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Sample records for metal complexes formed

  1. Ring and Volcano Structures Formed by a Metal Dipyrromethene Complex

    Son, Seung Bae; Hahn, Jae Ryang [Chonbuk National Univ., Jeonju (Korea, Republic of); Miao, Qing; Shin, Jiyoung; Dolphin, David [Univ. of British Columbia, Columbia (Canada)

    2014-06-15

    Dichloromethane liquid droplets containing a cobalt dipyrromethene trimer deposited on a graphite surface were found to form coffee ring, toroid ring, or volcano dot structures due to the redistribution of the solute during solvent evaporation. The shapes and size distributions of the ring structures depended on the drying temperature. The shape differences were attributed to the fact that the solvent evaporation rate controlled the self-assembly process that yielded the coffee stain and pinhole structures.

  2. Rubber pad forming - Efficient approach for the manufacturing of complex structured sheet metal blanks for food industry

    Spoelstra, Paul; Djakow, Eugen; Homberg, Werner

    2017-10-01

    The production of complex organic shapes in sheet metals is gaining more importance in the food industry due to increasing functional and hygienic demands. Hence it is necessary to produce parts with complex geometries promoting cleanability and general sanitation leading to improvement of food safety. In this context, and especially when stainless steel has to be formed into highly complex geometries while maintaining desired surface properties, it is inevitable that alternative manufacturing processes will need to be used which meet these requirements. Rubber pad forming offers high potential when it comes to shaping complex parts with excellent surface quality, with virtually no tool marks and scratches. Especially in cases where only small series are to be produced, rubber pad forming processes offers both technological and economic advantages. Due to the flexible punch, variation in metal thickness can be used with the same forming tool. The investments to set-up Rubber pad forming is low in comparison to conventional sheet metal forming processes. The process facilitates production of shallow sheet metal parts with complex contours and bends. Different bending sequences in a multiple tool set-up can also be conducted. The planned contribution thus describes a brief overview of the rubber pad technology. It shows the prototype rubber pad forming machine which can be used to perform complex part geometries made from stainless steel (1.4301). Based on an analysis of the already existing systems and new machines for rubber pad forming processes, together with their process properties, influencing variables and areas of application, some relevant parts for the food industry are presented.

  3. Laser rapid forming technology of high-performance dense metal components with complex structure

    Huang, Weidong; Chen, Jing; Li, Yanming; Lin, Xin

    2005-01-01

    Laser rapid forming (LRF) is a new and advanced manufacturing technology that has been developed on the basis of combining high power laser cladding technology with rapid prototyping (RP) to realize net shape forming of high performance dense metal components without dies. Recently we have developed a set of LRF equipment. LRF experiments were carried out on the equipment to investigate the influences of processing parameters on forming characterizations systematically with the cladding powder materials as titanium alloys, superalloys, stainless steel, and copper alloys. The microstructure of laser formed components is made up of columnar grains or columnar dendrites which grow epitaxially from the substrate since the solid components were prepared layer by layer additionally. The result of mechanical testing proved that the mechanical properties of laser formed samples are similar to or even over that of forging and much better than that of casting. It is shown in this paper that LRF technology is providing a new solution for some difficult processing problems in the high tech field of aviation, spaceflight and automobile industries.

  4. MECHANISMS OF THE COMPLEX FORMATION BY d-METALS ON POROUS SUPPORTS AND THE CATALYTIC ACTIVITY OF THE FORMED COMPLEXES IN REDOX REACTIONS

    T. L. Rakitskaya

    2015-11-01

    Full Text Available The catalytic activity of supported complexes of d metals in redox reactions with participation of gaseous toxicants, PH3, CO, O3, and SO2, depends on their composition. Owing to the variety of physicochemical and structural-adsorption properties of available supports, their influence on complex formation processes, the composition and catalytic activity of metal complexes anchored on them varies over a wide range. The metal complex formation on sup-ports with weak ion-exchanging properties is similar to that in aqueous solutions. In this case, the support role mainly adds up to the ability to reduce the activity of water adsorbed on them. The interaction between a metal complex and a support surface occurs through adsorbed water molecules. Such supports can also affect complex formation processes owing to protolytic reactions on account of acidic properties of sorbents used as supports. The catalytic activity of metal complexes supported on polyphase natural sorbents considerably depends on their phase relationship. In the case of supports with the nonsimple structure and pronounced ion-exchanging properties, for instance, zeolites and laminar silicates, it is necessary to take into account the variety of places where metal ions can be located. Such location places determine distinctions in the coordination environment of the metal ions and the strength of their bonding with surface adsorption sites and, therefore, the catalytic activity of surface complexes formed by theses metal ions. Because of the energy surface inhomogeneity, it is important to determine a relationship between the strength of a metal complex bonding with a support surface and its catalytic activity. For example, bimetallic complexes are catalytically active in the reactions of oxidation of the above gaseous toxicants. In particular, in the case of carbon monoxide oxidation, the most catalytic activity is shown by palladium-copper complexes in which copper(II is strongly

  5. Dissolution of various metal oxides in different forms in dilute organic complexants

    Srinivasan, M.P.; Chandramohan, P.; Velmurugan, S.; Narasimhan, S.V.; Ranganathan, S.

