide, V2O3, is of major interest for both applications and fundamental physics. V2O3 has been characterized by MIT and concurrent structural transition at ˜155 K; however, the nature of the MIT has remained more elusive. We investigated the MIT and the electronic structure (in metallic phase) of the pulsed laser deposition grown strained vanadium sesquioxide thin films on Si. The strained thin films synthesized here show the suppression (by ˜23 K) of the MIT to lower temperatures, whilst the structural transition temperature decreases only by ˜10 K. Our results systematically confirm that albeit the structural changes are crucial in V2O3, electronic transition seems to be of Mott-Hubbard type. Stabilization of the metallic phase in the strained V2O3 thin film has been manifested from resistivity data and observations of the increased crystal field and quasiparticle features.

  17. Stabilized liquid membrane device (SLMD) for the passive, integrative sampling of labile metals in water

    USGS Publications Warehouse

    Brumbaugh, W.G.; Petty, J.D.; Huckins, J.N.; Manahan, S.E.

    2002-01-01

    A stabilized liquid membrane device (SLMD) is described for potential use as an in situ, passive, integrative sampler for cadmium (Cd), cobalt (Co), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) in natural waters. The SLMD (patent pending) consists of a 2.5-cm-wide by 15-cm-long strip of low-density polyethylene (LDPE) layflat tubing containing 1 mL of an equal mixture (v/v) of oleic acid (cis-9-octadecenoic acid) and EMO-8Q (7-[4-ethyl-1-methyloctyl]-8-quinolinol). The reagent mixture continuously diffuses to the exterior surface of the LDPE membrane, and provides for sequestration of several divalent metals for up to several weeks. Depending on sampler configuration, concentration factors of several thousand can be realized for these metal ions after just a few days. In addition to in situ deployment, the SLMD may be useful for laboratory determination of labile metal species in grab samples. Methods for minimizing the effects of water flow on the sampling rate are currently under investigation.

  18. Siderophore production by streptomycetes-stability and alteration of ferrihydroxamates in heavy metal-contaminated soil.

    PubMed

    Schütze, Eileen; Ahmed, Engy; Voit, Annekatrin; Klose, Michael; Greyer, Matthias; Svatoš, Aleš; Merten, Dirk; Roth, Martin; Holmström, Sara J M; Kothe, Erika

    2015-12-01

    Heavy metal-contaminated soil derived from a former uranium mining site in Ronneburg, Germany, was used for sterile mesocosms inoculated with the extremely metal-resistant Streptomyces mirabilis P16B-1 or the sensitive control strain Streptomyces lividans TK24. The production and fate of bacterial hydroxamate siderophores in soil was analyzed, and the presence of ferrioxamines E, B, D, and G was shown. While total ferrioxamine concentrations decreased in water-treated controls after 30 days of incubation, the sustained production by the bacteria was seen. For the individual molecules, alteration between neutral and cationic forms and linearization of hydroxamates was observed for the first time. Mesocosms inoculated with biomass of either strain showed changes of siderophore contents compared with the non-treated control indicating for auto-alteration and consumption, respectively, depending on the vital bacteria present. Heat stability and structural consistency of siderophores obtained from sterile culture filtrate were shown. In addition, low recovery (32 %) from soil was shown, indicating adsorption to soil particles or soil organic matter. Fate and behavior of hydroxamate siderophores in metal-contaminated soils may affect soil properties as well as conditions for its inhabiting (micro)organisms.

  19. Investigations of the structural stability of metal hydride composites by in-situ neutron imaging

    NASA Astrophysics Data System (ADS)

    Herbrig, Kai; Pohlmann, Carsten; Gondek, Łukasz; Figiel, Henryk; Kardjilov, Nikolay; Hilger, André; Manke, Ingo; Banhart, John; Kieback, Bernd; Röntzsch, Lars

    2015-10-01

    Metal hydride composites (MHC) with expanded natural graphite (ENG) exhibiting enhanced thermal conductivity and reduced porosity compared to metal hydride powders can enable a reversible, compact and safe way for hydrogen storage. In this study, neutron imaging during cyclic hydrogenation was utilized to investigate the structural stability and the spatial-temporal hydrogen concentration of application-oriented MHC with 40 mm in diameter compared to a loose metal hydride powder. In particular, swelling and shrinking effects of a radially confined MHC which could freely expand upwards were studied. It was found that the loose powder bed was easily torn apart during dehydrogenation, which leads to increased thermal resistance within the hydride bed. In contrast, the thermal resistance between MHC and container wall was minimized since the initial gap closes during initial hydrogenation and does not reopen thereafter. Further cyclic hydrogenation caused MHC volume changes, i.e. an almost reversible swelling/shrinking (so-called ;MHC breathing;). Moreover, neutron imaging allowed for the observation of reaction fronts within the MHC and the powder bed that are governed by the heat transfer.

  20. Table salt and other alkali metal chloride oligomers: structure, stability, and bonding.

    PubMed

    Bickelhaupt, F Matthias; Solà, Miquel; Guerra, Célia Fonseca

    2007-06-25

    We have investigated table salt and other alkali metal chloride monomers, ClM, and (distorted) cubic tetramers, (ClM)(4), with M = Li, Na, K, and Rb, using density functional theory (DFT) at the BP86/TZ2P level. Our objectives are to determine how the structure and thermochemistry (e.g., Cl-M bond lengths and strengths, oligomerization energies, etc.) of alkali metal chlorides depend on the metal atom and to understand the emerging trends in terms of quantitative Kohn-Sham molecular orbital (KS-MO) theory. The analyses confirm the high polarity of the Cl-M bond (dipole moment, VDD, and Hirshfeld atomic charges). They also reveal that bond overlap derived stabilization (approximately -26, -20, and -8 kcal/mol), although clearly larger than in the corresponding F-M bonds, contributes relatively little to the (trend in) bond strengths (-105, -90, and -94 kcal/mol) along M = Li, Na, and K. Thus, the Cl-M bonding mechanism resembles more closely that of the even more ionic F-M bond than that of the more covalent C-M or H-M bonds. Tetramerization causes the Cl-M bond to expand, and it reduces its polarity.

  1. The Analysis and Modeling of Phase Stability and Multiphase Designs in High Temperature Refractory Metal-Silicon-Boron Alloys

    DTIC Science & Technology

    2009-01-27

    to exhibit segregation and non-equilibrium boride phases that are difficult to remove by annealing or hot working. Initial efforts in powder...and hot isostatic pressing to react the components [06JEH, 04JEH]. Following synthesis, the microstructure retained a sub micron phase size and...moreover exhibited superplastic behavior at 1400°C. This observation indicates the possibility for fabricating final shapes by hot forging. However

  2. A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability.

    PubMed

    Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni; Guillou, Nathalie; Lamberti, Carlo; Bordiga, Silvia; Lillerud, Karl Petter

    2008-10-22

    Porous crystals are strategic materials with industrial applications within petrochemistry, catalysis, gas storage, and selective separation. Their unique properties are based on the molecular-scale porous character. However, a principal limitation of zeolites and similar oxide-based materials is the relatively small size of the pores, typically in the range of medium-sized molecules, limiting their use in pharmaceutical and fine chemical applications. Metal organic frameworks (MOFs) provided a breakthrough in this respect. New MOFs appear at a high and an increasing pace, but the appearances of new, stable inorganic building bricks are rare. Here we present a new zirconium-based inorganic building brick that allows the synthesis of very high surface area MOFs with unprecedented stability. The high stability is based on the combination of strong Zr-O bonds and the ability of the inner Zr6-cluster to rearrange reversibly upon removal or addition of mu3-OH groups, without any changes in the connecting carboxylates. The weak thermal, chemical, and mechanical stability of most MOFs is probably the most important property that limits their use in large scale industrial applications. The Zr-MOFs presented in this work have the toughness needed for industrial applications; decomposition temperature above 500 degrees C and resistance to most chemicals, and they remain crystalline even after exposure to 10 tons/cm2 of external pressure.

  3. Stabilization/solidification of battery debris & lead impacted material at Schuylkill Metals, Plant City, Florida

    SciTech Connect

    Anguiano, T.; Floyd, D.

    1997-12-31

    The Schuylkill Metals facility in Plant City Florida (SMPCI) operated as a battery recycling facility for approximately 13 years. During its operation, the facility disposed of battery components in surrounding wetland areas. In March of 1991 the U.S. EPA and SMPCI entered into a Consent Decree for the remediation of the SMPCI site using stabilization/solidification and on-site disposal. In November of 1994, ENTACT began remediation at the facility and to date has successfully stabilized/solidified over 228,000 tons of lead impacted battery components and lead impacted material. The ENTACT process reduces the size of the material to be treated to ensure that complete mixing of the phosphate/cement additive is achieved thereby promoting the chemical reactions of stabilization and solidification. ENTACT has met the following performance criteria for treated material at the SMPCI site: (1) Hydraulic Conductivity less than 1x10{sup -6} cm/s, (2) Unconfined Compressive Strength greater than 50 psi, (3) Lead, Cadmium, Arsenic, Chromium TCLP Leachability below hazardous levels.

  4. Batch and column studies of the stabilization of toxic heavy metals in dredged marine sediments by hematite after bioremediation.

    PubMed

    Mamindy-Pajany, Yannick; Geret, Florence; Hurel, Charlotte; Marmier, Nicolas

    2013-08-01

    The management of dredged sediments is an important issue in coastal regions where the marine sediments are highly polluted by metals and organic pollutants. In this paper, mineral-based amendments (hematite, zero-valent iron and zeolite) were used to stabilize metallic pollutants (As, Cd, Cu, Mo, Ni, Pb, and Zn) in a contaminated marine sediment sample. Mineral-based amendments were tested at three application rates (5 %, 10 %, and 15 %) in batch experiments in order to select the best amendment to perform column experiments. Batch tests have shown that hematite was the most efficient amendment to stabilize inorganic pollutants (As, Cd, Cu, Mo, Ni, Pb, and Zn) in the studied sediment. Based on batch tests, hematite was used at one application rate equal to 5 % to conduct column experiments. Column tests confirmed that hematite was able to decrease metal concentrations in leachates from stabilized sediment. The stabilization rates were particularly high for Cd (67 %), Mo (80 %), and Pb (90 %). The Microtox solid phase test showed that hematite could decrease significantly the toxicity of stabilized sediment. Based on batch and column experiments, it emerged that hematite could be a suitable adsorbent to stabilize metals in dredged marine sediment.

  5. Metal sulfide nanoparticles synthesized via enzyme treatment of biopolymer stabilized nanosuspensions

    NASA Astrophysics Data System (ADS)

    Kim, Yi-Yeoun; Walsh, Dominic

    2010-02-01

    Nanoparticles of CuS, CuxS, Ag2S and CdS were successfully prepared using a novel general and green synthetic process to give dextran biopolymer stabilised metal sulfifde nanosuspensions. Following preparation, dextranase enzyme was used to remove the bulk of the bound dextran to give pure stable metal sulfide nanocrystals for application in for example aspects of medicine, photonics and solar cells. Particles of good homogeneity were obtained and the CuS nanoparticle size was controlled to 9-27 nm by adjusting the reaction conditions. Cu2S nanoparticles were 14 nm, Ag2S nanoparticles were 20-50 nm and CdS nanoparticles were 9 nm is size. The complexing mechanism of nanoparticle sulfides to dextrans was further studied using carboxylmethyl dextran as a complexing agent and crosslinked Sephadex (dextran) `beads as substrate. Particles were characterized by TEM, XRD, TGA, FT-IR and zeta-potential measurement, and their UV-vis spectroscopic absorption properties were determined. Stabilization of the sulfide nanoparticles with soluble hydroxylated biopolymers such as dextran is previously unreported and is here interpreted in terms of viscosity, pH of the system and weak polar S-H or S(metal)OH2+ interactions with dextran depending on the material. Notably, the complexing mechanism appears to differ significantly from that taking place in known dextran-metal oxide systems. The process shown here has good potential for scale-up as a biosynthetic route for a range of functional sulfide nanoparticles.Nanoparticles of CuS, CuxS, Ag2S and CdS were successfully prepared using a novel general and green synthetic process to give dextran biopolymer stabilised metal sulfifde nanosuspensions. Following preparation, dextranase enzyme was used to remove the bulk of the bound dextran to give pure stable metal sulfide nanocrystals for application in for example aspects of medicine, photonics and solar cells. Particles of good homogeneity were obtained and the CuS nanoparticle size

  6. Metal sulfide nanoparticles synthesized via enzyme treatment of biopolymer stabilized nanosuspensions.

    PubMed

    Kim, Yi-Yeoun; Walsh, Dominic

    2010-02-01

    Nanoparticles of CuS, Cu(x)S, Ag(2)S and CdS were successfully prepared using a novel general and green synthetic process to give dextran biopolymer stabilised metal sulfifde nanosuspensions. Following preparation, dextranase enzyme was used to remove the bulk of the bound dextran to give pure stable metal sulfide nanocrystals for application in for example aspects of medicine, photonics and solar cells. Particles of good homogeneity were obtained and the CuS nanoparticle size was controlled to 9-27 nm by adjusting the reaction conditions. Cu(2)S nanoparticles were 14 nm, Ag(2)S nanoparticles were 20-50 nm and CdS nanoparticles were 9 nm is size. The complexing mechanism of nanoparticle sulfides to dextrans was further studied using carboxylmethyl dextran as a complexing agent and crosslinked Sephadex (dextran) ;beads as substrate. Particles were characterized by TEM, XRD, TGA, FT-IR and zeta-potential measurement, and their UV-vis spectroscopic absorption properties were determined. Stabilization of the sulfide nanoparticles with soluble hydroxylated biopolymers such as dextran is previously unreported and is here interpreted in terms of viscosity, pH of the system and weak polar S-H or S(metal)OH(2)(+) interactions with dextran depending on the material. Notably, the complexing mechanism appears to differ significantly from that taking place in known dextran-metal oxide systems. The process shown here has good potential for scale-up as a biosynthetic route for a range of functional sulfide nanoparticles.

  7. Treatment and Stabilization of Potentially Pyrophoric Radioactive Metal Chips and Turnings

    SciTech Connect

    Crocker, B.R.; Grondin, R.; Yarbrough, T.

    2006-07-01

    waste forms, were treated and disposed at the same land disposal facility in Utah. Complicating this task was the wide variety of hazardous and toxic contaminants, and great variability in the physical waste form. The chemical contaminants included mineral oil, polychlorinated biphenyls (PCBs), numerous volatile and semi-volatile organic contaminants, and toxic metals. Three main physical waste forms were included in the US DOE pyrophoric radioactive metal waste inventory: (1) chips and turnings in oil, (2) chips and turnings in soil, and (3) chips and turnings in sludge. The successful treatment method had to be capable of removing oil, PCBs, and volatile organics without resulting in ignition of the pyrophoric metals. After successful removal of hazardous and toxic organic contaminants, the toxic metals remaining in the waste required further stabilization to limit their potential for long-term leaching in land disposal facilities. The final waste form and its packaging also had to comply with the waste acceptance criteria of the land disposal facilities at the US DOE Hanford Site, in Richland, Washington, and the private disposal facility in Utah. This paper will describe the treatment process, the challenges encountered and overcome, the lessons learned, and final quality of the treated chip waste. Disposal and/or destruction of secondary wastes from the treatment process will also be discussed. (authors)

  8. Aspects of metal and silicon-based nanomaterials: Synthesis, stability and properties

    NASA Astrophysics Data System (ADS)

    Elechiguerra Joven, Jose Luis

    Metal and Si-based nanostructures have drawn increasing interest due to their potential uses in catalysis, biological sensors, and nanoelectronics among others. Therefore, in the present work, several nanostructures were produced, characterized and tested. In particular, the conventional synthesis of noble-metal nanostructures through the polyol method was modified by replacing poly-vinyl pyrrolidone PVP with poly-diallyl dimethyl ammonium chloride PDDA. As PDDA is a cationic polyelectrolyte, the initial strong electrostatic interaction between PDDA and the anionic metal precursors produce the formation of stable ion pairs, so the reactivity of the different species can be tailored and particles with different internal structure, i.e. crystallinity, can be produced. Additionally, metal nanostructures such as nanoparticles and nanowires have been proposed as building blocks for several applications in nanofabrication and nanoelectronics. However, even when atmospheric corrosion is common in metals, there is a lack of information about the stability of those nanostructures against such phenomenon. So, the atmospheric corrosion of silver nanowires and nanoparticles synthesized by the polyol method using PVP as capping agent was studied. Recently, five-fold twinned nanorods and nanowires of gold, copper and silver with pentagonal cross-sections have been synthesized by different techniques, including the polyol method. However, there is not a complete explanation of all the features presented in their electron diffraction patterns. Thus, a comprehensive study on the structure of these multi-twinned decahedral based nanorods and nanowires is presented. Another important application of noble-metal nanostructures is in the field of biology. In the present work, it has been demonstrated that silver nanoparticles undergo a size dependent interaction with HIV-1 via preferential binding to the gp120 glycoprotein knobs. Due to this interaction, silver nanoparticles inhibit the

  9. Effect of metal oxides on the stabilization of soil organic matter

    NASA Astrophysics Data System (ADS)

    Stelmach, Wioleta

    2017-04-01

    Soil organic matter (SOM) is protected from decomposition by three mechanisms: 1) biochemical stabilization through the accumulation of recalcitrant SOM compounds, 2) physical stabilization, i.e. spatial inaccessibility of SOM for microbes, and 3) chemical protection of SOM through intimate interaction with minerals and metal oxides. The latter mechanisms suggest that added organic substances (i.e. post-fermentation sludge) can be stabilized by metal oxides to increase C sequestration in soil. The aim of this study was to determine the effects of Fe2O3 - one of the dominant metal oxides in soil - on the sequestration of post-fermentation sludge C in soil by separately tracing the decomposition of sludge and of SOM to carbon dioxide (CO2). To determine changes in SOM turnover after the addition of post-fermentation sludge without/with Fe2O3, the isotopic signatures of both C sources (SOM and post-fermentation sludge) were used. Using differences in the 13C natural abundance of the soil (C3 originated, δ13C = -26) and the post-fermentation sludge (C4 originated, δ13C = -18), the CO2 fluxes arising from both C sources were tracked. Addition of post-fermentation sludge to the soil increased the CO2 production by 30% compared to soil without sludge. δ13C analysis of the total CO2 efflux revealed that post-fermentation sludge decreased SOM decomposition. Fe2O3 slightly suppressed sludge decomposition, and therefore increased C sequestration in soil. Only 30% of the post-fermentation sludge had been mineralized after one month of incubation in the soil. The collective results of my study reveal that application of post-fermentation sludge suppresses SOM decomposition, suggesting its use as a fertilizer could positively influence long-term soil quality. Finally, the success of the 13C natural abundance microcosm labeling approach in my study supports its use as an effective method of analyzing the effects of various fertilization techniques on soil nutrient retention

  10. Metal immobilization and phosphorus leaching after stabilization of pyrite ash contaminated soil by phosphate amendments.

    PubMed

    Zupančič, Marija; Lavrič, Simona; Bukovec, Peter

    2012-02-01

    In this study we would like to show the importance of a holistic approach to evaluation of chemical stabilization using phosphate amendments. An extensive evaluation of metal stabilization in contaminated soil and an evaluation of the leaching of phosphorus induced after treatment were performed. The soil was highly contaminated with Cu (2894 mg kg(-1)), Zn (3884 mg kg(-1)), As (247 mg kg(-1)), Cd (12.6 mg kg(-1)) and Pb (3154 mg kg(-1)). To immobilize the metals, mixtures of soil with phosphate (from H(3)PO(4) and hydroxyapatite (HA) with varying ratios) were prepared with a constant Pb : P molar ratio of 1: 10. The acetic acid extractable concentration of Pb in the mixture with the highest amount of added phosphoric acid (n(H(3)PO(4)) : n(HA) = 3 : 1) was reduced to 1.9% (0.62 mg L(-1)) of the extractable Pb concentration in the untreated soil, but the content of water extractable phosphorus in the samples increased from 0.04 mg L(-1) in the untreated soil sample up to 14.3 mg L(-1) in the same n(H(3)PO(4)) : n(HA) = 3 : 1 mixture. The high increase in arsenic mobility was also observed after phosphate addition. The PBET test showed phosphate induced reduction in Pb bioavailability. In attempting to stabilize Pb in the soil with the minimum treatment-induced leaching of phosphorus, it was found that a mixture of soil with phosphate addition in the molar ratio of H(3)PO(4) : HA of 0.75 : 1 showed the most promising results, with an acetic acid extractable Pb concentration of 1.35 mg L(-1) and a water extractable phosphorus concentration of 1.76 mg L(-1). The time-dependent leaching characteristics of metals and phosphorus for this mixture were evaluated by a column experiment, where irrigation of the soil mixture with the average annual amount of precipitation in Slovenia (1000 mm) was simulated. The phosphorus concentration in the leachates decreased from 2.60 mg L(-1) at the beginning of irrigation to 1.00 mg L(-1) at the end.