    2002-01-01

    The dissolution of iron containing metal oxides is of importance in various power plant industries from the point of crud and scale removal for efficient operation and better performance of plant. The removal of these oxides has to be accomplished with minimum corrosion to the structural material, with minimum cost and removal duration and also with minimum waste generation for easy disposal. Activity build-up due to pick up of 60 Co and fission products occurs on PHT system surfaces of nuclear power plants. The dissolution kinetics of these oxides are influenced by pH, redox potential, chelating strength, concentration and temperature of the solution, constitution of oxides, and the physical form of existence of oxides. In this paper the influence of the existence of different forms of iron oxides on the ability of the dissolution characteristics of the different formulations have been brought out. How the change in dissolution characteristics can be ingenuously used to characterize both qualitatively and quantitatively the mixtures of oxides have been brought out. How the magnetite dissolution behaviour varies for base metal unaided condition in different formulation in static condition, in regenerative mode is also brought out. The OCP values and iron release behaviour for magnetite coated CS surface and magnetite pellet were also described. (authors)

  6. Dissolution of various metal oxides in different forms in dilute organic complexants

    Srinivasan, M.P.; Chandramohan, P.; Velmurugan, S.; Narasimhan, S.V. [Water and Steam Chemistry Lab., BARC Facilities, Tamilnadu (India); Ranganathan, S. [Madras Univ. (India). Research Scholar

    2002-07-01

    The dissolution of iron containing metal oxides is of importance in various power plant industries from the point of crud and scale removal for efficient operation and better performance of plant. The removal of these oxides has to be accomplished with minimum corrosion to the structural material, with minimum cost and removal duration and also with minimum waste generation for easy disposal. Activity build-up due to pick up of {sup 60}Co and fission products occurs on PHT system surfaces of nuclear power plants. The dissolution kinetics of these oxides are influenced by pH, redox potential, chelating strength, concentration and temperature of the solution, constitution of oxides, and the physical form of existence of oxides. In this paper the influence of the existence of different forms of iron oxides on the ability of the dissolution characteristics of the different formulations have been brought out. How the change in dissolution characteristics can be ingenuously used to characterize both qualitatively and quantitatively the mixtures of oxides have been brought out. How the magnetite dissolution behaviour varies for base metal unaided condition in different formulation in static condition, in regenerative mode is also brought out. The OCP values and iron release behaviour for magnetite coated CS surface and magnetite pellet were also described. (authors)

  7. Micro metal forming

    2013-01-01

    Micro Metal Forming, i. e. forming of parts and features with dimensions below 1 mm, is a young area of research in the wide field of metal forming technologies, expanding the limits for applying metal forming towards micro technology. The essential challenges arise from the reduced geometrical size and the increased lot size. In order to enable potential users to apply micro metal forming in production, information about the following topics are given: tribological behavior: friction between tool and work piece as well as tool wear mechanical behavior: strength and formability of the work piece material, durability of the work pieces size effects: basic description of effects occurring due to the fact, that the quantitative relation between different features changes with decreasing size process windows and limits for forming processes tool making methods numerical modeling of processes and process chains quality assurance and metrology All topics are discussed with respect to the questions relevant to micro...

  8. Metal forming and lubrication

    Bay, Niels

    2000-01-01

    Lubrication is essential in most metal forming processes. The lubricant film has two basic functions, [1]: i. to separate the work piece and tool surfaces and ii. to cool the workpiece and the tool. Separation of the two surfaces implies lower friction facilitating deformation and lowering the tool...

  9. Enhanced diffusion of solute metals forming complexes with radiation defects in silica

    Pivin, J.C.; Garrido, E.; Rizza, G.; Thome, L.

    1998-01-01

    The mixing kinetics of Cu, Ag, W, Pt, and Au single layers embedded in silica when irradiated with heavy ions at temperatures (T) of 110 and 300 K was investigated by means of in situ RBS analyses in alternation with irradiations. The spreading of peaks related to the metallic species is generally anisotropic and obeys either a quadratic or a linear dependence on the ion dose according to the increasing T. The quadratic law is attributed to a control of the diffusion by the coupling of the large impurity atoms M with matrix defects, and a classical regime of radiation enhanced diffusion is observed when this coupling is made easier (higher T or mass of M). Other factors such as internal stresses affect the rates of M dissolution and diffusion. (orig.)

  10. Complexing in the systems of thorium tetrabromide-alkali metal bromide and structure of formed compounds

    Gershanovich, A.Ya.; Suglobova, I.G.