  11. The Effects of a High Magnetic Field on the Annealing of [(Fe0.5Co0.5)0.75B0.2Si0.05]96Nb₄ Bulk Metallic Glass.

    PubMed

    Jia, Peng; Wang, En-Gang; Han, Ke

    2016-11-04

    In contrast with amorphous alloys, nanocrystalline soft magnetic materials show improved thermal stability and higher soft magnetic properties. The nanocrystalline soft magnetic composites are usually fabricated by partially crystallizing from parent amorphous alloys. This paper reports our experimental observation on the sequence of crystallization in metallic glass under a high magnetic field (HMF). An application of a HMF to bulk metallic glass (BMG) of [(Fe0.5Co0.5)0.75B0.2Si0.05]96Nb₄ prioritizes the precipitation of α-(Fe,Co) phase separated from the subsequent precipitation of borides, (Fe,Co)23B₆, upon isothermal annealing at a glass transition temperature. Furthermore, it was observed that, through the annealing treatment under a HMF, a soft magnetic nanocomposite, in which only α-(Fe,Co) phase uniformly distributes in amorphous matrix, was achieved for boron-bearing BMG. The promotion of the α-Fe or (Fe,Co) phase and the prevention of the boride phases during the isothermal annealing process help to produce high-quality soft magnetic nanocomposite materials. The mechanism by which a HMF influences the crystallization sequence was interpreted via certain changes in Gibbs free energies for two ferromagnetic phases. This finding evidences that the annealing treatment under a HMF is suitable for enhancing the soft magnetic properties of high B content (Fe,Co)-based bulk amorphous and nanocrystalline materials.

  12. The Effects of a High Magnetic Field on the Annealing of [(Fe0.5Co0.5)0.75B0.2Si0.05]96Nb4 Bulk Metallic Glass

    PubMed Central

    Jia, Peng; Wang, En-gang; Han, Ke

    2016-01-01

    In contrast with amorphous alloys, nanocrystalline soft magnetic materials show improved thermal stability and higher soft magnetic properties. The nanocrystalline soft magnetic composites are usually fabricated by partially crystallizing from parent amorphous alloys. This paper reports our experimental observation on the sequence of crystallization in metallic glass under a high magnetic field (HMF). An application of a HMF to bulk metallic glass (BMG) of [(Fe0.5Co0.5)0.75B0.2Si0.05]96Nb4 prioritizes the precipitation of α-(Fe,Co) phase separated from the subsequent precipitation of borides, (Fe,Co)23B6, upon isothermal annealing at a glass transition temperature. Furthermore, it was observed that, through the annealing treatment under a HMF, a soft magnetic nanocomposite, in which only α-(Fe,Co) phase uniformly distributes in amorphous matrix, was achieved for boron-bearing BMG. The promotion of the α-Fe or (Fe,Co) phase and the prevention of the boride phases during the isothermal annealing process help to produce high-quality soft magnetic nanocomposite materials. The mechanism by which a HMF influences the crystallization sequence was interpreted via certain changes in Gibbs free energies for two ferromagnetic phases. This finding evidences that the annealing treatment under a HMF is suitable for enhancing the soft magnetic properties of high B content (Fe,Co)-based bulk amorphous and nanocrystalline materials. PMID:28774018

  13. Effect of High Configuration Entropy and Rare Earth Addition on Boride Precipitation and Mechanical Properties of Multi-principal-Element Alloys

    NASA Astrophysics Data System (ADS)

    Zhang, H.; Zhong, X. C.; He, Y. Z.; Li, W. H.; Wu, W. F.; Chen, G.; Guo, S.

    2017-08-01

    A series of multi-principal-element (MPE) alloys have been prepared by adding Ni, Mn, Al, Cu and Y into the reference CoCrFe-B alloy. The microstructure and mechanical properties of these MPE alloys have been investigated thoroughly. It is found that the addition of the elements can inhibit boride precipitation in the designed alloys and the solid solution strengthening effect induced by interstitial boron atoms is more significant than that by boride precipitation. The MPE alloys with the fcc phase as the main solid solution phase have a higher boron solubility and hence less boride precipitation, than those with the bcc phase as the main solid solution phase. The addition of yttrium can improve the boron solubility, decrease boride precipitation, control the boride morphology and, importantly, simultaneously improve the compressive strength and ductility of boron-containing MPE alloys.

  14. Stabilization of dissolved trace metals at hydrothermal vent sites: Impact on their marine biogeochemical cycles

    NASA Astrophysics Data System (ADS)

    Sander, Sylvia G.; Powell, Zach D.; Koschinsky, Andrea; Kuzmanovski, Stefan; Kleint, Charlotte

    2014-05-01

    Hydrothermal vents have long been neglected as a significant source of several bioactive trace metals as it was assumed that elements such as Fe, Mn, and Cu etc., precipitate in extensor forming poly-metallic sulfide and oxy-hydroxy sediments in the relative vicinity of the emanation site. However, recently this paradigm has been reviewed since the stabilization of dissolved Fe and Cu from hydrothermal vents was observed [1, 2] and increased concentrations of trace metals can be traced from their hydrothermal source thousands of kilometres through the ocean basins [3]. Furthermore several independent modelling attempts have shown that not only a stabilization of dissolved hydrothermal Fe and Cu is possible [4] but also that hydrothermalism must be a significant source of Fe to be able to balance the Fe-biogeochemical cycle [5]. Here we present new data that gives further evidence of the presence of copper stabilising organic and inorganic compounds in samples characterized by hydrothermal input. We can show that there are systematic differences in copper-complexing ligands at different vent sites such as 5°S on the Mid Atlantic Ridge, Brother Volcano on the Kermadec Arc, and some shallow hydrothermal CO2 seeps in the Bay of Plenty, New Zealand and the Mediterranean Sea. Quantitative and qualitative voltammetric data convincingly indicates that inorganic sulphur and organic thiols form the majority of the strong copper-complexing ligand pool in many of these hydrothermal samples. On average, the high temperature vents had a significantly higher copper binding capacity than the diffuse vents due to higher inorganic sulphur species concentrations. References: [1] Sander, S. G., et al. 2007. Organic complexation of copper in deep-sea hydrothermal vent systems. Environmental Chemistry 4: 81-89 [2] Bennett, S. A., et al. 2008. The distribution and stabilisation of dissolved Fe in deep-sea hydrothermal plumes. Earth and Planetary Science Letters 270: 157-167. [3] Wu J

  15. A test of the transition-metal nanocluster formation and stabilization ability of the most common polymeric stabilizer, poly(vinylpyrrolidone), as well as four other polymeric protectants.

    PubMed

    Ott, Lisa Starkey; Hornstein, Brooks J; Finke, Richard G

    2006-10-24

    Following an introduction to the nanocluster stabilization literature and DLVO (Derjaugin-Landau-Verwey-Overbeek) theory of colloidal stability, the most common steric stabilizer of transition-metal nanoclusters, poly(vinylpyrrolidone) (PVP), has been examined for its efficacy in the formation, stabilization, and subsequent catalytic activity of prototype, test case Ir(0)n nanoclusters. First, the five criteria established previously for ranking nanocluster protectants for their nanocluster formation and stabilization ability were evaluated for 1 monomer equiv of 10000 average molecular weight (MWav) PVP in the absence, and then presence, of the traditionally weakly coordinating anion BF4- as well as the absence and presence of the strongly coordinating, superior anionic stabilizer P2W15Nb3O62(9-), all in propylene carbonate solvent. It is found that neither 1 equiv of BF4- in propylene carbonate nor 1 monomer equiv of (undried) PVP alone allows for isolable and redissolvable nanoclusters without bulk Ir(0)n metal formation. Careful predrying of the PVP, and by implication other polymers, is shown to be necessary for the formation and stabilization of the nanoclusters. Next, 40 monomer equiv of 10000 MWav PVP and 1 equiv of BF4- in propylene carbonate are shown to allow isolable, redissolvable nanoclusters. Control experiments reveal little difference on nanocluster stabilization by 3500 or 55000 (i.e., vs 10,000) MWav PVP, but yield interesting effects on nanocluster nucleation by the 3500 MWav PVP, as well as by the polymer poly(bis(ethoxy)phosphazene) (PBEP). Four other key polymers reported in the literature to be nanocluster stabilizers are tested by the five criteria method for their efficacy in the formation and stabilization of Ir0n nanoclusters (now in acetone due to the polymers' solubility) and in comparison to each other, specifically, poly(methyl methacrylate) (PMMA), poly(styrene) (PS), poly(methylhydrosilane) (PMHS), and PBEP. Only 40 monomer equiv

  16. Effects of modified zeolite on the removal and stabilization of heavy metals in contaminated lake sediment using BCR sequential extraction.

    PubMed

    Wen, Jia; Yi, Yuanjie; Zeng, Guangming

    2016-08-01

    Sediment can be applied on land as a soil conditioner. However, toxic substances such as heavy metals within the sediment often lead to soil contamination if no proper management is conducted prior to land application. In order to reduce the bioavailable portion of heavy metals such as Pb, Cu, Zn and Cd, zeolite as a kind of stabilizer was investigated on the effect of metal stabilization in sediment. Zeolite was firstly modified and screened to get the best condition for removal of heavy metals. Results showed that the granulated zeolite with NaCl conditioning had the highest CEC and metal sorption. Using BCR sequential extraction, the selected modified zeolite effectively stabilized Pb, Cu, Zn and Cd in sediment to different extents. It was most suitable for Cd stabilization by reducing its acid exchangeable fraction while increasing the contents of the reducible and residual fractions. Modified zeolite also immobilized Cu, Zn and Pb in sediment by enhancing one stable fraction while decreasing the acid exchangeable fraction. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Scalable process for application of stabilized lithium metal powder in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Ai, Guo; Wang, Zhihui; Zhao, Hui; Mao, Wenfeng; Fu, Yanbao; Yi, Ran; Gao, Yue; Battaglia, Vincent; Wang, Donghai; Lopatin, Sergey; Liu, Gao

    2016-03-01

    A simple solution processing method is developed to achieve a uniform and scalable stabilized lithium metal powder (SLMP) coating on a Li-ion negative electrode. A solvent and binder system for the SLMP coating is developed, including the selection of solvent, polymer binder, and optimization of polymer concentration. The optimized binder solution is a 1% concentration of polymer binder in xylene; a mixture of poly(styrene-co-butadiene) rubber (SBR) and polystyrene (PS) is chosen as the polymer binder. Results show that long-sustained, uniformly dispersed SLMP suspension can be achieved with the optimized binder solution. The uniform SLMP coating can be achieved using a simple "doctor blade" coating method, and the resulting SLMP coating can be firmly glued on the anode surface. By using SLMP to prelithiate the negative electrode, improvements in electrochemical performances are demonstrated in both graphite/NMC and SiO/NMC full cells.

  18. Stability and aggregation of metal oxide nanoparticles in natural aqueous matrices.

    PubMed

    Keller, Arturo A; Wang, Hongtao; Zhou, Dongxu; Lenihan, Hunter S; Cherr, Gary; Cardinale, Bradley J; Miller, Robert; Ji, Zhaoxia

    2010-03-15

    There is a pressing need for information on the mobility of nanoparticles in the complex aqueous matrices found in realistic environmental conditions. We dispersed three different metal oxide nanoparticles (TiO(2), ZnO and CeO(2)) in samples taken from eight different aqueous media associated with seawater, lagoon, river, and groundwater, and measured their electrophoretic mobility, state of aggregation, and rate of sedimentation. The electrophoretic mobility of the particles in a given aqueous media was dominated by the presence of natural organic matter (NOM) and ionic strength, and independent of pH. NOM adsorbed onto these nanoparticles significantly reduces their aggregation, stabilizing them under many conditions. The transition from reaction to diffusion limited aggregation occurs at an electrophoretic mobility from around -2 to -0.8 microm s(-1) V(-1) cm. These results are key for designing and interpreting nanoparticle ecotoxicity studies in various environmental conditions.

  19. Copper benzene tricarboxylate metal-organic framework with wide permanent mesopores stabilized by Keggin polyoxometallate ions.

    PubMed

    Wee, Lik H; Wiktor, Christian; Turner, Stuart; Vanderlinden, Willem; Janssens, Nikki; Bajpe, Sneha R; Houthoofd, Kristof; Van Tendeloo, Gustaaf; De Feyter, Steven; Kirschhock, Christine E A; Martens, Johan A

    2012-07-04

    Porous solids with organized multiple porosity are of scientific and technological importance for broadening the application range from traditional areas of catalysis and adsorption/separation to drug release and biomedical imaging. Synthesis of crystalline porous materials offering a network of uniform micro- and mesopores remains a major scientific challenge. One strategy is based on variation of synthesis parameters of microporous networks, such as, for example, zeolites or metal-organic frameworks (MOFs). Here, we show the rational development of an hierarchical variant of the microporous cubic Cu(3)(BTC)(2) (BTC = 1,3,5-benzenetricarboxylate) HKUST-1 MOF having strictly repetitive 5 nm wide mesopores separated by uniform microporous walls in a single crystal structure. This new material coined COK-15 (COK = Centrum voor Oppervlaktechemie en Katalyse) was synthesized via a dual-templating approach. Stability was enhanced by Keggin type phosphotungstate (HPW) systematically occluded in the cavities constituting the walls between the mesopores.

  20. Does Increased Coefficient of Friction of Highly Porous Metal Increase Initial Stability at the Acetabular Interface?

    PubMed

    Goldman, Ashton H; Armstrong, Lucas C; Owen, John R; Wayne, Jennifer S; Jiranek, William A

    2016-03-01

    Highly porous metal acetabular components illustrate a decreased rate of aseptic loosening in short-term follow-up compared with previous registry data. This study compared the effect of component surface roughness at the bone-implant interface and the quality of the bone on initial pressfit stability. The null hypothesis is that a standard porous coated acetabular cup would show no difference in initial stability as compared with a highly porous acetabular cup when subjected to a bending moment. Second, would bone mineral density (BMD) be a significant variable under these test conditions. In a cadaveric model, acetabular cup micromotion was measured during a 1-time cantilever bending moment applied to 2 generations of pressfit acetabular components. BMD data were also obtained from the femoral necks available for associated specimen. The mean bending moment at 150 μm was not found to be significantly different for Gription (24.6 ± 14.0 N m) cups vs Porocoat (25 ± 10.2 N m; P > .84). The peak bending moment tolerated by Gription cups (33.9 ± 20.3 N m) was not found to be significantly different from Porocoat (33.5 ± 12.2 N m; P > .92). No correlation between BMD and bending moment at 150 μm of displacement could be identified. The coefficient of friction provided by highly porous metal acetabular shells used in this study did not provide better resistance to migration under bending load when compared with a standard porous coated component. Copyright © 2016 Elsevier Inc. All rights reserved.

  1. [Comparison of fixation effects of heavy metals between cement rotary kiln co-processing and cement solidification/stabilization].

    PubMed

    Zhang, Jun-li; Liu, Jian-guo; Li, Cheng; Jin, Yi-ying; Nie, Yong-feng

    2008-04-01

    Both cement rotary kiln co-processing hazardous wastes and cement solidification/stabilization could dispose heavy metals by fixation. Different fixation mechanisms lead to different fixation effects. The same amount of heavy metal compounds containing As, Cd, Cr, Cu, Pb, Zn were treated by the two kinds of fixation technologies. GB leaching test, TCLP tests and sequential extraction procedures were employed to compare the fixation effects of two fixation technologies. The leached concentration and chemical species distribution of heavy metals in two grounded mortar samples were analyzed and the fixation effects of two kinds of technologies to different heavy metals were compared. The results show the fixation effect of cement rotary kiln co-processing technology is better than cement solidification/stabilization technology to As, Pb, Zn. Calcinations in cement rotary kiln and then hydration help As, Pb, Zn contained in hazardous wastes transform to more steady chemical species and effectively dispose these heavy metals compounds. Cr3+ is liable to be converted to much more toxic and more mobile Cr6+ state in cement rotary kiln. And so Cr wastes are more fit for treatment by cement solidification/stabilization technology. The work could provide a basis when choosing disposal technologies for different heavy metals and be helpful to improve the application and development of cement rotary kiln co-processing hazardous wastes.

  2. Stabilization of metals in acidic mine spoil with amendments and red fescue (Festuca rubra L.) growth.

    PubMed

    Simon, László

    2005-12-01

    Stabilization of metals with amendments and red fescue (Festuca rubra, cv. Keszthelyi 2) growth was studied on an acidic and phytotoxic mine spoil (pH(KCl) 3.20-3.26; Cd 7.1 mg kg(-1), Cu 120 mg kg(-1), Pb 2154 mg kg(-1) and Zn 605 mg kg(-1)) from Gyöngyösoroszi, Hungary in a pot experiment. Raising the pH above 5.0 by lime (CaCO(3)), and supplementing with 40 mg kg(-1)nitrogen (NH(4)NO(3)) made this material suitable for plant growth. All cultures were limed with 0.5% (m/m) CaCO(3) (treatment 1), which was combined with 5% (m/m) municipal sewage sludge compost (treatment 2), 5% (m/m) peat (treatment 3), 7.5% (m/m) natural zeolite (clinoptilolite) (treatment 4), and 0.5 (m/m) KH(2)PO(4) (treatment 5). Treatments 1-5 were combined with each other (treatment 6). After 60 days of red fescue growth, pH of the limed mine spoil decreased in all cultures units. Application of peat caused the highest pH decrease (1.15), while decrease of pH was less than 0.23 in treatments 2, 5 or 6. Application of lime significantly reduced concentrations of metals in the 'plant available' fraction of mine spoil compared to non-limed mine spoil. Amendments added to limed mine spoil changed variously the ratio of Cd, Cu, Pb and Zn in exchangeable or 'plant available' fractions, differently influencing the phytoavailability of these metals. Most of the metals were captured in the roots of test plants. Treatment 2 caused the appearance of less Cd in shoots (<0.1 microg g(-1)) or roots (3.11 microg g(-1)), while treatment 5 resulted in the highest Cd concentration (2.13 microg g(-1)) in shoots. Treatments did not influence significantly the Cu accumulation in shoots. The Pb accumulation of roots (44.7 microg g(-1)) was most effectively inhibited by combined treatment, while the highest value (136 microg g(-1)) was found in the culture treated with potassium phosphate. Pb concentration in shoots was below the detection limit, except for treatments 5 and 6. Peat application resulted in higher

  3. Investigation of the fracture mechanics of boride composites

    NASA Technical Reports Server (NTRS)

    Clougherty, E. V.; Pober, R. L.; Kaufman, L.

    1972-01-01

    Significant results were obtained in fabrication studies of the role of metallic additives of Zr, Ti, Ni, Fe and Cr on the densification of ZrB2. All elemental additions lower the processing temperatures required to effect full densification of ZrB2. Each addition effects enhanced densification by a clearly distinguishable and different mechanism and the resulting fabricated materials are different. A significant improvement in strength and fracture toughness was obtained for the ZrB2/Ti composition. Mechanical characterization studies for the ZrB2/SiC/C composites and the new ZrB2/Metal materials produced data relevant to the effect of impacting load on measured impact energies, a specimen configuration for which controlled fracture could occur in a suitably hard testing apparatus, and fracture strength data. Controlled fracture--indicative of measurable fracture toughness--was obtained for the ZrB2-SiC-C composite, and a ZrB2/Ti composite fabricated from ZrB2 with an addition of 30 weight per cent Ti. The increased strength and toughness of the ZrB2/Ti composite is consistent with the presence of a significantly large amount of a fine grained acicular phase formed by reaction of Ti with ZrB2 during processing.

  4. Surface half-metallicity and stability of zinc-blende sodium monoselenide

    NASA Astrophysics Data System (ADS)

    Tabatabaeifar, A.; Davatolhagh, S.; Moradi, M.

    2017-02-01

    The electronic structure and magnetic properties of relaxed (001) surfaces of the sp-electron half-metallic ferromagnet NaSe in the zinc-blende phase, are calculated on the basis of first principle density functional theory within the framework of self-consistent field plane wave pseudo-potential method, using the generalized gradient approximation for the exchange-correlation functional. The results of this study reveal that both Na- and Se-terminated surfaces retain the robust bulk half-metallic property. The negative value found for the bulk formation energy indicates that this material is stable against phase separation. We also obtain the surface energies and discuss their stability via the calculated bulk formation energy. The Curie temperature is estimated to be 920 K within mean field approximation, which is well above the room temperature. In the light of the above, zinc-blende NaSe appears to be a good candidate for spintronic applications as spin injection material.

  5. Kinetic and Thermodynamic Stabilization of Metal Complexes by Introverted Coordination in a Calix[6]azacryptand.

    PubMed

    Inthasot, Alex; Brunetti, Emilio; Lejeune, Manuel; Menard, Nicolas; Prangé, Thierry; Fusaro, Luca; Bruylants, Gilles; Reinaud, Olivia; Luhmer, Michel; Jabin, Ivan; Colasson, Benoit

    2016-03-24

    The Huisgen thermal reaction between an organic azide and an acetylene was employed for the selective monofunctionalization of a X6 -azacryptand ligand bearing a tren coordinating unit [X6 stands for calix[6]arene and tren for tris(2-aminoethyl)amine]. Supramolecular assistance, originating from the formation of a host-guest inclusion complex between the reactants, greatly accelerates the reaction while self-inhibition affords a remarkable selectivity. The new ligand possesses a single amino-leg appended at the large rim of the calixarene core and the corresponding Zn(2+) complex was characterized both in solution and in the solid state. The coordination of Zn(2+) not only involves the tren cap but also the introverted amino-leg, which locks the metal ion in the cavity. Compared with the parent ligand deprived of the amino-leg, the affinity of the new monofunctionalized X6 tren ligand 6 for Zn(2+) is found to have a 10-fold increase in DMSO, which is a very competitive solvent, and with an enhancement of at least three orders of magnitude in CDCl3 /CD3 OD (1:1, v/v). In strong contrast with the fast binding kinetics, decoordination of Zn(2+) as well as transmetallation appeared to be very slow processes. The monofunctionalized X6 tren ligand 6 fully protects the metal ion from the external medium thanks to the combination of a cavity and a closed coordination sphere, leading to greater thermodynamic and kinetic stabilities.

  6. Zinc-blende half-metallic ferromagnets are rarely stabilized by coherent epitaxy

    NASA Astrophysics Data System (ADS)

    Zhao, Yu-Jun; Zunger, Alex

    2005-04-01

    The need for spin-injectors having the same zinc-blende-type crystal structure as conventional semiconductor substrates has created significant interests in theoretical predictions of possible metastable “half-metallic” zinc-blende ferromagnets, which are normally more stable in other structure-types, e.g., NiAs. Such predictions were based in the past on differences Δbulk in the total energies of the respective bulk crystal forms (zinc blende and NiAs). We show here that the appropriate criterion is comparing difference Δepi(as) in epitaxial total energies. This reveals that even if Δbulk is small, still for MnAs, CrSb, CrAs, CrTe, Δepi(as)>0 for all substrate lattice constant as , so the zinc-blende phase is not stabilized. For CrS we find Δepi(as)<0 , but the system is antiferromagnetic, thus not half-metallic. Finally, zinc-blende CrSe is predicted to be epitaxially stable for as>6.2Å and is half metallic.

  7. Radiological Stability after Revision of Infected Total Knee Arthroplasty Using Modular Metal Augments

    PubMed Central

    Lee, Kyung-Jae; Cho, Chul-Hyun; Son, Eun-Seok; Jung, Jae-Won

    2016-01-01

    Purpose To evaluate the radiological stability according to the number of modular augments after revision of infected total knee arthroplasty (TKA). Materials and Methods Between February 2006 and September 2013, 37 patients (39 knees) followed ≥2 years after revision of infected TKA using modular metal augments for bone defects were reviewed retrospectively. We divided the patients into 3 groups according to the number of augments into group A (≤2 augments, 14 knees), group B (3–4 augments, 18 knees), and group C (5≥ augments, 7 knees) and evaluated the width of radiolucent zones around the implant at the last follow-up. Results There were 3 Anderson Orthopedic Research Institute type I, 33 type II, and 3 type III bone defects. The mean number of radiolucent zones of group A was 3 and the sum of width averaged 4.4 mm. In group B, the values were 4.8 and 6.2 mm, respectively. In group C, the values were 8.1 and 12.9 mm, respectively. The differences between the three groups were statistically significant. Conclusions In revision TKA with modular metal augmentation caused by infected TKA, increased modularity can result in radiological instability. PMID:26955613

  8. Thermal Stability of Copper-Aluminum Alloy Thin Films for Barrierless Copper Metallization on Silicon Substrate

    NASA Astrophysics Data System (ADS)

    Wang, C. P.; Dai, T.; Lu, Y.; Shi, Z.; Ruan, J. J.; Guo, Y. H.; Liu, X. J.

    2017-08-01

    Copper thin films with thickness of about 500 nm doped with different aluminum concentrations have been prepared by magnetron sputtering on Si substrate and their crystal structure, microstructure, and electrical resistivity after annealing at various temperatures (200°C to 600°C) for 1 h or at 400°C for different durations (1 h to 11 h) investigated by grazing-incidence x-ray diffraction (GIXRD) analysis, scanning electron microscopy (SEM), and four-point probe (FPP) measurements. Cu-1.8Al alloy thin film exhibited good thermal stability and low electrical resistivity (˜5.0 μΩ cm) after annealing at 500°C for 1 h or 400°C for 7 h. No copper silicide was observed at the Cu-Al/Si interface by GIXRD analysis or SEM for this sample. This result indicates that doping Cu thin film with small amounts of Al can achieve high thermal stability and low electrical resistivity, suggesting that Cu-1.8Al alloy thin film could be used for barrierless Cu metallization on Si substrate.

  9. Dimensional accuracy and stability of polymethyl methacrylate reinforced with metal wire or with continuous glass fiber.

    PubMed

    Vallittu, P K

    1996-06-01

    The aim of this study was to determine the dimensional accuracy and stability of denture base polymethyl methacrylate (PMMA), which was reinforced in various ways. Autopolymerizing PMMA and heat-cured PMMA were reinforced either with semicircular steel wire or with a prefabricated experimental reinforcement made of continuous E-glass fiber. Control specimens had no reinforcement. The width of each U-shaped test specimen was measured with a digital micrometer under a light microscope immediately after the test specimen was cured and when stored in water for 1, 2, 7, and 14 days. The results revealed that both the type of PMMA and the type of reinforcement affected the dimensional accuracy of the test specimens, especially after 7 and 14 days in water storage (p < 0.001). The greatest dimensional accuracy was found with the unreinforced test specimen made from autopolymerizing PMMA and with test specimens reinforced with the metal wire made from heat-cured PMMA. In terms of the width of the test specimens, the lowest dimensional accuracy was found in unreinforced and glass fiber reinforced specimens made from heat-cured PMMA. Storage in water did not affect the stability of the width (p > 0.1). The results suggest that the polymerization shrinkage of PMMA causes lower dimensional accuracy of the test specimens reinforced with glass fiber. This should be considered when glass-fiber reinforcement is used clinically.

  10. Highly stabilized gadolinium chelates functionalized on metal nanoparticles as magnetic resonance imaging contrast agent

    NASA Astrophysics Data System (ADS)

    Siddiqui, Talha S.

    Magnetic resonance imaging (MRI) is a non-invasive method for imaging and diagnosing tissue damage, organ function and the vascular system. Magnevist(TM) a complex of diethylenetriaminepentaacetic acid (DTPA) and Gd3+ is a clinically approved contrast agent for MRI. A derivative of DTPA was formed by the addition of two cysteine groups (DTPA-L-Cys) through amide linkage. The Gd complex of this ligand bonds with the silver surfaces through the cysteine thiols. GdDTPA-L-Cys was bound to ˜10nm diameter Ag nanoparticles for use as a multifunctional MRI contrast agent. The ligand and complex were characterized by 1H and 13C NMR, ESI-MS and IR spectroscopy. The silver construct was characterized by TEM, TGA and UV-Vis absorption spectra. The per metal complex r1 relaxivity of GdDTPA-L-Cys{Ag} greater than that of Magnavist(TM) with the same molarity for both compounds. The synthesis of a DTPA derivative is described that allows it to bind to silver or gold nanoparticles through a single thiol linkage (DTPASH). The resulting Gd complex, GdDTPASH, was bound to Ag nanoparticles to create a single monolayer on the surface. The construct was further stabilized in buffered solution with the addition of a thiolated PEG chain. The highly stabilized nanoparticle construct delivers a high payload of Gd compelex and is an effective T1 brightening agent. The production of this type of construct opens the way for engineered multimodal MRI contrast agents.

  11. Hydrogen segregation and its roles in structural stability and metallization: silane under pressure

    NASA Astrophysics Data System (ADS)

    Cui, Wenwen; Shi, Jingming; Liu, Hanyu; Yao, Yansun; Wang, Hui; Iitaka, Toshiaki; Ma, Yanming

    2015-08-01

    We present results from first-principles calculations on silane (SiH4) under pressure. We find that a three dimensional P-3 structure becomes the most stable phase above 241 GPa. A prominent structural feature, which separates the P-3 structure from previously observed/predicted SiH4 structures, is that a fraction of hydrogen leaves the Si-H bonding environment and forms segregated H2 units. The H2 units are sparsely populated in the system and intercalated with a polymeric Si-H framework. Calculations of enthalpy of formation suggest that the P-3 structure is against the decomposition into Si-H binaries and/or the elemental crystals. Structural stability of the P-3 structure is attributed to the electron-deficient multicenter Si-H-Si interactions when neighboring silicon atoms are linked together through a common hydrogen atom. Within the multicenter bonds, electrons are delocalized and this leads to a metallic state, possibly also a superconducting state, for SiH4. An interesting outcome of the present study is that the enthalpy sum of SiH4 (P-3 structure) and Si (fcc structure) appears to be lower than the enthalpy of disilane (Si2H6) between 200 and 300 GPa (for all previously predicted crystalline forms of Si2H6), which calls for a revisit of the stability of Si2H6 under high pressure.

  12. Hydrogen segregation and its roles in structural stability and metallization: silane under pressure

    PubMed Central

    Cui, Wenwen; Shi, Jingming; Liu, Hanyu; Yao, Yansun; Wang, Hui; Iitaka, Toshiaki; Ma, Yanming

    2015-01-01

    We present results from first-principles calculations on silane (SiH4) under pressure. We find that a three dimensional P-3 structure becomes the most stable phase above 241 GPa. A prominent structural feature, which separates the P-3 structure from previously observed/predicted SiH4 structures, is that a fraction of hydrogen leaves the Si-H bonding environment and forms segregated H2 units. The H2 units are sparsely populated in the system and intercalated with a polymeric Si-H framework. Calculations of enthalpy of formation suggest that the P-3 structure is against the decomposition into Si-H binaries and/or the elemental crystals. Structural stability of the P-3 structure is attributed to the electron-deficient multicenter Si-H-Si interactions when neighboring silicon atoms are linked together through a common hydrogen atom. Within the multicenter bonds, electrons are delocalized and this leads to a metallic state, possibly also a superconducting state, for SiH4. An interesting outcome of the present study is that the enthalpy sum of SiH4 (P-3 structure) and Si (fcc structure) appears to be lower than the enthalpy of disilane (Si2H6) between 200 and 300 GPa (for all previously predicted crystalline forms of Si2H6), which calls for a revisit of the stability of Si2H6 under high pressure. PMID:26266340

  13. Hydrogen segregation and its roles in structural stability and metallization: silane under pressure.

    PubMed

    Cui, Wenwen; Shi, Jingming; Liu, Hanyu; Yao, Yansun; Wang, Hui; Iitaka, Toshiaki; Ma, Yanming

    2015-08-12

    We present results from first-principles calculations on silane (SiH4) under pressure. We find that a three dimensional P-3 structure becomes the most stable phase above 241 GPa. A prominent structural feature, which separates the P-3 structure from previously observed/predicted SiH4 structures, is that a fraction of hydrogen leaves the Si-H bonding environment and forms segregated H2 units. The H2 units are sparsely populated in the system and intercalated with a polymeric Si-H framework. Calculations of enthalpy of formation suggest that the P-3 structure is against the decomposition into Si-H binaries and/or the elemental crystals. Structural stability of the P-3 structure is attributed to the electron-deficient multicenter Si-H-Si interactions when neighboring silicon atoms are linked together through a common hydrogen atom. Within the multicenter bonds, electrons are delocalized and this leads to a metallic state, possibly also a superconducting state, for SiH4. An interesting outcome of the present study is that the enthalpy sum of SiH4 (P-3 structure) and Si (fcc structure) appears to be lower than the enthalpy of disilane (Si2H6) between 200 and 300 GPa (for all previously predicted crystalline forms of Si2H6), which calls for a revisit of the stability of Si2H6 under high pressure.

  14. Peroxidase-Mimicking Nanozyme with Enhanced Activity and High Stability based on Metal-Support Interaction.

    PubMed

    Li, Zhihao; Yang, Xiangdong; Yang, Yanbing; Tan, Yaning; He, Yue; Liu, Meng; Liu, Xinwen; Yuan, Quan

    2017-10-09

    Peroxidase-mimicking nanozyme offers unique advantages of high stability and low cost over natural peroxidase for applications in bioanalysis, biomedicine and pollution treatment. However, the design of high-efficiency peroxidase-mimicking nanozymes remains a grand challenge. In this work, we adopted a structural design approach through hybridization of cube-CeO2 and Pt nanoparticles to create a novel peroxidase-mimicking nanozyme with high efficiency and excellent stability. Compared to pure cube-CeO2 and Pt nanoparticles, the as-hybridized Pt/cube-CeO2 nanocomposites display much improved activity because of the strong metal-support interaction. Meanwhile, the nanocomposites also maintain high catalytic activity after long-term storage and several-time recycle. Based on their excellent properties, Pt/cube-CeO2 nanocomposites were used to construct high-performance colorimetric biosensors for the sensitive detection of metabolites including H2O2 and glucose. Our findings highlight opportunities for the development of high-efficiency peroxidase-mimicking nanozyme with potentially various applications in diagnostic, biomedicine and pollution treatment. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Stabilization and highly metallic properties of heavy group-V hydrides at high pressures

    NASA Astrophysics Data System (ADS)

    Abe, Kazutaka; Ashcroft, N. W.

    2015-12-01

    Compressed hydrides of the heavy group-15 elements Bi and Sb are investigated using ab initio methods. While the hydrides of Bi and Sb are known to be quite unstable at one atmosphere, our calculations predict that they can be stabilized at high pressures. Thus, at the composition of XH 3 (X =Bi or Sb), possible Bi hydrides are BiH2(P n m a ) + H beyond 105 GPa and BiH3(I 41/a m d ) beyond 250 GPa; for Sb hydrides, SbH2 + H hardly appears, and SbH3(P n m a ) is stabilized beyond 150 GPa. All of these hydrides are metallic with very dispersive electronic structures, this being in accordance with the predictions of the Goldhammer-Herzfeld criterion. Superconducting transition temperatures have also been estimated from the extended McMillan equation, and they turn out to be 39 K for BiH2 at 125 GPa, 65 K for BiH3 at 270 GPa, and 68 K for SbH3 at 170 GPa.

  16. Heavy metal stabilization by means of innovative alumino-silicate matrix.

    PubMed

    Cioffi, R; Pagliuca, C; Santoro, L; Verdolotti, L

    2003-05-01

    Powdered tuff mixed with NaOH solution has been hydrothermally cured at temperatures ranging from 90 to 150 degrees C. Hardening takes place due to the formation of an amorphous binding phase. At the lowest temperature tested a non-autoclaved process can be carried out. Values of unconfined compressive strength were found to vary from 15.5 MPa to 28.9 MPa depending on reaction conditions. The matrix was tested as a binder for the stabilization of model systems containing cadmium, chromium and lead and for a real system containing a secondary lead smelter slag. The stabilization process was tested from both the environmental and technological points of view by means of leahcing tests and compressive strength measurement. Basic characterization leaching tests carried out with the model systems showed that metal release from hardened paste is below 1%. Compliance leaching test carried out with the real system showed that lead release is below the limit set by law. From the technological pont of view, it was found that unconfined compressive strength is always higher for the real system. Specifically, this system showed compressive strength increasing with slag content to values exceeding 86.5 MPa.

  17. Improvement in Thermal Stability of Sucralose by γ-Cyclodextrin Metal-Organic Frameworks.

    PubMed

    Lv, Nana; Guo, Tao; Liu, Botao; Wang, Caifen; Singh, Vikaramjeet; Xu, Xiaonan; Li, Xue; Chen, Dawei; Gref, Ruxandra; Zhang, Jiwen

    2017-02-01

    To explain thermal stability enhancement of an organic compound, sucralose, with cyclodextrin based metal organic frameworks. Micron and nanometer sized basic CD-MOFs were successfully synthesized by a modified vapor diffusion method and further neutralized with glacial acetic acid. Sucralose was loaded into CD-MOFs by incubating CD-MOFs with sucralose ethanol solutions. Thermal stabilities of sucralose-loaded basic CD-MOFs and neutralized CD-MOFs were investigated using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and high performance liquid chromatography with evaporative light-scattering detection (HPLC-ELSD). Scanning electron microscopy (SEM) and powder X-ray diffraction (PXRD) results showed that basic CD-MOFs were cubic crystals with smooth surface and uniform sizes. The basic CD-MOFs maintained their crystalline structure after neutralization. HPLC-ELSD analysis indicated that the CD-MOF crystal size had significant influence on sucralose loading (SL). The maximal SL of micron CD-MOFs (CD-MOF-Micro) was 17.5 ± 0.9% (w/w). In contrast, 27.9 ± 1.4% of sucralose could be loaded in nanometer-sized basic CD-MOFs (CD-MOF-Nano). Molecular docking modeling showed that sucralose molecules preferentially located inside the cavities of γ-CDs pairs in CD-MOFs. Raw sucralose decomposed fast at 90°C, with 86.2 ± 0.2% of the compound degraded within only 1 h. Remarkably, sucralose stability was dramatically improved after loading in neutralized CD-MOFs, with only 13.7 ± 0.7% degradation at 90°C within 24 h. CD-MOFs efficiently incorporated sucralose and maintained its integrity upon heating at elevated temperatures.

  18. Intrinsic air stability mechanisms of two-dimensional transition metal dichalcogenide surfaces: basal versus edge oxidation

    NASA Astrophysics Data System (ADS)

    Longo, Roberto C.; Addou, Rafik; KC, Santosh; Noh, Ji-Young; Smyth, Christopher M.; Barrera, Diego; Zhang, Chenxi; Hsu, Julia W. P.; Wallace, Robert M.; Cho, Kyeongjae

    2017-06-01

    Layered transition metal dichalcogenides (TMDs) are being considered as a promising alternative channel material in ultra-thin and low power nanoelectronics, due to the significant tunability of their electronic properties via mechanisms such as mechanical strain, control of the material thickness, application of an external field, impurities, doping, alloying, or altering the substrate nature. Initially, monolayer TMDs as counterparts to graphene captured the attention of the scientific community owing to their semiconductor nature with sizable band gaps. However, certain physical and chemical properties of TMDs, such as their oxygen reactivity and stability in air need to be more completely understood in order to crystallize the promising superior performance of TMD-based electronic devices. Here, a comparative analysis of the stability of various TMDs (MX2: \\text{M}=\\text{Mo} , W; \\text{X}=\\text{S} , Se) in air is performed using density-functional theory (DFT) as well as x-ray photoelectron spectroscopy (XPS). We find that the surface chemistry of the basal plane of sulfides and selenides is relatively stable in air although for completely different reasons, which can be explained by investigating oxygen dissociative adsorption kinetics and thermodynamics. On the contrary, the edge of MX2 nanoribbons shows strong driving forces towards O2 dissociation and chemisorption. Our combined theoretical and experimental investigation reveals that the air stability of TMDs should not be placed in the same footing that other 2D materials, like graphene. Thus, this work highlights the importance of having controlled oxygen environment during crystal exfoliation/growth and defect passivation in order to provide high quality uniform materials for TMD-based device fabrication.