    1981-01-01

    Phase diagrams of the ThBr 4 -MBr binary systems (M=Na, K, Rb, Cs) are obtained using the methods of thermographic and X-ray phase analyses. Congruently melting compounds of the M 2 ThBr 6 form (M=K, Rb, Cs) with melting temperatures of 635, 650 and 680 deg C, respectively, and the NaThBr 5 decomposing in the solid phase reaction at 356 deg C, realized in the systems. The presence of eutectic points is established, their composition and melting temperatures are determined. Roentgenograms of all compounds prepared by the polycrystal method are obtained. K 2 ThBr 6 and Rb 2 ThBr 6 crystallize in the hexagonal crystal system (Rb 2 MnF 6 structure type) with 2 formula units in the lattice cell. The parameters of the K 2 ThBr 6 cell are a=0.752 nm, c=1.180 nm. The cell parameters of the Rb 2 ThBr 6 cell are a=0.758 nm, c=1.224 nm. The Cs 2 ThBr 6 has a pseudocubic tetragonal structure with 4 formula units in a cell. Parameters of the Cs 2 ThBr 6 cell are a=1.137 nm; c=1.069 nm [ru

  11. Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln2+ Complexes and Unusual [Li(2.2.2-cryptand)]1+ Cations.

    Huh, Daniel N; Darago, Lucy E; Ziller, Joseph W; Evans, William J

    2018-02-19

    The utility of lithium compared to other alkali metals in generating Ln 2+ rare-earth metal complexes via reduction of Ln 3+ precursors in reactions abbreviated as LnA 3 /M (Ln = rare-earth metal; A = anionic ligand; M = alkali metal) is described. Lithium reduction of Cp' 3 Ln (Cp' = C 5 H 4 SiMe 3 ; Ln = Y, Tb, Dy, Ho) under Ar in the presence of 2.2.2-cryptand (crypt) forms new examples of crystallographically characterizable Ln 2+ complexes of these metals, [Li(crypt)][Cp' 3 Ln]. In each complex, lithium is found in an N 2 O 4 donor atom coordination geometry that is unusual for the cryptand ligand. Magnetic susceptibility data on these new examples of nontraditional divalent lanthanide complexes are consistent with 4f n 5d 1 electronic configurations. The Dy and Ho complexes have exceptionally high single-ion magnetic moments, 11.35 and 11.67 μ B , respectively. Lithium reduction of Cp' 3 Y under N 2 at -35 °C forms the Y 2+ complex (Cp' 3 Y) 1- , which reduces dinitrogen upon warming to room temperature to generate the (N 2 ) 2- complex [Cp' 2 Y(THF)] 2 (μ-η 2 :η 2 -N 2 ). These results provide insight on the factors that lead to reduced dinitrogen complexes and/or stable divalent lanthanide complexes as a function of the specific reducing agent and conditions.

  12. Conducting metal dithiolate complexes

    Underhill, A. E.; Ahmad, M. M.; Turner, D. J.

    1985-01-01

    Further work on the chemical composition of the one-dimensional metallic metal dithiolene complex Li-Pt(mnt) is reported. The electrical conduction and thermopower properties of the nickel and palladium complexes are reported and compared with those of the platinum compound......Further work on the chemical composition of the one-dimensional metallic metal dithiolene complex Li-Pt(mnt) is reported. The electrical conduction and thermopower properties of the nickel and palladium complexes are reported and compared with those of the platinum compound...

  13. Oligocyclopentadienyl transition metal complexes

    de Azevedo, Cristina G.; Vollhardt, K. Peter C.

    2002-01-18

    Synthesis, characterization, and reactivity studies of oligocyclopentadienyl transition metal complexes, namely those of fulvalene, tercyclopentadienyl, quatercyclopentadienyl, and pentacyclopentadienyl(cyclopentadienyl) are the subject of this account. Thermal-, photo-, and redox chemistries of homo- and heteropolynuclear complexes are described.

  14. Constant Electric and Magnetic Fields Effect on the Structuring and Thermomechanical and Thermophysical Properties of Nanocomposites Formed from Pectin-Cu(2+)-Polyethyleneimine Interpolyelectrolyte-Metal Complexes.

    Demchenko, V; Shtompel', V; Riabov, S; Lysenkov, E

    2015-12-01

    Applying wide-angle X-ray scattering method, thermomechanical analysis, and differential scanning calorimetry, the structural organization and properties of nanocomposites formed by chemical reduction of Сu(2+) cations in the interpolyelectrolyte-metal complex (pectin-Cu(2+)-polyethyleneimine) under the influence of a constant magnetic and electric fields have been studied. It has been found that the chemical reduction of Cu(2+) cations in the interpolyelectrolyte-metal complex bulk under constant electric and magnetic fields leads to formation of nanocomposite consisting of interpolyelectrolyte complex, including pectin-polyethyleneimine and nanoparticles of the metal Cu phase, whereas nanocomposite with Cu/Cu2O nanoparticles is formed in original state (without any field). It was observed that, under constant field, nanocomposites obtained have higher structural glass-transition temperatures and thermal stability.

  15. Formation of aqueous complexes of metal ions formed during the reprocessing of nuclear fuels with ortho-phenanthroline and dibutylphosphate

    Musikas, C.; Le Marois, G.; Racinoux, J.

    1979-01-01

    In this work the formation of aqueous complexes of metalions (lanthanides, actinides) was investigated that occurs during reprocessing of nuclear combustibles with ortho-phenanthroline and dibutylphosphate. Complexes with different ligand numbers and solubility are formed. Cationic and anionic forms according to the DBP concentration in the extraction solution. Acid-base titrations, absorption spectra and solubility determinations were used for the characterization. (RB) [de

  16. Advances in metal forming expert system for metal forming

    Hingole, Rahulkumar Shivajirao

    2015-01-01

    This comprehensive book offers a clear account of the theory and applications of advanced metal forming. It provides a detailed discussion of specific forming processes, such as deep drawing, rolling, bending extrusion and stamping. The author highlights recent developments of metal forming technologies and explains sound, new and powerful expert system techniques for solving advanced engineering problems in metal forming. In addition, the basics of expert systems, their importance and applications to metal forming processes, computer-aided analysis of metalworking processes, formability analysis, mathematical modeling and case studies of individual processes are presented.

  17. Spectrophotometric Study of Ternary Complex Forming Systems of Some Lanthanide Metal Ions with Eriochrome Cyanine R in Presence of Cetylpyridinium Bromide for Microdetermination

    A. S. Dhepe

    2011-01-01

    Full Text Available Study of coordination compounds of lanthanide elements has received a great attention due to growing applications in science and technology. Number of chromogenic reagents form water soluble colored complexes with lanthanides. Eriochrome cyanine R (ECR a member of triphenylmethane type of dye has been reported to form green colored complexes with lanthanides and has been used for microdetermination of these metal ions. Addition of cationic surfactant, Cetylpyridinium bromide (CPB, a cationic surfactant sensitizes the color reactions of Gd(III, Tb(III, Dy(III, Ho(III and Lu(III with ECR. Formation of water soluble, highly colored ternary complexes with a considerable bathochromic shift of about 50 nm in presence of surfactant has been observed. Optimum reaction conditions and other analytical parameters were also evaluated. Stoichiometric ratio 1:3:3 of Ln: ECR: CPB are responsible for the observed rise in molar absorptivity and sensitivity. Beer’s law was obeyed between 0.50 to 13.00 ppm. Effective photometric range and molar absorptivity of these ternary complexes have been calculated. Effect of some common interfering ions on determination of these lanthanide metal ions was studied. A simple, rapid and highly sensitive spectrophotometeric method has been proposed for the determination of metal ions understudy.

  18. Metal-Ligand Cooperative Reactivity in the (pseudo)-Dearomatized PNX(P) Systems: the Influence of the Zwitterionic Form in Dearomatized Pincer Complexes

    Goncalves, Theo

    2017-09-01

    The concept of aromaticity in pincer ligands and complexes was discussed in order to provide insights into their metal-ligand cooperative activities. The aromatic PNx(P) and dearomatized PNx(P)* pincer ligands and the corresponding transition metal complexes were studied with the nucleus-independent chemical shift (NICSzz), anisotropy of the current (induced) density (ACID), isochemical shielding surfaces (ICSSzz), harmonic oscillator model of aromaticity (HOMA), MCBO, Shannon aromaticity, and natural bond order (NBO) analyses. The study on the model systems showed that for the dearomatized species the decrease of the NICS(1)zz value comes with the larger contribution of the aromatic zwitterionic mesomeric form. In all examples, the incorporation of the metal center into the pincer ligand decreases the NICS(1)zz values. The DFT calculations support the dearomatized pyridine ring in PNP* or PNN* ligand indeed being nonaromatic, in contrast to the PN3(P)* ligand which has partial aromatic character due to the larger contribution of the zwitterionic resonance structure. The difference in aromaticity between the rings contributes to the thermodynamic balance of the metal ligand cooperative reactions, changing the energetics of the process when different dearomatized pincer ligands are used. This was further exemplified by aromaticity analysis of the heterolytic hydrogen cleavage reaction of ruthenium PNN complexes of Milstein and the PN3 of Huang, with similar geometries but distinctive thermodynamic preference.

  19. Metal-Ligand Cooperative Reactivity in the (pseudo)-Dearomatized PNX(P) Systems: the Influence of the Zwitterionic Form in Dearomatized Pincer Complexes

    Goncalves, Theo; Huang, Kuo-Wei

    2017-01-01

    The concept of aromaticity in pincer ligands and complexes was discussed in order to provide insights into their metal-ligand cooperative activities. The aromatic PNx(P) and dearomatized PNx(P)* pincer ligands and the corresponding transition metal complexes were studied with the nucleus-independent chemical shift (NICSzz), anisotropy of the current (induced) density (ACID), isochemical shielding surfaces (ICSSzz), harmonic oscillator model of aromaticity (HOMA), MCBO, Shannon aromaticity, and natural bond order (NBO) analyses. The study on the model systems showed that for the dearomatized species the decrease of the NICS(1)zz value comes with the larger contribution of the aromatic zwitterionic mesomeric form. In all examples, the incorporation of the metal center into the pincer ligand decreases the NICS(1)zz values. The DFT calculations support the dearomatized pyridine ring in PNP* or PNN* ligand indeed being nonaromatic, in contrast to the PN3(P)* ligand which has partial aromatic character due to the larger contribution of the zwitterionic resonance structure. The difference in aromaticity between the rings contributes to the thermodynamic balance of the metal ligand cooperative reactions, changing the energetics of the process when different dearomatized pincer ligands are used. This was further exemplified by aromaticity analysis of the heterolytic hydrogen cleavage reaction of ruthenium PNN complexes of Milstein and the PN3 of Huang, with similar geometries but distinctive thermodynamic preference.