  19. Color stability of glass-fiber-reinforced polypropylene for non-metal clasp dentures.

    PubMed

    Nagakura, Manamu; Tanimoto, Yasuhiro; Nishiyama, Norihiro

    2017-07-04

    The purpose of this study was to investigate the color stability of a glass-fiber-reinforced thermoplastic (GFRTP), for use in non-metal clasp dentures (NMCDs). GFRTPs composed of E-glass fibers and polypropylene with 2 mass% of pigments were fabricated using injection molding. According to our previous study on the optimum fiber content for GFRTPs, we prepared GFRTPs with fiber contents of 0, 10, and 20 mass% (GF0, GF10, and GF20). Commercially available NMCD and PMMA materials were used as controls. The color changes of GFRTPs at 24h, and at 1, 2, and 4 weeks of coffee immersion at 37°C were measured by colorimetry, using the Commission Internationale de l'Eclairage (CIE) Lab system. The color stabilities of the GFRTPs were evaluated in two units: the color difference (ΔE(∗)) and National Bureau of Standards (NBS) units. After immersion, none of the GFRTPs showed visible color change. From the colorimetry measurement using the CIE Lab system, the ΔE(∗) values of the GFRTPs were 0.65-2.45. The NBS values of the GFRTPs were 0.60-2.25, all lower than the threshold level of 3.0, demonstrating clinically acceptable color changes. On the other hand, an available polyamide-based NMCD material exhibited "appreciable" color change, as measured in NBS units. The results indicate that the GFRTPs showed clinically acceptable color stability and might be satisfactory for clinical use. Therefore, GFRTPs are expected to become attractive materials for esthetic dentures. Copyright © 2017 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

  20. Synthesis and characterization of functionalized ionic liquid-stabilized metal (gold and platinum) nanoparticles and metal nanoparticle/carbon nanotube hybrids.

    PubMed

    Zhang, Hao; Cui, Hua

    2009-03-03

    Carboxylic acid- and amino-functionalized ionic liquids were used as the stabilizer for the systhesis of metal nanoparticles in aqueous solution. Smaller gold nanoparticles (3.5 nm) and platinum nanoparticles (2.5 nm) were prepared with NaBH4 as the reductant. Larger gold nanospheres (23, 42, and 98 nm) were synthesized using different quantities of trisodiumcitrate reductant. The morphology and the surface state of the metal nanoparticles were characterized by high-resolution transmission electron microscopy, UV-visible spectroscopy, and X-ray photoelectron spectroscopy. X-ray photoelectron spectroscopy spectra indicated that binding energies of C 1s and N 1s from ionic liquids on the surface of metal nanoparticles shifted negatively compared with that from pure ionic liquids. The mechanism of stabilization is proposed to be due to the interactions between imidazolium ions/functional groups in ionic liquids and metal atoms. Resonance Rayleigh scattering property of the functionalized ionic liquid-stabilized metal nanoparticles was also explored. It was found that amino-functionalized ionic liquid-stabilized gold nanoparticles exhibited lower resonance Rayleigh scattering intensity than trisodiumcitrate stabilized gold nanoparticles, which is expected to decrease the background of the resonance Rayleigh scattering intensity in the determination of various analytes. Moreover, it was found that all the as-prepared metal nanoparticles could be easily assembled on the multiwalled carbon nanotubes, which was confirmed by high-resolution transmission electron microscopy and energy dispersive X-ray spectroscopy. In this case, ionic liquids acted as a linker to connect metal nanoparticles with carbon nanotubes. The imidazolium ring moiety of ionic liquids might interact with the pi-electronic nanotube surface by virtue of cation-pi and/or pi-pi interactions, and the functionalized group moiety of ionic liquids might interact with the metal NPs surface. Finally, it was

  1. Crystal structures and compressibility of novel iron borides Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} synthesized at high pressure and high temperature

    SciTech Connect

    Bykova, E.; Gou, H.; Bykov, M.; Hanfland, M.; Dubrovinsky, L.; Dubrovinskaia, N.

    2015-10-15

    We present here a detailed description of the crystal structures of novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} with various iron content (x=1.01(1), 1.04(1), 1.32(1)), synthesized at high pressures and high temperatures. As revealed by high-pressure single-crystal X-ray diffraction, the structure of Fe{sub 2}B{sub 7} possesses short incompressible B–B bonds, which make it as stiff as diamond in one crystallographic direction. The volume compressibility of Fe{sub 2}B{sub 7} (the bulk modulus K{sub 0}= 259(1.8) GPa, K{sub 0}′= 4 (fixed)) is even lower than that of FeB{sub 4} and comparable with that of MnB{sub 4}, known for high bulk moduli among 3d metal borides. Fe{sub x}B{sub 50} adopts the structure of the tetragonal δ-B, in which Fe atoms occupy an interstitial position. Fe{sub x}B{sub 50} does not show considerable anisotropy in the elastic behavior. - Graphical abstract: Crystal structures of novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} (x=1.01(1), 1.04(1), 1.32(1)). - Highlights: • Novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50}, were synthesized under HPHT conditions. • Fe{sub 2}B{sub 7} has a unique orthorhombic structure (space group Pbam). • Fe{sub 2}B{sub 7} possesses short incompressible B–B bonds that results in high bulk modulus. • Fe{sub x}B{sub 50} adopts the structure of the tetragonal δ-B composed of B{sub 12} icosahedra. • In Fe{sub x}B{sub 50} intraicosahedral bonds are stiffer than intericosahedral ones.

  2. Bulk metallic glasses and their composites: Composition optimization, thermal stability, and microstructural tunability

    NASA Astrophysics Data System (ADS)

    Khalifa, Hesham Ezzat

    A design protocol utilizing common elements for bulk metallic glass formation has been employed to develop novel, low cost Fe-, and Ti- based bulk metallic glasses. A critical obstacle that was successfully overcome in this work is the omission of beryllium in these alloys. Beryllium is of vital importance in many bulk metallic glass forming systems, but it is expensive and poses considerable health risks. Bulk metallic glasses in these novel Fe-, and Ti-based systems exhibit extremely high mechanical strength and excellent thermal stability. Devitrification and cooling rate experiments were used to identify crystalline phase formation and assess activation energy for crystallization, as well as to explore and develop ductile BMG composites. To better control microstructure in these BMG composites, a novel processing technique, called semi-solid forging was developed, wherein the alloy melt is heated to above the melt temperature of the glass, but below the melt temperature of the ductile crystalline phase. Such an approach permits the maintenance of a glassy, or nanocrystalline matrix phase, while simultaneously coarsening and homogenizing the ductile, secondary phase. This processing approach leads to enhanced ductility in the alloys, which, to this point, has not been observed using conventional casting methods. The combination of novel, low-cost, alloy compositions with semi-solid forging has been successfully utilized to develop new high strength structural materials with enhanced ductility and toughness. Microstrutural and mechanical properties of these novel, toughened, BMG composites are presented. A comprehensive analysis of the relationship between deformation mechanisms and microstructure reveals that enhanced ductility is predicated on matching fundamental mechanical and microstructural length scales in a Ti-Ni-Si-Mo BMG composite. Under optimized microstructural conditions, a maximum compressive strength exceeding 2400 MPa with ˜ 30% total strain to

  3. Hydrogen-incorporation stabilization of metallic VO2(R) phase to room temperature, displaying promising low-temperature thermoelectric effect.

    PubMed

    Wu, Changzheng; Feng, Feng; Feng, Jun; Dai, Jun; Peng, Lele; Zhao, Jiyin; Yang, Jinlong; Si, Cheng; Wu, Ziyu; Xie, Yi

    2011-09-07

    Regulation of electron-electron correlation has been found to be a new effective way to selectively control carrier concentration, which is a crucial step toward improving thermoelectric properties. The pure electronic behavior successfully stabilized the nonambient metallic VO(2)(R) to room temperature, giving excellent thermoelectric performance among the simple oxides with wider working temperature ranges.

  4. A Highly Energetic N-Rich Zeolite-Like Metal-Organic Framework with Excellent Air Stability and Insensitivity.

    PubMed

    Qin, Jun-Sheng; Zhang, Ji-Chuan; Zhang, Min; Du, Dong-Ying; Li, Jing; Su, Zhong-Min; Wang, Yuan-Yuan; Pang, Si-Ping; Li, Sheng-Hua; Lan, Ya-Qian

    2015-12-01

    A stable N-rich aromatic ligand is employed to prepare energetic zeolite-like metal-organic frameworks. IFMC-1 shows excellent air stability, and the lowest sensitivity toward impact, friction, and electrostatic discharge and the highest predicted heat of detonation among the reported coordination polymers, and even commercial materials (such as trinitrotoluene (TNT)).

  5. Transition-state metal aryl bond stability determines regioselectivity in palladium acetate mediated C-H bond activation of heteroarenes.

    PubMed

    Petit, Alban; Flygare, Josh; Miller, Alex T; Winkel, Gerrit; Ess, Daniel H

    2012-07-20

    Density functional calculations reveal that the stability of developing metal aryl bonds in Pd(II)-acetate C-H activation transition states determines regioselectivity in arene and heteroarene compounds. This kinetic-thermodynamic connection explains the general preference for activation of the strongest C-H bond and provides the possibility for regioselectivity prediction.

  6. Bio-oil Stabilization by Hydrogenation over Reduced Metal Catalysts at Low Temperatures

    SciTech Connect

    Wang, Huamin; Lee, Suh-Jane; Olarte, Mariefel V.; Zacher, Alan H.

    2016-08-30

    Biomass fast pyrolysis integrated with bio-oil upgrading represents a very attractive approach for converting biomass to hydrocarbon transportation fuels. However, the thermal and chemical instability of bio-oils presents significant problems when they are being upgraded, and development of effective approaches for stabilizing bio-oils is critical to the success of the technology. Catalytic hydrogenation to remove reactive species in bio-oil has been considered as one of the most efficient ways to stabilize bio-oil. This paper provides a fundamental understanding of hydrogenation of actual bio-oils over a Ru/TiO2 catalyst under conditions relevant to practical bio-oil hydrotreating processes. Bio-oil feed stocks, bio-oils hydrogenated to different extents, and catalysts have been characterized to provide insights into the chemical and physical properties of these samples and to understand the correlation of the properties with the composition of the bio-oil and catalysts. The results indicated hydrogenation of various components of the bio-oil, including sugars, aldehydes, ketones, alkenes, aromatics, and carboxylic acids, over the Ru/TiO2 catalyst and 120 to 160oC. Hydrogenation of these species significantly changed the chemical and physical properties of the bio-oil and overall improved its thermal stability, especially by reducing the carbonyl content, which represented the content of the most reactive species (i.e., sugar, aldehydes, and ketones). The change of content of each component in response to increasing hydrogen additions suggests the following bio-oil hydrogenation reaction sequence: sugar conversion to sugar alcohols, followed by ketone and aldehyde conversion to alcohols, followed by alkene and aromatic hydrogenation, and then followed by carboxylic acid hydrogenation to alcohols. Hydrogenation of bio-oil samples with different sulfur contents or inorganic material contents suggested that sulfur poisoning of the reduced Ru metal catalysts was

  7. Investigation of selective doping method for producing stabilized grain structures in metals

    NASA Astrophysics Data System (ADS)

    Szozdowski, Paul T.

    Mechanical performance of a polycrystalline metal at high homologous temperature depends in part on grain structure. Grain boundary sliding is a localized plastic deformation and a mechanism for creep and rupture. Failure can occur when grains slide along boundaries transverse to the axis of an applied load. Stabilization of a structure consisting of overlapping grains of high aspect ratio is one approach to inhibiting grain boundary sliding. An overlapping grain structure is expected to offer superior resistance to creep and rupture compared with an equiaxed structure, because weak transverse grain boundaries are bridged by grains in adjacent layers. Selective doping is a method for realizing stabilized overlapping grain structures and consists of inserting discrete arrays of insoluble dopant into a matrix at regular intervals. At elevated temperature, the dopant forms arrays of bubbles of sub-micrometer size. The bubble arrays aid in the formation and stabilization of an overlapping grain structure at high temperature. Two methods of selective doping were investigated. The first approach consisted of doping the near-surface regions of molybdenum foil substrates with potassium by ion implantation and depositing molybdenum onto the doped substrates by physical vapor deposition to form three-layer specimens. The second approach consisted of doping the near-surface regions of tungsten foils with potassium by ion implantation and subsequently diffusion bonding the doped foils to form multi-layer specimens. Doped, multi-layer specimens were annealed for recrystallization and grain growth. The size and spatial distributions of the potassium bubble arrays were documented by observing bubbles on intergranular fracture surfaces using scanning electron microscopy. Results showed that both approaches are viable for producing stabilized grain structures. Selective doping produced a dispersion of potassium bubbles with radii of tens of nanometers. The bubble arrays established

  8. Cassie-State Stability of Metallic Superhydrophobic Surfaces with Various Micro/Nanostructures Produced by a Femtosecond Laser.

    PubMed

    Long, Jiangyou; Pan, Lin; Fan, Peixun; Gong, Dingwei; Jiang, Dafa; Zhang, Hongjun; Li, Lin; Zhong, Minlin

    2016-02-02

    The Cassie-state stability plays a vital role in the applications of metallic superhydrophobic surfaces. Although a large number of papers have reported the superhydrophobic performance of various surface micro/nanostructures, the knowledge of which kind of micro/nanostructure contributes significantly to the Cassie-state stability especially under low temperature and pressure is still very limited. In this article, we fabricated six kinds of typical micro/nanostructures with different topography features on metal surfaces by a femtosecond laser, and these surfaces were modified by fluoroalkylsilane to generate superhydrophobicity. We then systematically studied the Cassie-state stability of these surfaces by means of condensation and evaporation experiments. The results show that some superhydrophobic surfaces, even with high contact angles and low sliding angles under normal conditions, are unstable under low temperature or external pressure. The Cassie state readily transits to a metastable state or even a Wenzel state under these conditions, which deteriorates their superhydrophobicity. Among the six micro/nanostructures, the densely distributed nanoscale structure is important for a stable Cassie state, and the closely packed micrometer-scale structure can further improve the stability. The dependence of the Cassie-state stability on the fabricated micro/nanostructures and the laser-processing parameters is also discussed. This article clarifies optimized micro/nanostructures for stable and thus more practical metallic superhydrophobic surfaces.

  9. Electron emission from nanometer-size metallic clusters: Electronic states and structural stability of supported Au clusters

    SciTech Connect

    Lin, M.E.; Ramachandra, A.; Andres, R.P.; Reifenberger, R.

    1992-12-31

    Techniques developed to measure the thermodynamic and electronic properties of a single metallic cluster with nanometer-size dimensions are described. Using these techniques, experiments that resolve the quantized energy spectrum of electrons in a nanometer-size cluster of metallic atoms at room temperature have been performed. Studies on the stability of the electron emission current from an individual nanometer-size cluster supported on a tungsten tip have been performed to learn more about the intrinsic stability of these nanometer-size objects. The data show abrupt jumps between different emission states that are revisited as time progresses. This phenomenon is attributed to a rearrangement of the duster structure and/or orientation on the substrate and provides new evidence of multiple `isomeric` structures for small clusters of metallic atoms.

  10. Novel borothermal process for the synthesis of nanocrystalline oxides and borides of niobium.

    PubMed

    Jha, Menaka; Ramanujachary, Kandalam V; Lofland, Samuel E; Gupta, Govind; Ganguli, Ashok K

    2011-08-21

    A new process has been developed for the synthesis of nanocrystalline niobium oxide and niobium diboride using an amorphous niobium precursor obtained via the solvothermal route. On varying the ratio of niobium precursor to boron and the reaction conditions, pure phases of nanostructured niobium oxides (Nb(2)O(5), NbO(2)), niobium diboride (NbB(2)) and core-shell nanostructures of NbB(2)@Nb(2)O(5) could be obtained at normal pressure and low temperature of 1300 °C compared to a temperature of 1650 °C normally used. The above borothermal process involves the in situ generation of B(2)O(2) to yield either oxide or diboride. The niobium oxides and borides have been characterized in detail by XRD, HRTEM and EDX studies. The core-shell structure has been investigated by XPS depth profiling, EFTEM and EELS (especially to characterize the presence of boron and the shell thickness). The niobium diboride nanorods (with high aspect ratio) show a superconducting transition with the T(c) of 6.4 K. In the core-shell of NbB(2)@Nb(2)O(5), the superconductivity of NbB(2) is masked by the niobium oxide shell and hence no superconductivity was observed. The above methodology has the benefits of realizing both oxides and borides of niobium in nanocrystalline form, in high purity and at much lower temperatures.

  11. Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

    2016-08-01

    The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.

  12. Amorphous nickel boride membrane on a platinum–nickel alloy surface for enhanced oxygen reduction reaction

    PubMed Central

    He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

    2016-01-01

    The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum–nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum–nickel catalyst, and this composite catalyst composed of crystalline platinum–nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon. PMID:27503412

  13. Phase Evolution in Boride-Based Cermets and Reaction Bonding onto Plain Low Carbon Steel Substrate

    NASA Astrophysics Data System (ADS)

    Palanisamy, B.; Upadhyaya, A.

    2012-04-01

    Reaction sinter bonding is a process that aims to bond two materials for improvement in properties through reactive sintering technique. The process has been effectively used to sinter hard materials like borides in situ which not only possess excellent oxidation resistance, good corrosion resistance but also resistant to abrasive wear. Sinter bonding is a unique surface modification process achieved through powder metallurgy and is competent with other techniques like boronizing sintering and sinter-brazing since it eliminates the additional operations of heat treatment and assembly and removes the inherent setbacks with these processes. This study focuses on identifying the phase evolution mechanism using characterization tools like x-ray diffractometry and energy dispersive spectroscopy and study of sinter bonding of the boron containing precursors (Mo-Cr-Fe-Ni-FeB-MoB) onto plain carbon steel. A microstructure containing Fe-based matrix dispersed with complex borides develops with temperature in the tape cast sheets. A fivefold increase in hardness between plain carbon steel in wrought condition and sinter bonded steel was observed. The multilayer consisted of a reaction zone adjacent to the interface and was investigated with the composition profile and hardness measurements. A model of sinter bonding between the cermet and the steel has also been proposed.

  14. Role of Metal Oxide Electron-Transport Layer Modification on the Stability of High Performing Perovskite Solar Cells.

    PubMed

    Singh, Trilok; Singh, Jai; Miyasaka, Tsutomu

    2016-09-22

    Organic-inorganic hybrid perovskite light absorbers have recently emerged as a "holy grail" for next generation thin-film photovoltaics with excellent optoelectronics properties and low fabrication cost. In a very short span of time, we have witnessed a pronounced and unexpected progress in organic- inorganic perovskite solar cells (PSCs) with a vertical rise in power conversion efficiency from 3.8 to 22.1 %. In this manuscript we focus specifically on the recent development of metal oxide-based electron-transporting layer (ETL) modification for high performing PSCs and their stability. This review highlights various methodologies to modify existing compact/scaffold layers for improving device performance and stability. Various aspects of the ETL are discussed with different metal oxide compact layers in their relation to modification in mesoporous layers towards the design of a cell structure with high performance and stability.

  15. Influence of the stabilizers on the toxicity of metallic nanomaterials in aquatic organisms and human cell lines.

    PubMed

    Andreani, Tatiana; Nogueira, Verónica; Pinto, Vera V; Ferreira, Maria José; Rasteiro, Maria Graça; Silva, Amélia M; Pereira, Ruth; Pereira, Carlos M

    2017-12-31

    In this study, following a systematic approach, we used aquatic species (bacteria Vibrio fischeri and microalgae Raphidocelis subcapitata) and different human cell lines (Caco-2, HepG2, SV-80 and HaCaT) representing different tissues and exposure pathways, to investigate how two organic stabilizers (PVA and DMSO) used for NMs dispersion influence their physicochemical properties, the persistence of metals in suspension and the toxicity/ecotoxicity of two metallic NMs (nano-Ag and nano-Cu). Although the stabilizers are expected to contribute to improve the dispersion and stability of NMs, the results obtained clearly showed that no similar changes in toxicity and morphological properties of the nano-Ag can be expected after its stabilization with PVA. Thus, regarding human cell lines, the reduction in the average size of the PVA-nano-Ag was followed by a reduction or maintenance of its toxicity, but the opposite was observed for the aquatic species tested since an increase in the average size enhanced its toxicity. As far as nano-Cu is considered DMSO contributed for a better dispersion of this nanomaterial, however this was not translated in a similar toxicity/ecotoxicity modification. In summary, even for nano-Cu, for which few or no data exists regarding its toxicity after stabilization with organic compounds, it was confirmed with consistent data, that the toxicity of metallic NMs is a complex combination of average size, chemical composition, solubilization or persistence in suspension of the metallic forms, interaction with test medium components and sensitivity of test species and cell lines. The combination of all of these factors makes the toxicity of metallic NMs unpredictable and points for the need of an extensive evaluation of each new formulation. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Fibrous Carbon-Metallic Materials and a Method of Manufacturing Carbon-Metallic Fibrous Materials,

    DTIC Science & Technology

    1983-05-12

    fibers associated with a carbon binder and an additive in the form of boron nitride, boron silicide and heat-resistant metal borides. On the other hand...Great Britain patent description No. 1302331 refers to metal parts reinforced by carbon fibers with a galvanized coating or as a result of a...carbon fibers, a carbonaceous binder and additives such as boron, niobium , silicon, tantalum and others. United States patent deocription No. 3622283

  17. Formation, stability, and solubility of metal oxide nanoparticles: Surface entropy, enthalpy, and free energy of ferrihydrite

    NASA Astrophysics Data System (ADS)

    Hiemstra, Tjisse

    2015-06-01

    -line Fh, log Kso ∼ -39.5 ± 0.1. The smallest Fh particles in a suspension react according to the Ostwald-Freundlich equation (RTΔlnKso = 2/3 γA), but the suspension as a whole apparently reacts according to the Ostwald equation (RTΔlnKso = γA). This difference can be explained by the observed linear relation between the minimum (dmin) and mean (dmean) particle size (dmin = 2/3 dmean) in Fh suspensions. With best estimates for the surface entropy of goethite, hematite, and lepidocrocite, predictions show that Fh becomes thermodynamically unstable above a diameter of ∼8.0 nm at 298 K, allowing formation of nano-goethite and nano-hematite, as experienced experimentally at Ostwald ripening. More generally, one observes that metal (hydr) oxides with the highest chemical stability also have the highest mean surface Gibbs free energy, which can be considered as the scientific explanation of the empirical rule of Ostwald-Lussac. In addition, it is shown that the surface Gibbs free energies of metal (hydr) oxides increase with the mean metal coordination number of oxygen in the lattices following the order: oxides > oxyhydroxides > hydroxides.

  18. Super-strengthening and stabilizing with carbon nanotube harnessed high density nanotwins in metals by shock loading

    PubMed Central

    Lin, Dong; Saei, Mojib; Suslov, Sergey; Jin, Shengyu; Cheng, Gary J.

    2015-01-01

    CNTs reinforced metal composites has great potential due to their superior properties, such as light weight, high strength, low thermal expansion and high thermal conductivity. The current strengthening mechanisms of CNT/metal composite mainly rely on CNTs’ interaction with dislocations and CNT’s intrinsic high strength. Here we demonstrated that laser shock loading the CNT/metal composite results in high density nanotwins, stacking fault, dislocation around the CNT/metal interface. The composites exhibit enhanced strength with excellent stability. The results are interpreted by both molecular dynamics simulation and experiments. It is found the shock wave interaction with CNTs induces a stress field, much higher than the applied shock pressure, surrounding the CNT/metal interface. As a result, nanotwins were nucleated under a shock pressure much lower than the critical values to generate twins in metals. This hybrid unique nanostructure not only enhances the strength, but also stabilize the strength, as the nanotwin boundaries around the CNTs help pin the dislocation movement. PMID:26493533

  19. Membrane filtration studies of aquatic humic substances and their metal species: a concise overview. Part 2. Evaluation of conditional stability constants by using ultrafiltration.

    PubMed

    Nifant'eva, T I; Shkinev, V M; Spivakov, B Y; Burba, P

    1999-02-01

    The assessment of conditional stability constants of aquatic humic substance (HS) metal complexes is overviewed with special emphasis on the application of ultrafiltration methods. Fundamentals and limitations of stability functions in the case of macromolecular and polydisperse metal-HS species in aquatic environments are critically discussed. The review summarizes the advantages and application of ultrafiltration for metal-HS complexation studies, discusses the comparibility and reliability of stability constants. The potential of ultrafiltration procedures for characterizing the lability of metal-HS species is also stressed.

  20. Temporal Stability of Metal-Chloride-Doped Chemical-Vapour-Deposited Graphene.

    PubMed

    Kang, Moon H; Milne, William I; Cole, Matthew T

    2016-08-18

    Graphene has proven to be a promising material for transparent flexible electronics. In this study, we report the development of a transfer and doping scheme of large-area chemical vapour deposited (CVD) graphene. A technique to transfer the as-grown material onto mechanically flexible and optically transparent polymeric substrates using an ultraviolet adhesive (UVA) is outlined, along with the temporal stability of the sheet resistance and optical transparency following chemical doping with various metal chlorides (Mx Cly The sheet resistance (RS ) and 550 nm optical transparency (%T550 ) of the transferred un-doped graphene was 3.5 kΩ sq(-1) (±0.2 kΩ sq(-1) ) and 84.1 % (±2.9 %), respectively. Doping with AuCl3 showed a notable reduction in RS by some 71.4 % (to 0.93 kΩ sq(-1) ) with a corresponding %T550 of 77.0 %. After 200 h exposure to air at standard temperature and pressure, the increase in RS was found to be negligible (ΔRS AuCl3 =0.06 kΩ sq(-1) ), indicating that, of the considered Mx Cly species, AuCl3 doping offered the highest degree of time stability under ambient conditions. There appears a tendency of increasing RS with time for the remaining metal chlorides studied. We attribute the observed temporal shift to desorption of molecular dopants. We find that desorption was most significant in RhCl3 -doped samples whereas, in contrast, after 200 h in ambient conditions, AuCl3 -doped graphene showed only marginal desorption. The results of this study demonstrate that chemical doping of UVA-transferred graphene is a promising means for enhancing large-area CVD graphene in order to realise a viable platform for next-generation optically transparent and mechanically flexible electronics.

  1. Glass Stability and Kinetic Analysis of Iron-Metalloid Bulk Metallic Glass

    NASA Astrophysics Data System (ADS)

    Santhaweesuk, Charuayporn

    Multicomponent Fe-based bulk metallic glasses (BMGs) with a combination of excellent properties such as good soft magnetic properties, high strength, high hardness, and high corrosion resistance have attracted increasing attention both from a basic science research standpoint and due to their industrial application potential. However, many of the elemental additions which lead to the easiest glass formation are expensive. The identification of alloys composed of abundant and inexpensive elements that still retain excellent properties would promote applications for engineering and industry. In short, the development of the Fe-based BMG without any glass-forming metal elements and with high glass forming ability is desired. This study shows that the thermal stability of the Fe-based alloys can be improved beyond a simple rule of mixtures prediction by utilizing a well-balance multi-metalloid approach. The kinetics aspect of glass-forming ability is studied experimentally for Fe-B-Si-P alloys. The systematic variation in alloy composition gives access to differences in phase selection and the final dimensions of glass formation. Two alloys, representing the best glass-forming composition and the poorest glass-forming composition, were studied in terms of their stability to crystallization, solidification microstructure evolution and thermal history. The utility of the wedge-casting technique is developed to examine bulk glass-forming alloys by combining multiple temperature profiles of the quenching melt with a measurement-based kinetic analysis of the phase selection competition and critical cooling rate conditions. Based upon direct thermal measurement, microstructural analysis and kinetic modeling, it was found that both representative alloys show a board spectrum of solidification microstructures which include a critical cooling rate range. The kinetic competition in the formation of certain phases can enhance or detract from the final dimension of bulk glass

  2. Ammine-Stabilized Transition-Metal Borohydrides of Iron, Cobalt, and Chromium: Synthesis and Characterization.

    PubMed

    Roedern, Elsa; Jensen, Torben R

    2015-11-02

    Iron and cobalt borohydrides stabilized by ammonia (NH3), [Fe(NH3)6](BH4)2 and [Co(NH3)6](BH4)2, were synthesized along with a solid solution, [Co(NH3)6](BH4)(2-x)Cl(x) (x ∼ 1), and a bimetallic compound, [Fe(NH3)6](Li2(BH4)4). The compounds were prepared by new low-temperature, solvent-based synthesis methods, using dimethyl sulfide or liquid NH3, which allow for the removal of inert metal halides. The crystal structures were determined from synchrotron radiation powder X-ray diffraction (SR-PXD) data. [M(NH3)6](BH4)2 (M = Fe, Co) and [Co(NH3)6](BH4)(2-x)Cl(x) crystallize in the cubic crystal system, where the transition metals are octahedrally coordinated by NH3. Polymeric chains of lithium coordinated by four bridging BH4(-) anions are found in [Fe(NH3)6](Li2(BH4)4). The new compounds have high hydrogen densities of ∼14 wt % H2 and ∼140 g H2/L and release a mixture of hydrogen and NH3 gas at low temperatures, T < 80 °C. The decomposition mechanisms of the prepared compounds along with the composites [Fe(NH3)6](BH4)2·nNH3BH3 (n = 2, 4, 6) were studied by thermal analysis and in situ SR-PXD.

  3. Stabilizing small molecules on metal oxide surfaces using atomic layer deposition.

    PubMed

    Hanson, Kenneth; Losego, Mark D; Kalanyan, Berç; Parsons, Gregory N; Meyer, Thomas J

    2013-10-09

    Device lifetimes and commercial viability of dye-sensitized solar cells (DSSCs) and dye-sensitized photoelectrosynthesis cells (DSPECs) are dependent on the stability of the surface bound molecular chromophores and catalysts. Maintaining the integrity of the solution-metal oxide interface is especially challenging in DSPECs for water oxidation where it is necessary to perform high numbers of turnovers, under irradiation in an aqueous environment. In this study, we describe the atomic layer deposition (ALD) of TiO2 on nanocrystalline TiO2 prefunctionalized with the dye molecule [Ru(bpy)2(4,4'-(PO3H2)bpy)](2+) (RuP) as a strategy to stabilize surface bound molecules. The resulting films are over an order of magnitude more photostable than untreated films and the desorption rate constant exponentially decreases with increased thickness of ALD TiO2 overlayers. However, the injection yield for TiO2-RuP with ALD TiO2 also decreases with increasing overlayer thickness. The combination of decreased injection yield and 95% quenched emission suggests that the ALD TiO2 overlayer acts as a competitive electron acceptor from RuP*, effectively nonproductively quenching the excited state. The ALD TiO2 also increases back electron transfer rates, relative to the untreated film, but is independent of overlayer thickness. The results for TiO2-RuP with an ALD TiO2 overlayer are compared with similar films having ALD Al2O3 overlayers.

  4. Optimized synthesis and crystalline stability of γ-cyclodextrin metal-organic frameworks for drug adsorption.

    PubMed

    Liu, Botao; Li, Haiyan; Xu, Xiaonan; Li, Xue; Lv, Nana; Singh, Vikramjeet; Stoddart, J Fraser; York, Peter; Xu, Xu; Gref, Ruxandra; Zhang, Jiwen

    2016-11-30

    The biocompatible and renewable cyclodextrin metal-organic frameworks (CD-MOFs) have addressed a range of opportunities in molecular storage and separation sciences. The reported protocols for their synthesis, however, were carried out at room temperature over long time periods of time (24h), producing crystals of relatively poor uniformity. In this investigation, micron sized γ-CD-MOFs were synthesized by an optimized vapor diffusion method at elevated temperature (50°C) within 6h, after which the size control, crystalline stability and drug adsorption behavior were investigated in detail. In this manner, uniform cubic γ-CD-MOF crystals were obtained when the reaction temperature was raised to 50°C with pre-addition of the reaction solvent. The size of γ-CD-MOFs was adjusted efficiently by changing the reactant concentrations, temperatures, time, γ-CD ratios to KOH and surfactant concentrations, without influencing the porosity and crystallinity of the material markedly. Varing degrees of reduction in crystallinity and change in morphology were observed when the γ-CD-MOF crystals are treated under conditions of high temperature (100°C), high humidity (92.5%) and polar solvents (e.g., MeOH and DMF). In relation to drug adsorption by γ-CD-MOFs, most of the drug molecules containing carboxyl groups showed relatively high adsorption (>5%), while low adsorption (<5%) was found for drugs with nitrogen-containing heterocyclic rings. In addition, the adsorption kinetics of captopril to standard γ-CD-MOFs matched a pseudo-second-order model rather well, whilst captopril adsorption to the damaged γ-CD-MOFs only partially matched the pseudo-second-order model. In summary, based upon the optimized synthesis and size control of γ-CD-MOFs, the crystalline stability and drug adsorption characteristics of γ-CD-MOF crystals have been evaluated as a fundamental requirement of a potential vehicle for drug delivery.

  5. Optimized synthesis and crystalline stability of γ-cyclodextrin metal-organic frameworks for drug adsorption.

    PubMed

    Liu, Botao; Li, Haiyan; Xu, Xiaonan; Li, Xue; Lv, Nana; Singh, Vikramjeet; Stoddart, J Fraser; York, Peter; Xu, Xu; Gref, Ruxandra; Zhang, Jiwen

    2016-09-26

    The biocompatible and renewable cyclodextrin metal-organic frameworks (CD-MOFs) have addressed a range of opportunities in molecular storage and separation sciences. The reported protocols for their synthesis, however, were carried out at room temperature over long time periods of time (24h), producing crystals of relatively poor uniformity. In this investigation, micron sized γ-CD-MOFs were synthesized by an optimized vapor diffusion method at elevated temperature (50°C) within 6h, after which the size control, crystalline stability and drug adsorption behavior were investigated in detail. In this manner, uniform cubic γ-CD-MOF crystals were obtained when the reaction temperature was raised to 50°C with pre-addition of the reaction solvent. The size of γ-CD-MOFs was adjusted efficiently by changing the reactant concentrations, temperatures, time, γ-CD ratios to KOH and surfactant concentrations, without influencing the porosity and crystallinity of the material markedly. Varing degrees of reduction in crystallinity and change in morphology were observed when the γ-CD-MOF crystals are treated under conditions of high temperature (100°C), high humidity (92.5%) and polar solvents (e.g., MeOH and DMF). In relation to drug adsorption by γ-CD-MOFs, most of the drug molecules containing carboxyl groups showed relatively high adsorption (>5%), while low adsorption (<5%) was found for drugs with nitrogen-containing heterocyclic rings. In addition, the adsorption kinetics of captopril to standard γ-CD-MOFs matched a pseudo-second-order model rather well, whilst captopril adsorption to the damaged γ-CD-MOFs only partially matched the pseudo-second-order model. In summary, based upon the optimized synthesis and size control of γ-CD-MOFs, the crystalline stability and drug adsorption characteristics of γ-CD-MOF crystals have been evaluated as a fundamental requirement of a potential vehicle for drug delivery.

  6. A diffusion model for describing the bilayer growth (FeB/Fe 2B) during the iron powder-pack boriding

    NASA Astrophysics Data System (ADS)

    Keddam, M.; Chentouf, S. M.

    2005-10-01

    In this paper, a diffusion model is proposed for studying the bilayer growth kinetics (FeB/Fe 2B) on pure iron substrate during the powder-pack boriding in the temperature range of 1023-1273 K. This model based on Fick's laws was solved, under certain assumptions, considering a parabolic growth of iron borides. For this purpose, a computer simulation program was created for predicting the boride layer thickness as a function of process parameters (temperature, time and surface boron content). A fairly good agreement was observed between the simulation calculations and experimental data derived from the literature.

  7. Simulation of the growth kinetics of the (FeB/Fe 2B) bilayer obtained on a borided stainless steel

    NASA Astrophysics Data System (ADS)

    Keddam, M.

    2011-01-01

    The present work is an attempt to simulate the growth kinetics of the (FeB/Fe 2B) bilayer grown on a substrate made of AISI 316 stainless steel by the application of the powder-pack boriding process, and using four different temperatures (1123, 1173, 1223 and 1273 K) and five exposure times (2, 4, 6, 8 and 10 h). The adopted diffusion model solves the mass balance equation at each growth front: (FeB/Fe 2B or FeB/substrate) under certain assumptions and without considering the diffusion zone. To consider the effect of the incubation times for the borides formation, the temperature-dependent function ϕ( T) was incorporated in the model. To validate this model, a computer code written in Matlab (version 6.5), was developed with the purpose of simulating the kinetics of the boride layers. This computer code uses the following parameters as input data: (the boriding temperature, the treatment time, the upper and lower limits of boron concentration in each iron boride, the diffusion coefficients of boron in the FeB and Fe 2B phases as well as the ϕ( T) parameter). The outputs of the computer code are the parabolic growth constant at each growth front and the thicknesses of the FeB and Fe 2B layers. A good agreement was obtained between the experimental parabolic growth constants taken from a reference work [I. Campos-Silva et al., Formation and kinetics of FeB/Fe 2B layers and diffusion zone at the surface of AISI 316 borided steels, Surf. Coat Technol., 205 (2010) 403-412] and the simulated values of the parabolic growth constants ( kFeB and k1). The present model was also able to predict the thicknesses of the FeB and Fe 2B layers at a temperature of 1243 K during 3 and 5 h. In addition, the mass gain at the material surface was also estimated as a function of the time and the upper boron content in each iron boride phase. It was shown that the simulated values of the generated mass gain are very sensitive to the increase of both temperature and the upper boron

  8. Half metallicity and magnetic stability of sp-electron superlattices in rock-salt structure: A first-principles study

    NASA Astrophysics Data System (ADS)

    Zhou, Baozeng; Dong, Shengjie; Chen, Shanxing; Zhang, Zidan; Zhao, Hui; Wu, Ping

    2014-08-01

    Density functional calculations were performed to study the structural, electronic, and magnetic properties of sp-electron half-metallic superlattices (KS)1/(CaS)1, (RbS)1/(SrS)1, and (CsS)1/(BaS)1 (001) in rock-salt structure. All the superlattices are found to be spin polarized, and the calculated band structure suggests a 100% polarization of the conduction carriers. The p-p hybridization is shown to be essential for the formations of localized orbitals and spin-splitting. The half-metallic electronic structure will be destroyed upon an excessive lattice compression, accompanying with a metallic transition. Moreover, the analysis of the orbital-decomposed partial density of states and spin density reveal that S atoms in different layers of the superlattice show distinct polarization directions. Discussion of volume-conserving deformations further demonstrates the stability of half metallicity in sp-electron superlattices.

  9. Direct Measurement of the Nanomechanical Stability of a Redox Protein Active Site and Its Dependence upon Metal Binding.

    PubMed

    Giannotti, Marina I; Cabeza de Vaca, Israel; Artés, Juan M; Sanz, Fausto; Guallar, Victor; Gorostiza, Pau

    2015-09-10

    The structural basis of the low reorganization energy of cupredoxins has long been debated. These proteins reconcile a conformationally heterogeneous and exposed metal-chelating site with the highly rigid copper center required for efficient electron transfer. Here we combine single-molecule mechanical unfolding experiments with statistical analysis and computer simulations to show that the metal-binding region of apo-azurin is mechanically flexible and that high mechanical stability is imparted by copper binding. The unfolding pathway of the metal site depends on the pulling residue and suggests that partial unfolding of the metal-binding site could be facilitated by the physical interaction with certain regions of the redox protein.

  10. Functionalization of Metal-Organic Frameworks for Enhanced Stability under Humid Carbon Dioxide Capture Conditions.

    PubMed

    Andirova, Dinara; Lei, Yu; Zhao, Xiaodan; Choi, Sunho

    2015-10-26

    Metal-organic frameworks (MOFs) have been highlighted recently as promising materials for CO2 capture. However, in practical CO2 capture processes, such as capture from flue gas or ambient air, the adsorption properties of MOFs tend to be harmed by the presence of moisture possibly because of the hydrophilic nature of the coordinatively unsaturated sites (CUSs) within their framework. In this work, the CUSs of the MOF framework are functionalized with amine-containing molecules to prevent structural degradation in a humid environment. Specifically, the framework of the magnesium dioxybenzenedicarboxylate (Mg/DOBDC) MOF was functionalized with ethylenediamine (ED) molecules to make the overall structure less hydrophilic. Structural analysis after exposure to high-temperature steam showed that the ED-functionalized Mg/DOBDC (ED-Mg/DOBDC) is more stable under humid conditions, than Mg/DOBDC, which underwent drastic structural changes. ED-Mg/DOBDC recovered its CO2 adsorption capacity and initial adsorption rate quite well as opposed to the original Mg/DOBDC, which revealed a significant reduction in its capture capacity and kinetics. These results suggest that the amine-functionalization of the CUSs is an effective way to enhance the structural stability of MOFs as well as their capture of humid CO2 .