  20. Metal complexes with 5-aminotetrazole

    Lavrenova, L.G.; Larionov, S.V.; Grankina, Z.A.; Ikorskij, V.N.

    1983-01-01

    Nitrate and chloride complexes of Co(2), Ni(2), Cu(2), Cd(2), Hg(2), Pb(2) with 5 aminotetrazole (ATE) and compoUnds Zn(ATE') 2 and Cd(ATEE') 2 , where ATE' is a 5 aminotetrazole ano /nion. On the base of spectroscopic data (spectrophotometry, IR- spectra, EPR and magnetic measurements assumptions on M(2) coordination in complexes are made. Most probably ATE is a bridge ligand which is joined by two nitrogen atoms to various M(2) ions. In Co(2), Ni(2) and Cu(ATE) 3 -Cl 2 compounds the metal has a distorted actahedral coordination and forms MN 6 unit, which suggests the interaction of metal ions with ATE nitrogen atoms along the Z-axis. In the Cu(ATE) 2 (NO 3 ) 2 octahedral complex the CuN 4 O 2 coordination unit is realized at the expense of participation of nitratogroups in coordination

  1. Selenophene transition metal complexes

    White, Carter James [Iowa State Univ., Ames, IA (United States)

    1994-07-27

    This research shows that selenophene transition metal complexes have a chemistry that is similar to their thiophene analogs. Selenophene coordination has been demonstrated and confirmed by molecular structure in both the η5- and the η1(Se)-coordination modes. The reaction chemistry of selenophene complexes closely resembles that of the analogous thiophene complexes. One major difference, however, is that selenophene is a better donor ligand than thiophene making the selenophene complexes more stable than the corresponding thiophene complexes. The 77Se NMR chemical shift values for selenophene complexes fall within distinct regions primarily depending on the coordination mode of the selenophene ligand. In the final paper, the C-H bond activation of η1(S)-bound thiophenes, η1(S)-benzothiophene and η1(Se)-bound selenophenes has been demonstrated. The deprotonation and rearrangement of the η1(E)-bound ligand to the carbon bound L-yl complex readily occurs in the presence of base. Reprotonation with a strong acid gives a carbene complex that is unreactive towards nucleophilic attack at the carbene carbon and is stable towards exposure to air. The molecular structure of [Cp(NO)(PPh3)Re(2-benzothioenylcarbene)]O3SCF3 was determined and contains a Re-C bond with substantial double bond character. Methyl substitution for the thienylcarbene or selenylcarbene gives a carbene that rearranges thermally to give back the η1(E)-bound complex. Based on these model reactions, a new mechanism for the H/D exchange of thiophene over the hydrodesulfurization catalyst has been proposed.

  2. Physicochemical impact studies of gamma rays on "aspirin" analgesics drug and its metal complexes in solid form: Synthesis, spectroscopic and biological assessment of Ca(II), Mg(II), Sr(II) and Ba(II) aspirinate complexes

    Refat, Moamen S.; Sharshar, T.; Elsabawy, Khaled M.; Heiba, Zein K.

    2013-09-01

    Metal aspirinate complexes, M2(Asp)4, where M is Mg(II), Ca(II), Sr(II) or Ba(II) are formed by refluxed of aspirin (Asp) with divalent non-transition metal ions of group (II) and characterized by elemental analysis and spectroscopic measurements (infrared, electronic, 1H NMR, Raman, X-ray powder diffraction and scanning electron microscopy). Elemental analysis of the chelates suggests the stoichiometry is 1:2 (metal:ligand). Infrared spectra of the complexes agree with the coordination to the central metal atom through three donation sites of two oxygen atoms of bridge bidentate carboxylate group and oxygen atom of sbnd Cdbnd O of acetyl group. Infrared spectra coupled with the results of elemental analyzes suggested a distorted octahedral structure for the M(II) aspirinate complexes. Gamma irradiation was tested as a method for stabilization of aspirin as well as their complexes. The effect of gamma irradiation, with dose of 80 Gy, on the properties of aspirinate complexes was studied. The aspirinate chelates have been screened for their in vitro antibacterial activity against four bacteria, gram-positive (Bacillus subtilis and Staphylococcus aureus) and gram-negative (Escherichia coli and Pseudomonas aeruginosa) and two strains of fungus (Aspergillus flavus and Candida albicans). The metal chelates were shown to possess more antibacterial activity than the free aspirin chelate.

  3. Green Lubricants for Metal Forming

    Bay, Niels

    2010-01-01

    The increasing focus on legislation towards diminishing the impact on working environment as well as external environment has driven efforts to develop new, environmentally benign lubricants for metal forming. The present paper gives an overview of these efforts to substitute environmentally...