  11. CaO-based CO2 sorbents stabilized effectively by metal oxides.

    PubMed

    Müller, Christoph R; Awais Naeem, Muhammad; Armutlulu, Andac; Imtiaz, Qasim

    2017-08-18

    Calcium looping (i.e. CO2 capture by CaO) is a promising second-generation CO2 capture technology. CaO derived from naturally occurring limestone offers an inexpensive solution, but due to the harsh operating conditions of the process, limestone-derived sorbents undergo a rapid capacity decay induced by the sintering of CaCO3. Here, we report a Pechini method to synthesize cyclically stable, CaO-based CO2 sorbents with a high CO2 uptake capacity. The sorbents synthesized feature compositional homogeneity in combination with a nanostructured and highly porous morphology. The presence of a single (Al2O3 or Y2O3) or bi-metal oxide (Al2O3-Y2O3) provides cyclic stability, except for MgO which undergoes a significant increase in its particle size with cycle number. We also demonstrate a direct relationship between the CO2 uptake and the morphology of the sorbents synthesized. After 30 cycles of calcination and carbonation, the best performing sorbent containing an equimolar mixture of Al2O3 and Y2O3 exhibits a CO2 uptake capacity of 8.7 mmol CO2/g sorbent which is approximately 360% higher than that of the reference limestone. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. High Temperature Stability of Dissimilar Metal Joints in Fission Surface Power Systems

    SciTech Connect

    Locci, Ivan E.; Nesbitt, James A.; Ritzert, Frank J.; Bowman, Cheryl L.

    2007-01-30

    Future generations of power systems for spacecraft and lunar surface systems will likely require a strong dependence on nuclear power. The design of a space nuclear power plant involves integrating together major subsystems with varying material requirements. Refractory alloys are repeatedly considered for major structural components in space power reactor designs because refractory alloys retain their strength at higher temperatures than other classes of metals. The relatively higher mass and lower ductility of the refractory alloys make them less attractive for lower temperature subsystems in the power plant such as the power conversion system. The power conversion system would consist more likely of intermediate temperature Ni-based superalloys. One of many unanswered questions about the use of refractory alloys in a space power plant is how to transition from the use of the structural refractory alloy to more traditional structural alloys. Because deleterious phases can form when complex alloys are joined and operated at elevated temperatures, dissimilar material diffusion analyses of refractory alloys and superalloys are needed to inform designers about options of joint temperature and operational lifetime. Combinations of four superalloys and six refractory alloys were bonded and annealed at 1150 K and 1300 K to examine diffusional interactions in this study. Joints formed through hot pressing and hot isostatic pressing were compared. Results on newer alloys compared favorably to historical data. Diffusional stability is promising for some combinations of Mo-Re alloys and superalloys at 1150 K, but it appears that lower joint temperatures would be required for other refractory alloy couples.

  13. Relative edge energy in the stability of transition metal nanoclusters of different motifs.

    PubMed

    Zhao, X J; Xue, X L; Guo, Z X; Li, S F

    2016-07-07

    When a structure is reduced to a nanometer scale, the proportion of the edge atoms increases significantly, which can play a crucial role in determining both their geometric and electronic properties, as demonstrated by the recently established generalized Wulff construction principle [S. F. Li, et al., Phys. Rev. Lett., 2013, 111, 115501]. Consequently, it is of great interest to clarify quantitatively the role of the edge atoms that dominate the motifs of these nanostructures. In principle, establishing an effective method valid for determining the absolute value of the surface energy and particularly the edge energy for a given nanostructure is expected to resolve such a problem. However, hitherto, it is difficult to obtain the absolute edge energy of transition metal clusters, particularly when their sizes approach the nanometer regime. In this paper, taking Ru nanoclusters as a prototypical example, our first-principles calculations introduce the concept of relative edge energy (REE), reflecting the net edge atom effect over the surface (facet) atom effect, which is fairly powerful to quasi-quantitatively estimate the critical size at which the crossover occurs between different configurations of a given motif, such as from an icosahedron to an fcc nanocrystal. By contrast, the bulk effect should be re-considered to rationalize the power of the REE in predicting the relative stability of larger nanostructures between different motifs, such as fcc-like and hcp-like nanocrystals.

  14. Facile synthesis of glucoamylase embedded metal-organic frameworks (glucoamylase-MOF) with enhanced stability.

    PubMed

    Nadar, Shamraja S; Rathod, Virendra K

    2017-02-01

    The self-assembled glucoamylase metal-organic framework (glucoamylase-MOF) was synthesized by facile one-step method within 20min by simply mixing aqueous solution of 2-methylimidazole (160mM), glucoamylase (5mg/mL) and zinc acetate (40mM) at room temperature (28±2°C). The prepared glucoamylase-MOF was characterized by using FT-IR, confocal scanning laser microscopy, XRD and SEM. The robustness and thermal stability of glucoamylase embedded MOF was evaluated in terms of half-life (in the range of 60-80°C) which showed 6 folds increment as against free form. Further, in Michaelis-Menten kinetics studies, glucoamylase entrapped MOF exhibited higher Km value and lower Vmax value as compared to native enzyme. Moreover, the immobilized glucoamylase exhibited up to 57% of residual activity after six consecutive cycles of reuse, whereas it retained 91% of residual activity till 25days of storage. Finally, the conformational changes occurred after the encapsulation of glucoamylase in the interior of MOF, which was analyzed by using FT-IR data analysis tools. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Numerical Modeling of the Stability of Face-Centered Cubic Metals with High Vacancy Concentration

    SciTech Connect

    Brian P. Somerday; M. I. Baskes

    1998-12-01

    The objective of this research is to assess the possibility of forming an atomically porous structure in a low-density metal, e.g., Al with vacancies up to 0.20/lattice site; and to examine the effects of hydrogen and vacancy concentration on the stability of an atomically porous structure that has been experimentally produced in nickel. The approach involves numerical modeling using the Embedded-Atom Method (EAM). High vacancy concentrations cause the Al lattice to disorder at 300K. In contrast, Ni retains the face-centered-cubic structure at 300K for vacancy concentrations up to 0.15 Vac/lattice site. Unexpectedly, the lattice with 0.15 Vac/lattice site is more stable than the lattice with 0.10 or 0.20 Vac/lattice site. The Ni systems with 0.10 and 0.15 Vac/lattice site exhibit domains consisting of uniform lattice rotations. The Ni lattice with 0.15 Vac/lattice site is more stable with an initial distribution of random vacancies compared to ordered vacancies. The equilibrium lattice structures of Ni a d Al containing vacancies and H are less ordered to structures with vacancies only at 300K.

  16. Criterion for stability of Goldstone modes and Fermi liquid behavior in a metal with broken symmetry

    PubMed Central

    Watanabe, Haruki; Vishwanath, Ashvin

    2014-01-01

    There are few general physical principles that protect the low-energy excitations of a quantum phase. Of these, Goldstone’s theorem and Landau–Fermi liquid theory are the most relevant to solids. We investigate the stability of the resulting gapless excitations—Nambu–Goldstone bosons (NGBs) and Landau quasiparticles—when coupled to one another, which is of direct relevance to metals with a broken continuous symmetry. Typically, the coupling between NGBs and Landau quasiparticles vanishes at low energies, leaving the gapless modes unaffected. If, however, the low-energy coupling is nonvanishing, non-Fermi liquid behavior and overdamped bosons are expected. Here we prove a general criterion that specifies when the coupling is nonvanishing. It is satisfied by the case of a nematic Fermi fluid, consistent with earlier microscopic calculations. In addition, the criterion identifies a new kind of symmetry breaking—of magnetic translations—where nonvanishing couplings should arise, opening a previously unidentified route to realizing non-Fermi liquid phases. PMID:25349386

  17. Thermoelastic Stability Analysis of Solidification of Pure Metals on a Coated Planar Mold of Finite Thickness

    NASA Astrophysics Data System (ADS)

    Demir, Mehmet Hakan; Yigit, Faruk

    2016-12-01

    A theoretical model for investigating the thermoelastic instability/mechanism during pure metal solidification on a coated mold of finite thickness is developed. This study extends the previous theoretical works on growth instability during solidification process by investigating the effects of an added coating layer. Mold coating is one of the most important factors controlling the heat transfer rate, and hence it has a very important role on the solidification rate and the development of microstructure. In this model, thermal and mechanical problems are coupled through the pressure-dependent contact resistances at mold/coating and coating/shell interfaces. The thermal diffusivities of solidified shell, coating, and mold materials are assumed to be zero. This assumption provides us to solve heat transfer problem analytically. A linear perturbation method is used to simplify complexity of the modeled solidification problem, and governing equations are solved numerically using a variable step variable order predictor-corrector algorithm. The effects of coating layer thickness and coupling rates at shell/coating and coating/mold interfaces are investigated in detail. The results show that coating thickness has destabilizing effect on the growth instability when the coupling rates are small. However, when these coupling rates are increased individually or together, the destabilizing effect of coating thickness turns to be stabilizing. On the other hand, coupling rates have generally destabilizing effects on the process, but an increase in the thickness of coating leads to diminishing coupling rates effect in some cases.

  18. A Combined Experimental and Computational Study on the Stability of Nanofluids Containing Metal Organic Frameworks

    SciTech Connect

    Annapureddy, Harsha Vardhan Reddy; Nune, Satish K.; Motkuri, Radha K.; McGrail, B. Peter; Dang, Liem X.

    2015-01-08

    Computational studies on nanofluids composed of metal organic frameworks (MOFs) were performed using molecular modeling techniques. Grand Canonical Monte Carlo (GCMC) simulations were used to study adsorption behavior of 1,1,1,3,3-pentafluoropropane (R-245fa) in a MIL-101 MOF at various temperatures. To understand the stability of the nanofluid composed of MIL-101 particles, we performed molecular dynamics simulations to compute potentials of mean force between hypothetical MIL-101 fragments terminated with two different kinds of modulators in R-245fa and water. Our computed potentials of mean force results indicate that the MOF particles tend to disperse better in water than in R-245fa. The reasons for this observation were analyzed and discussed. Our results agree with experimental results indicating that the employed potential models and modeling approaches provide good description of molecular interactions and the reliabilities. Work performed by LXD was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Work performed by HVRA, SKN, RKM, and PBM was supported by the Office of Energy Efficiency and Renewable Energy, Geothermal Technologies Program. Pacific Northwest National Laboratory is a multiprogram national laboratory operated for DOE by Battelle.

  19. 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.

  20. Thermoelastic Stability Analysis of Solidification of Pure Metals on a Coated Planar Mold of Finite Thickness

    NASA Astrophysics Data System (ADS)

    Demir, Mehmet Hakan; Yigit, Faruk

    2017-04-01

    A theoretical model for investigating the thermoelastic instability/mechanism during pure metal solidification on a coated mold of finite thickness is developed. This study extends the previous theoretical works on growth instability during solidification process by investigating the effects of an added coating layer. Mold coating is one of the most important factors controlling the heat transfer rate, and hence it has a very important role on the solidification rate and the development of microstructure. In this model, thermal and mechanical problems are coupled through the pressure-dependent contact resistances at mold/coating and coating/shell interfaces. The thermal diffusivities of solidified shell, coating, and mold materials are assumed to be zero. This assumption provides us to solve heat transfer problem analytically. A linear perturbation method is used to simplify complexity of the modeled solidification problem, and governing equations are solved numerically using a variable step variable order predictor-corrector algorithm. The effects of coating layer thickness and coupling rates at shell/coating and coating/mold interfaces are investigated in detail. The results show that coating thickness has destabilizing effect on the growth instability when the coupling rates are small. However, when these coupling rates are increased individually or together, the destabilizing effect of coating thickness turns to be stabilizing. On the other hand, coupling rates have generally destabilizing effects on the process, but an increase in the thickness of coating leads to diminishing coupling rates effect in some cases.

  1. Effects of Metal Ions on Stability and Activity of Hyperthermophilic Pyrolysin and Further Stabilization of This Enzyme by Modification of a Ca2+-Binding Site

    PubMed Central

    Zeng, Jing; Gao, Xiaowei; Dai, Zheng; Tang, Bing

    2014-01-01

    Pyrolysin is an extracellular subtilase produced by the marine hyperthermophilic archaeon Pyrococcus furiosus. This enzyme functions at high temperatures in seawater, but little is known about the effects of metal ions on the properties of pyrolysin. Here, we report that the supplementation of Na+, Ca2+, or Mg2+ salts at concentrations similar to those in seawater destabilizes recombinant pyrolysin but leads to an increase in enzyme activity. The destabilizing effect of metal ions on pyrolysin appears to be related to the disturbance of surface electrostatic interactions of the enzyme. In addition, mutational analysis of two predicted high-affinity Ca2+-binding sites (Ca1 and Ca2) revealed that the binding of Ca2+ is important for the stabilization of this enzyme. Interestingly, Asn substitutions at residues Asp818 and Asp820 of the Ca2 site, which is located in the C-terminal extension of pyrolysin, resulted in improvements in both enzyme thermostability and activity without affecting Ca2+-binding affinity. These effects were most likely due to the elimination of unfavorable electrostatic repulsion at the Ca2 site. Together, these results suggest that metal ions play important roles in modulating the stability and activity of pyrolysin. PMID:24561589

  2. Post Gold King Mine Spill Investigation of Metal Stability in Water and Sediments of the Animas River Watershed.

    PubMed

    Rodriguez-Freire, Lucia; Avasarala, Sumant; Ali, Abdul-Mehdi S; Agnew, Diane; Hoover, Joseph H; Artyushkova, Kateryna; Latta, Drew E; Peterson, Eric J; Lewis, Johnnye; Crossey, Laura J; Brearley, Adrian J; Cerrato, José M

    2016-11-01

    We applied spectroscopy, microscopy, diffraction, and aqueous chemistry methods to investigate the persistence of metals in water and sediments from the Animas River 13 days after the Gold King Mine spill (August 5, 2015). The Upper Animas River watershed, located in San Juan Colorado, is heavily mineralized and impacted by acid mine drainage, with low pH water and elevated metal concentrations in sediments (108.4 ± 1.8 mg kg(-1) Pb, 32.4 ± 0.5 mg kg(-1) Cu, 729.6 ± 5.7 mg kg(-1) Zn, and 51 314.6 ± 295.4 mg kg(-1) Fe). Phosphate and nitrogen species were detected in water and sediment samples from Farmington, New Mexico, an intensive agricultural area downstream from the Animas River, while metal concentrations were low compared to those observed upstream. Solid-phase analyses of sediments suggest that Pb, Cu, and Zn are associated with metal-bearing jarosite and other minerals (e.g., clays, Fe-(oxy)hydroxides). The solubility of jarosite at near-neutral pH and biogeochemical processes occurring downstream could affect the stability of metal-bearing minerals in river sediments. This study contributes relevant information about the association of metal mixtures in a heavy mineralized semiarid region, providing a foundation to better understand long-term metal release in a public and agricultural water supply.

  3. Structures and stability of metal-doped GenM (n = 9, 10) clusters

    SciTech Connect

    Qin, Wei; Lu, Wen-Cai; Xia, Lin-Hua; Zhao, Li-Zhen; Zang, Qing-Jun; Wang, C. Z.; Ho, K. M.

    2015-06-26

    The lowest-energy structures of neutral and cationic Ge nM (n = 9, 10; M = Si, Li, Mg, Al, Fe, Mn, Pb, Au, Ag, Yb, Pm and Dy) clusters were studied by genetic algorithm (GA) and first-principles calculations. The calculation results show that doping of the metal atoms and Si into Ge9 and Ge10 clusters is energetically favorable. Most of the metal-doped Ge cluster structures can be viewed as adding or substituting metal atom on the surface of the corresponding ground-state Gen clusters. However, the neutral and cationic FeGe9,10,MnGe9,10 and Ge10Al are cage-like with the metal atom encapsulated inside. Such cage-like transition metal doped Gen clusters are shown to have higher adsorption energy and thermal stability. Our calculation results suggest that Ge9,10Fe and Ge9Si would be used as building blocks in cluster-assembled nanomaterials because of their high stabilities.

  4. Enhanced biological stabilization of heavy metals in sediment using immobilized sulfate reducing bacteria beads with inner cohesive nutrient.

    PubMed

    Li, Xin; Dai, Lihua; Zhang, Chang; Zeng, Guangming; Liu, Yunguo; Zhou, Chen; Xu, Weihua; Wu, Youe; Tang, Xinquan; Liu, Wei; Lan, Shiming

    2017-02-15

    A series of experiments were conducted for treating heavy metals contaminated sediments sampled from Xiangjiang River, which combined polyvinyl alcohol (PVA) and immobilized sulfate reducing bacteria (SRB) into beads. The sodium lactate was served as the inner cohesive nutrient. Coupling the activity of the SRB with PVA, along with the porous structure and huge specific surface area, provided a convenient channel for the transmission of matter and protected the cells against the toxicity of metals. This paper systematically investigated the stability of Cu, Zn, Pb and Cd and its mechanisms. The results revealed the performance of leaching toxicity was lower and the removal efficiencies of Cu, Zn, Pb and Cd were 76.3%, 95.6%, 100% and 91.2%, respectively. Recycling experiments showed the beads could be reused 5 times with superbly efficiency. These results were also confirmed by continuous extraction at the optimal conditions. Furthermore, X-ray diffraction (XRD) and energy-dispersive spectra (EDS) analysis indicated the heavy metals could be transformed into stable crystal texture. The stabilization of heavy metals was attributed to the carbonyl and acyl amino groups. Results presented that immobilized bacteria with inner nutrient were potentially and practically applied to multi-heavy-metal-contamination sediment. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Structures and stability of metal-doped Ge{sub n}M (n = 9, 10) clusters

    SciTech Connect

    Qin, Wei Xia, Lin-Hua; Zhao, Li-Zhen; Zang, Qing-Jun; Lu, Wen-Cai; Wang, C. Z.; Ho, K. M.

    2015-06-15

    The lowest-energy structures of neutral and cationic Ge{sub n}M (n = 9, 10; M = Si, Li, Mg, Al, Fe, Mn, Pb, Au, Ag, Yb, Pm and Dy) clusters were studied by genetic algorithm (GA) and first-principles calculations. The calculation results show that doping of the metal atoms and Si into Ge{sub 9} and Ge{sub 10} clusters is energetically favorable. Most of the metal-doped Ge cluster structures can be viewed as adding or substituting metal atom on the surface of the corresponding ground-state Ge{sub n} clusters. However, the neutral and cationic FeGe{sub 9,10},MnGe{sub 9,10} and Ge{sub 10}Al are cage-like with the metal atom encapsulated inside. Such cage-like transition metal doped Ge{sub n} clusters are shown to have higher adsorption energy and thermal stability. Our calculation results suggest that Ge{sub 9,10}Fe and Ge{sub 9}Si would be used as building blocks in cluster-assembled nanomaterials because of their high stabilities.

  6. The stability and the metal ions binding properties of mutant A85M of CopC.

    PubMed

    Song, Zhen; Dong, Jinlong; Yuan, Wen; Zhang, Caifeng; Ren, Yuehong; Yang, Binsheng

    2016-08-01

    In this work, the mutant A85M of CopC was obtained. The stability of mutant A85M of CopC and the binding properties of metal ions were clarified through various spectroscopic techniques. The binding capacity of A85M to metal ions was measured by fluorescence spectroscopy and UV differential absorbance. The results suggested that Cu(2+) can bind with A85M in 1:1 form, and the constant of A85M was nearly the same as that of CopC. Ag(+) can occupy the Cu(+) binding site located at C-terminal, and the binding constant was (2.64±0.48)×10(6)L/mol. Hg(2+) not only can occupy the Cu(+) binding site located at C-terminal, but also can occupy the Cu(2+) binding site located at N-terminal. The stability of A85M was measured by chemical unfolding experiment. The intermediate was observed in the unfolding pathway of A85M-Cu(2+) induced by urea. In addition, the interaction of SDS with A85M also can result in the formation of the intermediate. The effect of metal ions on the stability of intermediate suggested that the C terminal region of intermediate was unfolded and the N terminal region suffered few effects. Compared with CopC, the stability of A85M was decreased. The main reason was the lower stability of N terminal region. The results of molecular dynamic simulation suggested that when the alanine at 85 site was mutated to methionine, the hydrophobic almost unchanged, but the distance between the phenylalanine at 25 site and tryptophan at 83 site increased because of the spatial effect. And it made the stacking interaction of aromatic rings decreased, which was the main reason for the decreasing stability of N terminal region for A85M.