  4. Metal Compression Forming of aluminum alloys and metal matrix composites

    Viswanathan, S.; Ren, W.; Porter, W.D.; Brinkman, C.R.; Sabau, A.S.; Purgert, R.M.

    2000-02-01

    Metal Compression Forming (MCF) is a variant of the squeeze casting process, in which molten metal is allowed to solidify under pressure in order to close porosity and form a sound part. However, the MCF process applies pressure on the entire mold face, thereby directing pressure on all regions of the casting and producing a uniformly sound part. The process is capable of producing parts with properties close to those of forgings, while retaining the near net shape, complexity in geometry, and relatively low cost of the casting process.

  5. Methods for forming complex oxidation reaction products including superconducting articles

    Rapp, R.A.; Urquhart, A.W.; Nagelberg, A.S.; Newkirk, M.S.

    1992-01-01

    This patent describes a method for producing a superconducting complex oxidation reaction product of two or more metals in an oxidized state. It comprises positioning at least one parent metal source comprising one of the metals adjacent to a permeable mass comprising at least one metal-containing compound capable of reaction to form the complex oxidation reaction product in step below, the metal component of the at least one metal-containing compound comprising at least a second of the two or more metals, and orienting the parent metal source and the permeable mass relative to each other so that formation of the complex oxidation reaction product will occur in a direction towards and into the permeable mass; and heating the parent metal source in the presence of an oxidant to a temperature region above its melting point to form a body of molten parent metal to permit infiltration and reaction of the molten parent metal into the permeable mass and with the oxidant and the at least one metal-containing compound to form the complex oxidation reaction product, and progressively drawing the molten parent metal source through the complex oxidation reaction product towards the oxidant and towards and into the adjacent permeable mass so that fresh complex oxidation reaction product continues to form within the permeable mass; and recovering the resulting complex oxidation reaction product

  6. Mesoporous metal catalysts formed by ultrasound

    Schaeferhans, Jana; Pazos Perez, Nicolas; Andreeva, Daria [Physikalische Chemie II, Universitaet Bayreuth (Germany)

    2010-07-01

    We study the ultrasound-driven formation of mesoporous metal sponges. The collapse of acoustic cavitations leads to very high temperatures and pressures on very short scales. Therefore, structures may be formed and quenched far from equilibrium. Mechanism of metal modification by ultrasound is complex and involves a variety of aspects. We propose that modification of metal particles and formation of mesoporous inner structures can be achieved due to thermal etching of metals by ultrasound stimulated high speed jets of liquid. Simultaneously, oxidation of metal surfaces by free radicals produced in water during cavitation stabilizes developed metal structures. Duration and intensity of the ultrasonication treatment is able to control the structure and morphology of metal sponges. We expect that this approach to the formation of nanoscale composite sponges is universal and opens perspective for a whole new class of catalytic materials that can be prepared in a one-step process. The developed method makes it possible to control the sponge morphology and can be used for formation of modern types of catalysts. For example, the sonication technique allows to combine the fabrication of mesoporous support and distribution of metal (Cu, Pd, Au, Pt etc.) nanoparticles in its pores into a single step.

  7. Complex metal hydrides

    Ley, Morten Brix

    2014-01-01

    og batterier de to mest lovende energibærere til mobile applikationer. Komplekse metalhydrider er blevet undersøgt i vid udstrækning over de sidste tyve år, siden de gravimetrisk og volumetrisk kan indeholde store mængder brint. Derfor er metal borhydrider velegnet til faststofopbevaring af brint...

  8. benzimidazole metal complexes

    aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, Université des Frères. Mentouri .... determine the quantum chemical parameters for the title ..... retical study of benzazole thioether and its zinc complex.

  9. METAL COMPLEXES OF SALICYLHYDROXAMIC ACID AND 1,10 ...

    Preferred Customer

    Metal complexes which are formed in biological systems between a ligand and a metal ion are in dynamic ... In a continuation of our research work oriented towards studying the .... Antimicrobial activity techniques. Preparation of test samples.

  10. A new lubricant carrier for metal forming

    Arentoft, Mogens; Bay, Niels; Tang, Peter Torben

    2009-01-01

    A lubricant carrier for metal forming processes is developed. Surfaces with pores of micrometer size for entrapping lubricant are generated by electrochemical deposition of an alloy, consisting of two immiscible metals, of which one metal subsequently is etched away leaving 5 mu m layers with a s...... extrusion at high reduction and excessive stroke comparing with conventionally lubrication using phosphate coating and soap....

  11. Transition Metal Complexes and Catalysis

    approaches towards the study of bonding in transition metal complexes. Despite .... industrial scale reactions for the production of organic compounds using transition ..... It has found several applications as an engineering thermoplastic. .... and processes of interest to the company, that is, applied research. It is this very ...

  12. AI applications in sheet metal forming

    Hussein, Hussein

    2017-01-01

    This book comprises chapters on research work done around the globe in the area of artificial intelligence (AI) applications in sheet metal forming. The first chapter offers an introduction to various AI techniques and sheet metal forming, while subsequent chapters describe traditional procedures/methods used in various sheet metal forming processes, and focus on the automation of those processes by means of AI techniques, such as KBS, ANN, GA, CBR, etc. Feature recognition and the manufacturability assessment of sheet metal parts, process planning, strip-layout design, selecting the type and size of die components, die modeling, and predicting die life are some of the most important aspects of sheet metal work. Traditionally, these activities are highly experience-based, tedious and time consuming. In response, researchers in several countries have applied various AI techniques to automate these activities, which are covered in this book. This book will be useful for engineers working in sheet metal industri...

  13. Contour forming of metals by laser peening

    Hackel, Lloyd; Harris, Fritz

    2002-01-01

    A method and apparatus are provided for forming shapes and contours in metal sections by generating laser induced compressive stress on the surface of the metal workpiece. The laser process can generate deep compressive stresses to shape even thick components without inducing unwanted tensile stress at the metal surface. The precision of the laser-induced stress enables exact prediction and subsequent contouring of parts. A light beam of 10 to 100 J/pulse is imaged to create an energy fluence of 60 to 200 J/cm.sup.2 on an absorptive layer applied over a metal surface. A tamping layer of water is flowed over the absorptive layer. The absorption of laser light causes a plasma to form and consequently creates a shock wave that induces a deep residual compressive stress into the metal. The metal responds to this residual stress by bending.

  14. Multiscale friction modeling for sheet metal forming

    Hol, J.; Cid Alfaro, M.V.; de Rooij, Matthias B.; Meinders, Vincent T.; Felder, Eric; Montmitonnet, Pierre

    2010-01-01

    The most often used friction model for sheet metal forming simulations is the relative simple Coulomb friction model. This paper presents a more advanced friction model for large scale forming simulations based on the surface change on the micro-scale. The surface texture of a material changes when

  15. Metal ammine complexes for hydrogen storage

    Christensen, Claus H.; Sørensen, Rasmus Zink; Johannessen, Tue

    2005-01-01

    The hopes of using hydrogen as an energy carrier are severely dampened by the fact that there is still no safe, high-density method available for storing hydrogen. We investigate the possibility of using metal ammine complexes as a solid form of hydrogen storage. Using Mg(NH3)(6)Cl-2 as the example......, we show that it can store 9.1% hydrogen by weight in the form of ammonia. The storage is completely reversible, and by combining it with an ammonia decomposition catalyst, hydrogen can be delivered at temperatures below 620 K....

  16. Hydro mechanical deep-drawing and high pressure sheet metal forming as forming technologies for the production of complex parts made of magnesium sheet metal AZ31B-0; Hydromechanisches Tiefziehen und Hochdruckblechumformung als Verfahren zur Herstellung komplexer Bauteile aus Magnesiumfeinblechen des Typs AZ31B-0

    Viehweger, B.; Richter, G.; Duering, M.; Karabet, A. [Lehrstuhlleiter, BTU Cottbus, Lehrstuhl Konstruktion und Fertigung, Konrad-Wachsmann Allee 1, 03046 Cottbus (Germany); Sviridov, A.; Hartmann, H.; Richter, U. [Forschungs- und Qualitaetszentrum Oderbruecke gGmbH Eisenhuettenstadt (Germany)

    2004-07-01

    Semi - finished sheet - metal products made of magnesium alloys such as AZ31B are known as better deformable at temperatures in the range of 175 C - 240 C. By means of hydroforming technologies, as there are hydro mechanical deep-drawing and high pressure sheet metal forming, the influence of different forming parameters on the forming results has been investigated. A more complex experimental geometry was deformed applying forming temperatures of 175 C, 200 C, 225 C and 240 C and accordingly adjusted forces of the blank holder. Concerning the applied forming - methods and experimental parameters the forming results have been evaluated and compared regarding the decrease of sheet thickness and the development of small radii. For some experimental parts, which have been deformed by means of high pressure sheet metal forming at temperatures of 175 C and 225 C, supplementary investigations have been carried out in order to determine the evolution of characteristic surface values in dependence on the forming operation. On the basis of these results practical recommendations for the limits of application of aforementioned forming technologies for AZ31B-0 magnesium sheet metal are given. (Abstract Copyright [2004], Wiley Periodicals, Inc.) [German] Eine gute Umformbarkeit von Blechhalbzeugen aus Magnesiumknetlegierungen stellt sich bekanntlich bei Anwendung von Umformtemperaturen im Bereich von 175 C - 240 C ein. Anhand der wirkmedienbasierten Umformverfahren hydromechanisches Tiefziehen und Hochdruckblechumformung ist an handelsueblichen AZ31B-0 Feinblechen die Einstellung unterschiedlicher Umformparameter erprobt worden. Unter Verwendung von Umformtemperaturen von 175 C, 200 C, 225 C und 240 C und entsprechend angepassten Niederhalterdruecken ist eine praxisnahe Versuchsgeometrie ''Minihood'' ausgeformt worden. Im Hinblick auf angewendete Umformverfahren und Versuchsparameter wurde an den Versuchsbauteilen die Blechdickenabnahme und die

  17. Optimization and control of metal forming processes

    Havinga, Gosse Tjipke

    2016-01-01

    Inevitable variations in process and material properties limit the accuracy of metal forming processes. Robust optimization methods or control systems can be used to improve the production accuracy. Robust optimization methods are used to design production processes with low sensitivity to the

  18. Advanced friction modeling for sheet metal forming

    Hol, J.; Cid Alfaro, M.V.; de Rooij, Matthias B.; Meinders, Vincent T.