  7. Multi-decker tricarbonyl-bridged sandwich complexes of transition metals: structure, stability and electron-counting rules.

    PubMed

    Gribanova, Tatyana N; Minyaev, Ruslan M; Minkin, Vladimir I

    2012-11-21

    Structures and stabilities of a new family of multi-decker tricarbonyl-bridged sandwich complexes of transition metals (Cr, Mn, Fe) have been studied using DFT B3LYP/6-311+G(df,p) calculations. Stable structures satisfy the (12n + 6) electron-counting rule, where n is the number of metal atoms. Lengthening of the molecular chains is accompanied by growth of aromaticity of the inner basal cycles, lowering of the aromaticity of the terminal basal cycles and decrease in the energy gap between the frontier orbitals.

  8. Metal Preferences and Metallation*

    PubMed Central

    Foster, Andrew W.; Osman, Deenah; Robinson, Nigel J.

    2014-01-01

    The metal binding preferences of most metalloproteins do not match their metal requirements. Thus, metallation of an estimated 30% of metalloenzymes is aided by metal delivery systems, with ∼25% acquiring preassembled metal cofactors. The remaining ∼70% are presumed to compete for metals from buffered metal pools. Metallation is further aided by maintaining the relative concentrations of these pools as an inverse function of the stabilities of the respective metal complexes. For example, magnesium enzymes always prefer to bind zinc, and these metals dominate the metalloenzymes without metal delivery systems. Therefore, the buffered concentration of zinc is held at least a million-fold below magnesium inside most cells. PMID:25160626

  9. Electronic structures of intermetallic borides RPd3Bx ( R= rare-earth metals)

    NASA Astrophysics Data System (ADS)

    Loison, C.; Leithe-Jasper, A.; Rosner, H.

    2007-05-01

    The electronic structure and the theoretical lattice parameters for the intermetallic antiperovskites RPd3B ( R from La to Yb) are calculated within the density-functional theory using the LSDA+U functional (LSDA is local spin density approximation) to include strong electronic correlations at the R site. Exemplarily, the electronic structure of LaPd3B is discussed and compared with the isoelectronic and isostructural superconductor MgCNi3 . The coherent potential approximation is applied to calculate the lattice parameters of RPd3Bx , where R=La and Lu, as a function of the boron content x . Contrarily to what was reported by Dhar [Mater. Res. Bull. 16, 1557 (1981)], a regular increase is observed in the whole range xɛ[0,1] . Moreover, the calculated lattice parameters obtained for the whole family RPd3B , with R from La to Yb, are much higher than the experimental lattice parameters published by Dhar , questioning their synthesis of stoichiometric compounds RPd3B . Attempts to synthesize RPd3B with R=La , Yb failed for LaPd3B . Instead, in the case of exposure to air, LaPd3Ox is obtained. On the contrary, YbPd3Bx could be obtained (0⩽x⩽0.6) . For this phase, the LSDA+U calculations indicate a valence instability. Thus, boron insertion in RPd3 seems eased by the tendency of the rare earth to become divalent.

  10. In situ stabilization of heavy metals in multiple-metal contaminated paddy soil using different steel slag-based silicon fertilizer.

    PubMed

    Ning, Dongfeng; Liang, Yongchao; Song, Alin; Duan, Aiwang; Liu, Zhandong

    2016-12-01

    Steel slag has been widely used as amendment and silicon fertilizer to alleviate the mobility and bioavailability of heavy metals in soil. The objective of this study was to evaluate the influence of particle size, composition, and application rate of slag on metal immobilization in acidic soil, metals uptake by rice and rice growth. The results indicated that application of slag increased soil pH, plant-available silicon concentrations in soil, and decreased the bioavailability of metals compared with control treatment, whereas pulverous slag (S1) was more effective than granular slag (S2 and S3). The acid-extractable fraction of Cd in the spiked soil was significantly decreased with application of S1 at rates of 1 and 3 %, acid-extractable fractions of Cu and Zn were decreased when treated at 3 %. Use of S1 at both rates resulted in significantly lower Cd, Cu, and Zn concentrations in rice tissues than in controls by 82.6-92.9, 88.4-95.6, and 67.4-81.4 %, respectively. However, use of pulverous slag at 1 % significantly promotes rice growth, restricted rice growth when treated at 3 %. Thus, the results explained that reduced particle size and suitable application rate of slag could be beneficial to rice growth and metals stabilization.

  11. Evaluating the Long-Term Stability of Metals Precipitated In-Situ

    EPA Science Inventory

    Because metals (including metals and metalloids) cannot be destroyed, unlike organic contaminants, in-situ approaches for their removal from groundwater necessarily involves fixation/immobilization in the solid aquifer matrix. Consequently, the success of precipitation based in...

  12. Evaluating the Long-Term Stability of Metals Precipitated In-Situ

    EPA Science Inventory

    Because metals (including metals and metalloids) cannot be destroyed, unlike organic contaminants, in-situ approaches for their removal from groundwater necessarily involves fixation/immobilization in the solid aquifer matrix. Consequently, the success of precipitation based in...

  13. Effect of filler metal composition on the strength of yttria stabilized zirconia joints brazed with Pd-Ag-CuOx

    SciTech Connect

    Darsell, Jens T.; Weil, K. Scott

    2008-09-08

    The Ag-CuOx system is of interest to be used to be used as an air braze filler metal for joining high temperature electrochemical devices. Previous work has shown that the melting temperatures can be increased by adding palladium to Ag-CuOx and it is expected that this may aid high temperature stability. This work compares the room temperature bend strength of joints made between yttria-stabilized zirconia (YSZ) air brazed using Ag-CuOx without palladium and with 5 and 15mol% palladium additions. It has been found that in general palladium decreases joint strength, especially in low copper oxide compositions filler metals. At high copper oxide contents, brittle fracture through both copper oxide rich phases and the YSZ limits joint strength.

  14. Effect of electrolytical hydrogenation on the thermal stability and crystallization kinetics of metallic glass Fe79Si9B12

    NASA Astrophysics Data System (ADS)

    Górecki, Cz; Górecki, T.

    2011-04-01

    The effect of electrolytical hydrogenation on both the surface and volume crystallization kinetics and thermal stability of amorphous alloy Fe79Si9B12 has been investigated. The parameters of the surface and volume crystallization (temperature, activation energy) have been determined applying the exoelectron emission (EEE) and differential thermal analysis (DTA) methods, respectively. It has been found that the surface crystallization of investigated material occurs at temperature much lower and with activation energy smaller than the volume crystallization. The determination of the activation energies for the volume and surface crystallization by the combination of DTA and EEE techniques enables the determination of activation energies for both the nucleation and growth of the crystalline phase in metallic glasses and other amorphous materials. Hydrogenation of the investigated metallic glass reduces its thermal stability, what is manifested by an decrease in the activation energies for both the surface and volume crystallization.

  15. Identification of delamination failure of boride layer on common Cr-based steels

    NASA Astrophysics Data System (ADS)

    Taktak, Sukru; Tasgetiren, Suleyman

    2006-10-01

    Adhesion is an important aspect in the reliability of coated components. With low-adhesion of interfaces, different crack paths may develop depending on the local stress field at the interface and the fracture toughness of the coating, substrate, and interface. In the current study, an attempt has been made to identify the delamination failure of coated Cr-based steels by boronizing. For this reason, two commonly used steels (AISI H13, AISI 304) are considered. The steels contain 5.3 and 18.3 wt.% Cr, respectively. Boriding treatment is carried out in a slurry salt bath consisting of borax, boric acid, and ferrosilicon at a temperature range of 800 950 °C for 3, 5, and 7 h. The general properties of the boron coating are obtained by mechanical and metallographic characterization tests. For identification of coating layer failure, some fracture toughness tests and the Daimler-Benz Rockwell-C adhesion test are used.

  16. Titanium boride equation of state determined by in-situ X-ray diffraction.

    PubMed

    Ono, Shigeaki; Kikegawa, Takumi

    2016-12-01

    The equation of state (EOS) of titanium boride, TiB2, was investigated by in situ X-ray diffraction in a diamond anvil cell and multianvil high-pressure apparatus. The pressure-volume-temperature (P-V-T) data were collected at up to 111 GPa and room temperature for the diamond-anvil cell experiments and at up to 15 GPa and 1300 K for the multianvil experiments. No phase transition was observed through the entire range of experimental conditions. The pressure-volume data at room temperature were fitted using a Vinet EOS to obtain the isothermal bulk modulus, BT0 = 256.7 GPa, and its pressure derivative, B' T0 = 3.83. When fitting a thermal EOS using the P-V-T data for the multianvil experiments, we find that [Formula: see text] = 0.095 (GPa/K) and α 0 = 2.49 × 10(-5) K(-1).

  17. The microstructure and superplastic behavior of clean mechanically alloyed titanium - titanium boride alloys

    SciTech Connect

    Brown, A.P.; Brydson, R.; Hammond, C.; Wisbey, A.; Godfrey, T.M.T.

    2000-07-01

    The superplastic forming (SPF) of titanium alloys is an established technology. A reduction in grain size from that of the typical sheet materials would lead to enhanced SPF properties and hence a reduction in production cycle times. This study describes the microstructural development and superplastic behavior of fine-grained Ti-6%Al-4%V alloys. Ball-milling Ti-6%Al-4%V powder produces a nanocrystalline material; however on consolidation by hot isostatic pressing rapid grain growth occurs. Addition of boron powder during milling leads to boride precipitates in the matrix of the consolidated alloy. The precipitates are dispersed inhomogeneously, resulting in localized grain refinement. Superplastic testing revealed cavitation formation but in comparison to conventional sheet material, large elongations were achieved at relatively high strain rates.

  18. Relative edge energy in the stability of transition metal nanoclusters of different motifs

    NASA Astrophysics Data System (ADS)

    Zhao, X. J.; Xue, X. L.; Guo, Z. X.; Li, S. F.

    2016-06-01

    When a structure is reduced to a nanometer scale, the proportion of the lowly-coordinated edge atoms increases significantly, which can play a crucial role in determining both their geometric and electronic properties, as demonstrated by the recently established generalized Wulff construction principle [S. F. Li, et al., Phys. Rev. Lett., 2013, 111, 115501]. Consequently, it is of great interest to clarify quantitatively the role of the edge atoms that dominate the motifs of these nanostructures. In principle, establishing an effective method valid for determining the absolute value of the surface energy and particularly the edge energy for a given nanostructure is expected to resolve such a problem. However, hitherto, it is difficult to obtain the absolute edge energy of transition metal clusters, particularly when their sizes approach the nanometer regime. In this paper, taking Ru nanoclusters as a prototypical example, our first-principles calculations introduce the concept of relative edge energy (REE), reflecting the net edge atom effect over the surface (facet) atom effect, which is fairly powerful to quasi-quantitatively estimate the critical size at which the crossover occurs between different configurations of a given motif, such as from an icosahedron to an fcc nanocrystal. By contrast, the bulk effect should be re-considered to rationalize the power of the REE in predicting the relative stability of larger nanostructures between different motifs, such as fcc-like and hcp-like nanocrystals.When a structure is reduced to a nanometer scale, the proportion of the lowly-coordinated edge atoms increases significantly, which can play a crucial role in determining both their geometric and electronic properties, as demonstrated by the recently established generalized Wulff construction principle [S. F. Li, et al., Phys. Rev. Lett., 2013, 111, 115501]. Consequently, it is of great interest to clarify quantitatively the role of the edge atoms that dominate the

  19. Metal–Organic Frameworks Stabilize Mono(phosphine)–Metal Complexes for Broad-Scope Catalytic Reactions

    SciTech Connect

    Sawano, Takahiro; Lin, Zekai; Boures, Dean; An, Bing; Wang, Cheng; Lin, Wenbin

    2016-08-10

    Mono(phosphine)–M (M–PR3; M = Rh and Ir) complexes selectively prepared by postsynthetic metalation of a porous triarylphosphine-based metal–organic framework (MOF) exhibited excellent activity in the hydrosilylation of ketones and alkenes, the hydrogenation of alkenes, and the C–H borylation of arenes. The recyclable and reusable MOF catalysts significantly outperformed their homogeneous counterparts, presumably via stabilizing M–PR3 intermediates by preventing deleterious disproportionation reactions/ligand exchanges in the catalytic cycles.

  20. Thermal metamorphism of mantle chromites and the stability of noble-metal nanoparticles

    NASA Astrophysics Data System (ADS)

    González-Jiménez, José M.; Reich, Martin; Camprubí, Antoni; Gervilla, Fernando; Griffin, William L.; Colás, Vanessa; O'Reilly, Suzanne Y.; Proenza, Joaquín A.; Pearson, Norman J.; Centeno-García, Elena

    2015-08-01

    The Loma Baya complex in south-western Mexico is a volume of chromitite-bearing oceanic mantle that records a complex metamorphic history, defined by a first stage of hydrous metamorphism overprinted by a short-lived thermal event associated with an Eocene granite intrusion. During the hydrous metamorphism, the primary magmatic chromite-olivine assemblage was replaced by a secondary, porous intergrowth of Fe2+-rich chromite and chlorite. The heat supplied by an Eocene-age granite intrusion reversed the hydration reaction, producing chromite rims with perfectly developed crystal faces. This third-generation chromite is in equilibrium with highly magnesian (neoformed) olivine and defines a chemical trend analogous to the original magmatic one. The preservation of both reactions in the Loma Baya chromitite provides compelling evidence that the hydration of chromite can be reversed by either prograde metamorphism or any heating event, confirming previous thermodynamic predictions. Understanding these complex features is of particular interest due to the fact that changes in temperature and variable degrees of fluid/rock interaction during metamorphism and intrusion have also significantly affected the chromite-hosted IPGE carrier phases. Here, we propose that the metamorphic fluids involved in the hydrous metamorphism have caused the desulphurization of laurite RuS2, releasing minute particles of Ru-Os-Ir alloys <50 nm in diameter. The following short-lived thermal event that promoted dehydration in the chromitite had the opposite effect on nanoparticle stability, producing a significant coarsening of metal nanoparticles to dimensions larger than a micron. Based on such observations, we argue that IPGE nanoparticles can be exsolved and grown (or coarsen) from sulphide matrices during prograde metamorphism or heating and not exclusively upon cooling under magmatic conditions as it has been previously suggested. These results provide new insights on the relevant role of

  1. High Temperature Stability of Dissimilar Metal Joints in Fission Surface Power Systems

    NASA Technical Reports Server (NTRS)

    Locci, Ivan E.; Nesbitt, James A.; Ritzert, Frank J.; Bowman, Cheryl L.

    2007-01-01

    Future generations of power systems for spacecraft and lunar surface systems will likely require a strong dependence on nuclear power. The design of a space nuclear power plant involves integrating together major subsystems with varying materia1 requirements. Refractory alloys are repeatedly considered for major structural components in space power reactor designs because refractory alloys retain their strength at higher temperatures than other classes of metals. The relatively higher mass and lower ductility of the refractory alloys make them less attractive for lower temperature subsystems in the power plant such as the power conversion system. The power conversion system would consist more likely of intermediate temperature Ni-based superalloys. One of many unanswered questions about the use of refractory alloys in a space power plant is how to transition from the use of the structural refractory alloy to more traditional structural alloys. Because deleterious phases can form when complex alloys are joined and operated at elevated temperatures, dissimilar material diffusion analyses of refractory alloys and superalloys are needed to inform designers about options of joint temperature and operational lifetime. Combinations of four superalloys and six refractory alloys were bonded and annealed at 1150 K and 1300 K to examine diffusional interactions in this study. Joints formed through hot pressing and hot isostatic pressing were compared. Results on newer alloys compared favorably to historical data. Diffusional stability is promising for some combinations of Mo-Re alloys and superalloys at 1150 K, but it appears that lower joint temperatures would be required for other refractory alloy couples.

  2. Estimation of stability constants for metal-ligand complexes containing neutral nitrogen donor atoms with applications to natural organic matter

    NASA Astrophysics Data System (ADS)

    Atalay, Yasemin B.; Di Toro, Dominic M.; Carbonaro, Richard F.

    2013-12-01

    Linear free energy relationships (LFERs) were developed for estimating 1:1 metal-ligand stability constants (log KML) for small organic molecules containing neutral nitrogen donor atoms. A data set of 44 monodentate and 112 bidentate ligands for six metal ions: Mn2+, Co2+, Ni2+, Cu2+, Zn2+ and Cd2+ was employed to parameterize the LFER equations. Monodentate and bidentate log KML values were adequately described using Irving-Rossotti LFERs previously developed for ligands containing negatively-charged oxygen functional groups. Modifications to the LFER equations were necessary to account for steric hindrances to metal complexation by primary, secondary, and tertiary amines. The resulting LFER equations can be used to estimate log KML values for monodentate and bidentate ligands with neutral nitrogen donor groups where such values do not currently exist in the literature. Comparison of these results to our previous work with negatively-charged oxygen donor atoms reveals that neutral nitrogen functional groups are weaker than their oxygen counterparts for metal ions classified as “hard” on the basis of Hard-Soft Acid-Base (HSAB) theory. For “soft” metals, the opposite is true. These LFERs can be used to incorporate nitrogen functional groups in models for metal ion binding to natural organic matter (NOM).

  3. Thermal Shock Resistance of Stabilized Zirconia/Metal Coat on Polymer Matrix Composites by Thermal Spraying Process

    NASA Astrophysics Data System (ADS)

    Zhu, Ling; Huang, Wenzhi; Cheng, Haifeng; Cao, Xueqiang

    2014-12-01

    Stabilized zirconia/metal coating systems were deposited on the polymer matrix composites by a combined thermal spray process. Effects of the thicknesses of metal layers and ceramic layer on thermal shock resistance of the coating systems were investigated. According to the results of thermal shock lifetime, the coating system consisting of 20 μm Zn and 125 μm 8YSZ exhibited the best thermal shock resistance. Based on microstructure evolution, failure modes and failure mechanism of the coating systems were proposed. The main failure modes were the formation of vertical cracks and delamination in the outlayer of substrate, and the appearance of coating spallation. The residual stress, thermal stress and oxidation of substrate near the substrate/metal layer interface were responsible for coating failure, while the oxidation of substrate near the substrate/coating interface was the dominant one.

  4. Metal-coupled folding as the driving force for the extreme stability of Rad50 zinc hook dimer assembly

    PubMed Central

    Kochańczyk, Tomasz; Nowakowski, Michał; Wojewska, Dominika; Kocyła, Anna; Ejchart, Andrzej; Koźmiński, Wiktor; Krężel, Artur

    2016-01-01

    The binding of metal ions at the interface of protein complexes presents a unique and poorly understood mechanism of molecular assembly. A remarkable example is the Rad50 zinc hook domain, which is highly conserved and facilitates the Zn2+-mediated homodimerization of Rad50 proteins. Here, we present a detailed analysis of the structural and thermodynamic effects governing the formation and stability (logK12 = 20.74) of this evolutionarily conserved protein assembly. We have dissected the determinants of the stability contributed by the small β-hairpin of the domain surrounding the zinc binding motif and the coiled-coiled regions using peptides of various lengths from 4 to 45 amino acid residues, alanine substitutions and peptide bond-to-ester perturbations. In the studied series of peptides, an >650 000-fold increase of the formation constant of the dimeric complex arises from favorable enthalpy because of the increased acidity of the cysteine thiols in metal-free form and the structural properties of the dimer. The dependence of the enthalpy on the domain fragment length is partially compensated by the entropic penalty of domain folding, indicating enthalpy-entropy compensation. This study facilitates understanding of the metal-mediated protein-protein interactions in which the metal ion is critical for the tight association of protein subunits. PMID:27808280

  5. Metal-coupled folding as the driving force for the extreme stability of Rad50 zinc hook dimer assembly

    NASA Astrophysics Data System (ADS)

    Kochańczyk, Tomasz; Nowakowski, Michał; Wojewska, Dominika; Kocyła, Anna; Ejchart, Andrzej; Koźmiński, Wiktor; Krężel, Artur

    2016-11-01

    The binding of metal ions at the interface of protein complexes presents a unique and poorly understood mechanism of molecular assembly. A remarkable example is the Rad50 zinc hook domain, which is highly conserved and facilitates the Zn2+-mediated homodimerization of Rad50 proteins. Here, we present a detailed analysis of the structural and thermodynamic effects governing the formation and stability (logK12 = 20.74) of this evolutionarily conserved protein assembly. We have dissected the determinants of the stability contributed by the small β-hairpin of the domain surrounding the zinc binding motif and the coiled-coiled regions using peptides of various lengths from 4 to 45 amino acid residues, alanine substitutions and peptide bond-to-ester perturbations. In the studied series of peptides, an >650 000-fold increase of the formation constant of the dimeric complex arises from favorable enthalpy because of the increased acidity of the cysteine thiols in metal-free form and the structural properties of the dimer. The dependence of the enthalpy on the domain fragment length is partially compensated by the entropic penalty of domain folding, indicating enthalpy-entropy compensation. This study facilitates understanding of the metal-mediated protein-protein interactions in which the metal ion is critical for the tight association of protein subunits.

  6. Effect of the Anion Activity on the Stability of Li Metal Anodes in Lithium-Sulfur Batteries

    SciTech Connect

    Cao, Ruiguo; Chen, Junzheng; Han, Kee Sung; Xu, Wu; Mei, Donghai; Bhattacharya, Priyanka; Engelhard, Mark H.; Mueller, Karl T.; Liu, Jun; Zhang, Ji-Guang

    2016-03-29

    With the significant progress made in the development of cathodes in lithium-sulfur (Li-S) batteries, the stability of Li metal anodes becomes a more urgent challenge in these batteries. Here we report the systematic investigation of the stability of the anode/electrolyte interface in Li-S batteries with concentrated electrolytes containing various lithium salts. It is found that Li-S batteries using LiTFSI-based electrolytes are more stable than those using LiFSI-based electrolytes. The decreased stability is because the N-S bond in the FSI- anion is fairly weak and the scission of this bond leads to the formation of lithium sulfate (LiSOx) in the presence of polysulfide species. In contrast, even the weakest bond (C-S) in the TFSI- anion is stronger than the N-S bond in the FSI- anion. In the LiTFSI-based electrolyte, the lithium metal anode tends to react with polysulfide to form lithium sulfide (LiSx) which is more reversible than LiSOx formed in the LiTFSI-based electrolyte. This fundamental difference in the bond strength of the salt anions in the presence of polysulfide species leads to a large difference in the stability of the anode-electrolyte interface and performance of the Li-S batteries with electrolytes composed of these salts. Therefore, anion selection is one of the key parameters in the search for new electrolytes for stable operation of Li-S batteries.

  7. Promotion of activity and thermal stability of chloroperoxidase by trace amount of metal ions (M2+/M3+).

    PubMed

    Li, Haiyun; Gao, Jinwei; Wang, Limin; Li, Xiaohong; Jiang, Yucheng; Hu, Mancheng; Li, Shuni; Zhai, Quanguo

    2014-03-01

    The effect of M(2+) (Zn(2+), Cu(2+), Cd(2+), Mn(2+), Pb(2+)) and M(3+) (Cr(3+), La(3+), Fe(3+), Ce(3+), Y(3+), Al(3+)) metal ions on the activity and thermal stability of chloroperoxidase (CPO) was investigated in this work. It was found that the lower concentration of metal ions was favorable to CPO activity whereas the higher concentration reversed the results. CPO activity could be increased to 116.4-127.1% in the presence of a trace amount of these M(2+)/M(3+) metal ions at a concentration range of 0-25 μmol L(-1) after 2 h of incubation at 25 °C. The activating effect of M(3+) is better than that of M(2+), and Cr(3+) was mostly efficient. The thermal stability of the enzyme was also improved significantly. Only 30.3% of CPO activity was retained at 50 °C whereas 82.6% of CPO activity was maintained in the presence of Cr(3+) after 2 h of incubation at the same temperature. The activation of CPO by metal ions at their low concentration was studied through intrinsic fluorescence, circular dichroism (CD), and UV-Vis spectra assay. A favorable environment around the active site was achieved in the presence of metal ions. Intrinsic fluorescence and CD spectra indicated that the α-helix structure of CPO was strengthened in metal ion-contained media. More exposure of the heme ring was achieved for easy access of the substrate, which was suggested by UV-Vis spectrum analysis. This strategy for enhancing CPO activity is very simple and useful. It will be favorable to the practical application of this enzyme.

  8. A Modulator-Induced Defect-Formation Strategy to Hierarchically Porous Metal-Organic Frameworks with High Stability.

    PubMed

    Cai, Guorui; Jiang, Hai-Long

    2017-01-09

    The pore size enlargement and structural stability have been recognized as two crucial targets, which are rarely achieved together, in the development of metal-organic frameworks (MOFs). Herein, we have developed a versatile modulator-induced defect-formation strategy, in the presence of monocarboxylic acid as a modulator and an insufficient amount of organic ligand, successfully realizing the controllable synthesis of hierarchically porous MOFs (HP-MOFs) with high stability and tailorable pore characters. Remarkably, the integration of high stability and large mesoporous property enables these HP-MOFs to be important porous platforms for applications involving large molecules, especially in catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Improved electrochemical performance of micro-sized SiO-based composite anode by prelithiation of stabilized lithium metal powder

    NASA Astrophysics Data System (ADS)

    Pan, Qingrui; Zuo, Pengjian; Mu, Tiansheng; Du, Chunyu; Cheng, Xinqun; Ma, Yulin; Gao, Yunzhi; Yin, Geping

    2017-04-01

    The micro-sized SiO-based composite anode material (d-SiO/G/C) for lithium-ion batteries (LIBs) is achieved via the disproportionation reaction of SiO followed by a pitch pyrolysis reaction. The d-SiO/G/C composite exhibits an initial reversible capacity of 905 mAh g-1 and excellent cycling stability. The initial Coulombic efficiency of the d-SiO/G/C composite can be significantly improved from 68.1% to 98.5% by the prelithiation of the composite anode using stabilized lithium metal powders (SLMP), which counteracts the irreversible capacity loss caused by the solid electrolyte interphase (SEI) formation and irreversible conversion reaction during the first lithiation. The micro-sized d-SiO/G/C composite anode with SLMP prelithiation maintains an excellent cycling stability, suggesting its great potential in practical application for high specific energy lithium ion batteries.

  10. Stabilization of heavy metals in municipal sewage sludge by freeze-thaw treatment with a blend of diatomite, FeSO4, and Ca(OH)2.

    PubMed

    Wang, Jing; Fu, Rongbing; Xu, Zhen

    2017-08-01

    In this work, the effects of diatomite with 15% FeSO4•7H2O and 7.5% Ca(OH)2 on sludge stabilization were investigated using batch leaching tests. The influence of cell rupture caused by freezing and thawing on stabilization was also evaluated. The results indicated that the optimal diatomite percentage was 2%. Cell rupture by freezing and thawing reduced heavy metal leachability, followed by cell death and decrease of organic groups. The concentration of heavy metals in sludge leachate increased after cell rupture, indicating that the heavy metal leachability was reduced after freezing and thawings. Moreover, the stabilization effects were generally improved after freezing and thawing. As compared with the stabilization of the original sludge, the unstable fractions decreased and the residual fractions of the heavy metals increased in the stabilized sludge after cell rupture. This study developed a method to stabilize heavy metals in municipal sewage sludge. Diatomite combined with FeSO4·7H2O and Ca(OH)2 improved the treatment of sewage sludge contaminated by heavy metals. Cell lysis by freeze-thaw treatment reduced the risk of leaching heavy metals caused by cell death and decreased major organic groups in the sludge.

  11. The importance of sulphide binding for leaching of heavy metals from contaminated Norwegian marine sediments treated by stabilization/solidification.

    PubMed

    Sparrevik, Magnus; Eek, Espen; Grini, Randi Skirstad

    2009-07-01

    Over time, Norwegian fjords and harbour areas have received contaminants from industrial activities and urban run-off, and measures to remediate contaminated marine sediments are therefore needed. Stabilization/solidification (S/S) technology, in which the contaminated marine sediments are mixed with cement and other binding agents, has been shown to be a promising remediation technology. This paper summarizes a study of the environmental effect of stabilization, highlighting the importance of sulphide binding governing the leaching of heavy metals from the S/S of contaminated marine sediments. The study is a part of a research project focusing on developing effective methods for S/S of contaminated seabed sediments for use in new construction areas. Four cementitious binders were tested on sediments from six different locations: Bergen, Gilhus, Grenland, Hammerfest, Sandvika and Trondheim. The sediments differed with respect to properties such as concentration of contaminants, water content, organic content and grain size distribution. Portland cement, Portland cement with fly ash, industry cement, and sulphate resistant cement, were tested as binders. The leaching from the S/S sediments after 28 days of curing was measured by using a standard leaching batch test (EN 12457-2: 2003), with seawater as leaching agent. The eluate was analysed for pH and redox, as well as content of heavy metals and organic contaminants. Available volatile sulphide (AVS) and simultaneously extractable metals (SEM) were also measured in the sediments. This paper focuses on the leaching of lead (Pb) and copper (Cu). A reduced leaching of Pb after stabilization was observed for the mixtures, whereas the leaching of Cu from Hammerfest sediments increased substantially after stabilization for all cementitious additions. Experiments show that Hammerfest samples had lower values of AVS than the other sediments. This was confirmed by the SEM/AVS analysis, highlighting the importance of

  12. The Nature of the Microstructure and Interface Boundary Formation in Directionally Solidified Ceramic Boride Composites

    DTIC Science & Technology

    2011-05-01

    21 2.1.6. Main mechanical properties of LaB6-(TixZr1-x)B2 composites .............................. 22 2.2. Eutectic composition determination in... properties of alloys in the LaB6-MeB2 system. Table 2. – Lattice parameters of metallic Ti and Zr [14] and of Ti-Zr solid solutions Table 3. – Lattice...solidified eutectics (DSEs) have attracted considerable attention because of their thermodynamic compatibility and microstructural stability up to the

  13. Effects of Dopant Metal Variation and Material Synthesis Method on the Material Properties of Mixed Metal Ferrites in Yttria Stabilized Zirconia for Solar Thermochemical Fuel Production

    DOE PAGES

    Leonard, Jeffrey; Reyes, Nichole; Allen, Kyle M.; ...

    2015-01-01

    Mixed metal ferrites have shown much promise in two-step solar-thermochemical fuel production. Previous work has typically focused on evaluating a particular metal ferrite produced by a particular synthesis process, which makes comparisons between studies performed by independent researchers difficult. A comparative study was undertaken to explore the effects different synthesis methods have on the performance of a particular material during redox cycling using thermogravimetry. This study revealed that materials made via wet chemistry methods and extended periods of high temperature calcination yield better redox performance. Differences in redox performance between materials made via wet chemistry methods were minimal andmore » these demonstrated much better performance than those synthesized via the solid state method. Subsequently, various metal ferrite samples (NiFe 2 O 4 , MgFe 2 O 4 , CoFe 2 O 4 , and MnFe 2 O 4 ) in yttria stabilized zirconia (8YSZ) were synthesized via coprecipitation and tested to determine the most promising metal ferrite combination. It was determined that 10 wt.% CoFe 2 O 4 in 8YSZ produced the highest and most consistent yields of O 2 and CO. By testing the effects of synthesis methods and dopants in a consistent fashion, those aspects of ferrite preparation which are most significant can be revealed. More importantly, these insights can guide future efforts in developing the next generation of thermochemical fuel production materials.« less

  14. Trace Metals in Groundwater & the Vadose Zone Calcite: In Situ Containment & Stabilization of Strontium-90 & Other Divalent Metals & Radionuclides at Arid West DOE

    SciTech Connect

    Smith, Robert W.

    2004-12-01

    Radionuclide and metal contaminants such as strontium-90 are present beneath U.S. Department of Energy (DOE) lands in both the groundwater (e.g., 100-N area at Hanford, WA) and vadose zone (e.g., Idaho Nuclear Technology and Engineering Center at the Idaho National Engineering and Environmental Laboratory). In situ containment and stabilization of these contaminants is a cost-effective treatment strategy. However, implementing in situ containment and stabilization approaches requires definition of the mechanisms that control contaminant sequestration. We are investigating the in situ immobilization of radionuclides or contaminant metals (e.g., strontium-90) by their facilitated co-precipitation with calcium carbonate in groundwater and vadose zone systems. Our facilitated approach, shown schematically in Figure 1, relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal co-precipitation) by increasing pH and alkalinity. Subsurface urea hydrolysis is catalyzed by the urease enzyme, which may be either introduced with the urea or produced in situ by ubiquitous subsurface urea hydrolyzing microorganisms. Because the precipitation process tends to be irreversible and many western aquifers are saturated with respect to calcite, the co-precipitated metals and radionuclides will be effectively removed from the aqueous phase over the long-term. Another advantage of the ureolysis approach is that the ammonium ions produced by the reaction can exchange with radionuclides sorbed to subsurface minerals, thereby enhancing the availability of the radionuclides for re-capture in a more stable solid phase (co-precipitation rather than adsorption).

  15. Trace Metals in Groundwater & Vadose Zone Calcite: In Situ Containment & Stabilization of 90Strontium & Other Divalent Metals & Radionuclides at Arid West DOE Sites

    SciTech Connect

    Smith, Robert W.; Fujita, Yoshiko; Ferris, F. Grant; Cosgrove, Donna M.; Colwell, Rick S.

    2004-06-01

    Radionuclide and metal contaminants such as 90Sr are present beneath U.S. Department of Energy (DOE) lands in both the groundwater (e.g., 100-N area at Hanford, WA) and vadose zone (e.g., Idaho Nuclear Technology and Engineering Center (INTEC) at the Idaho National Engineering and Environmental Laboratory). In situ containment and stabilization of these contaminants is a cost-effective treatment strategy. However, implementing in situ containment and stabilization approaches requires definition of the mechanisms that control contaminant sequestration. We are investigating the in situ immobilization of radionuclides or contaminant metals (e.g., 90Sr) by their facilitated co-precipitation with calcium carbonate in groundwater and vadose zone systems. Our facilitated approach, shown schematically in Figure 1, relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal co-precipitation) by increasing pH and alkalinity. Subsurface urea hydrolysis is catalyzed by the urease enzyme, which may be either introduced with the urea or produced in situ by ubiquitous subsurface urea hydrolyzing microorganisms. Because the precipitation process tends to be irreversible and many western aquifers are saturated with respect to calcite, the co-precipitated metals and radionuclides will be effectively removed from the aqueous phase over the long-term. Another advantage of the ureolysis approach is that the ammonium ions produced by the reaction can exchange with radionuclides sorbed to subsurface minerals, thereby enhancing the availability of the radionuclides for re-capture in a more stable solid phase (co-precipitation rather than adsorption).

  16. Trace Metals in Groundwater & Vadose Zone Calcite: In Situ Containment & Stabilization of Stronthium-90 & Other Divalent Metals & Radionuclides at Arid West DOE

    SciTech Connect

    Smith, Robert W.

    2005-06-01

    Radionuclide and metal contaminants such as strontium-90 are present beneath U.S. Department of Energy (DOE) lands in both the groundwater (e.g., 100-N area at Hanford, WA) and vadose zone (e.g., Idaho Nuclear Technology and Engineering Center [INTEC] at the Idaho National Laboratory [INL]). In situ containment and stabilization of these contaminants is a cost-effective treatment strategy. However, implementing in situ containment and stabilization approaches requires definition of the mechanisms that control contaminant sequestration. We are investigating the in situ immobilization of radionuclides or contaminant metals (e.g., strontium-90) by their facilitated co-precipitation with calcium carbonate (primarily calcite) in groundwater and vadose zone systems. Our facilitated approach relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal co-precipitation) by (a) increasing pH and alkalinity and (b) liberating cations from the aquifer matrix by cation exchange reactions. Subsurface urea hydrolysis is catalyzed by the urease enzyme, which is produced in situ by native urea hydrolyzing microorganisms. Because the precipitation process tends to be irreversible and many western aquifers are saturated with respect to calcite, the co-precipitated metals and radionuclides will be effectively removed from the aqueous phase over the long term. We are currently conducting field based activities at both the INL Vadose Zone Research Park (VZRP), an uncontaminated surrogate site for the strontium-90 contaminated vadose zone at INTEC and at the strontium-90 contaminated aquifer of 100-N area of the Hanford site.

  17. Stabilization mechanism of γ-Mg17Al12 and β-Mg2Al3 complex metallic alloys

    NASA Astrophysics Data System (ADS)

    Vrtnik, S.; Jazbec, S.; Jagodič, M.; Korelec, A.; Hosnar, L.; Jagličić, Z.; Jeglič, P.; Feuerbacher, M.; Mizutani, U.; Dolinšek, J.

    2013-10-01

    Large-unit-cell complex metallic alloys (CMAs) frequently achieve stability by lowering the kinetic energy of the electron system through formation of a pseudogap in the electronic density of states (DOS) across the Fermi energy ɛF. By employing experimental techniques that are sensitive to the electronic DOS in the vicinity of ɛF, we have studied the stabilization mechanism of two binary CMA phases from the Al-Mg system: the γ-Mg17Al12 phase with 58 atoms in the unit cell and the β-Mg2Al3 phase with 1178 atoms in the unit cell. Since the investigated alloys are free from transition metal elements, orbital hybridization effects must be small and we were able to test whether the alloys obey the Hume-Rothery stabilization mechanism, where a pseudogap in the DOS is produced by the Fermi surface-Brillouin zone interactions. The results have shown that the DOS of the γ-Mg17Al12 phase exhibits a pronounced pseudogap centered almost exactly at ɛF, which is compatible with the theoretical prediction that this phase is stabilized by the Hume-Rothery mechanism. The disordered cubic β-Mg2Al3 phase is most likely entropically stabilized at high temperatures, whereas at lower temperatures stability is achieved by undergoing a structural phase transition to more ordered rhombohedral β‧ phase at 214 ° C, where all atomic sites become fully occupied. No pseudogap in the vicinity of ɛF was detected for the β‧ phase on the energy scale of a few 100 meV as determined by the ‘thermal observation window’ of the Fermi-Dirac function, so that the Hume-Rothery stabilization mechanism is not confirmed for this compound. However, the existence of a much broader shallow pseudogap due to several critical reciprocal lattice vectors \\buildrel{\\rightharpoonup}\\over{G} that simultaneously satisfy the Hume-Rothery interference condition remains the most plausible stabilization mechanism of this phase. At Tc = 0.85 K, the β‧ phase undergoes a superconducting transition

  18. Microstructural Characterization and Wear Behavior of Nano-Boride Dispersed Coating on AISI 304 Stainless Steel by Hybrid High Velocity Oxy-Fuel Spraying Laser Surface Melting

    NASA Astrophysics Data System (ADS)

    Sharma, Prashant; Majumdar, Jyotsna Dutta

    2015-07-01

    The current study concerns the detailed microstructural characterization and investigation of wear behavior of nano-boride dispersed coating developed on AISI 304 stainless steel by high velocity oxy-fuel spray deposition of nickel-based alloy and subsequent laser melting. There is a significant refinement and homogenization of microstructure with improvement in microhardness due to laser surface melting (1200 VHN as compared to 945 VHN of as-sprayed and 250 VHN of as-received substrate). The high temperature phase stability of the as-coated and laser melted surface has been studied by differential scanning calorimeter followed by detailed phase analysis at room and elevated temperature. There is a significant improvement in wear resistance of laser melted surface as compared to as-sprayed and the as-received one due to increased hardness and reduced coefficient of friction. The mechanism of wear has been investigated in details. Corrosion resistance of the coating in a 3.56 wt pct NaCl solution is significantly improved (4.43 E-2 mm/year as compared to 5 E-1 mm/year of as-sprayed and 1.66 mm/year of as-received substrate) due to laser surface melting as compared to as-sprayed surface.

  19. Emerging Technologies for the Remediation of Metals in Soils, Insitu Stabilization/Inplace Inactivation

    DTIC Science & Technology

    1997-12-01

    Technologies” document. 1.1 Background Heavy metal contamination in soils is widespread in the U.S. and other parts of the world. Unlike organic...compounds that can be destroyed, heavy metals can only be covered, buried, removed and recycled, moved to a safer location, or transformed into a less toxic... heavy metals in soils is an important consideration in determining the hazard to human health and the environment. Some chemical forms of some heavy

  20. Microbial stabilization and mass reduction of wastes containing radionuclides and toxic metals

    DOEpatents

    Francis, Arokiasamy J.; Dodge, Cleveland J.; Gillow, Jeffrey B.

    1991-01-01

    A process is provided to treat wastes containing radionuclides and toxic metals with Clostridium sp. BFGl to release a large fraction of the waste solids into solutin and convert the radionuclides and toxic metals to a more concentrated and stable form with concurrent volume and mass reduction. The radionuclides and toxic metals being in a more stable form are available for recovery, recycling and disposal.