    2012-01-01

    The Coulomb friction model is frequently used for sheet metal forming simulations. This model incorporates a constant coefficient of friction and does not take the influence of important parameters such as contact pressure or deformation of the sheet material into account. This article presents a

  19. Advanced friction modeling in sheet metal forming

    Hol, J.; Cid Alfaro, M.V.; Meinders, Vincent T.; Huetink, Han

    2011-01-01

    The Coulomb friction model is frequently used for sheet metal forming simulations. This model incorporates a constant coefficient of friction and does not take the influence of important parameters such as contact pressure or deformation of the sheet material into account. This article presents a

  20. Failure by fracture in bulk metal forming

    Silva, C.M.A.; Alves, Luis M.; Nielsen, Chris Valentin

    2015-01-01

    This paper revisits formability in bulk metal forming in the light of fundamental concepts of plasticity,ductile damage and crack opening modes. It proposes a new test to appraise the accuracy, reliability and validity of fracture loci associated with crack opening by tension and out-of-plane shear...

  1. Constitutive Modeling for Sheet Metal Forming

    Barlat, Frederic

    2005-01-01

    This paper reviews aspects of the plastic behaviour common in sheet metals. Macroscopic and microscopic phenomena occurring during plastic deformation are described succinctly. Constitutive models of plasticity suitable for applications to forming, are discussed in a very broad manner. Approaches to plastic anisotropy are described in a somewhat more detailed manner

  2. Internal shear cracking in bulk metal forming

    Christiansen, Peter; Nielsen, Chris Valentin; Bay, Niels Oluf

    2017-01-01

    This paper presents an uncoupled ductile damage criterion for modelling the opening and propagation of internal shear cracks in bulk metal forming. The criterion is built upon the original work on the motion of a hole subjected to shear with superimposed tensile stress triaxiality and its overall...... performance is evaluated by means of side-pressing formability tests in Aluminium AA2007-T6 subjected to different levels of pre-strain. Results show that the new proposed criterionis able to combine simplicity with efficiency for predicting the onset of fracture and the crack propagation path for the entire...... cracking to internal cracks formed undert hree-dimensional states of stress that are typical of bulk metal forming....

  3. Forming of bulk metallic glass microcomponents

    Wert, John A.; Thomsen, Christian; Jensen, Rune Debel

    2009-01-01

    The present article considers forward extrusion, closed-die forging and backward extrusion processes for fabrication of individual microcomponents from two bulk metallic glass (BMG) compositions: Mg60Cu30Y10 and Zr44Cu40Ag8Al8. Two types of tooling were used in the present work: relatively massive...... die sets characteristic of cold forming operations for crystalline metals and lightweight die sets adapted to the special characteristics of BMGs. In addition to demonstrating that microcomponents of several geometries can be readily fabricated from BMGs, rheological properties are combined...

  4. Multi Scale Models for Flexure Deformation in Sheet Metal Forming

    Di Pasquale Edmondo

    2016-01-01

    Full Text Available This paper presents the application of multi scale techniques to the simulation of sheet metal forming using the one-step method. When a blank flows over the die radius, it undergoes a complex cycle of bending and unbending. First, we describe an original model for the prediction of residual plastic deformation and stresses in the blank section. This model, working on a scale about one hundred times smaller than the element size, has been implemented in SIMEX, one-step sheet metal forming simulation code. The utilisation of this multi-scale modeling technique improves greatly the accuracy of the solution. Finally, we discuss the implications of this analysis on the prediction of springback in metal forming.

  5. Sheet-bulk metal formingforming of functional components from sheet metals

    Merklein Marion

    2015-01-01

    Full Text Available The paper gives an overview on the application of sheet-bulk metal forming operations in both scientific and industrial environment. Beginning with the need for an innovative forming technology, the definition of this new process class is introduced. The rising challenges of the application of bulk metal forming operations on sheet metals are presented and the demand on a holistic investigation of this topic is motivated. With the help of examples from established production processes, the latest state of technology and the lack on fundamental knowledge is shown. Furthermore, perspectives regarding new research topics within sheet-bulk metal forming are presented. These focus on processing strategies to improve the quality of functional components by the application of process-adapted semi-finished products as well as the local adaption of the tribological system.

  6. Lubricant Test Methods for Sheet Metal Forming

    Bay, Niels; Olsson, David Dam; Andreasen, Jan Lasson

    2008-01-01

    appearing in different sheet forming operations such as stretch forming, deep drawing, ironing and punching. The laboratory tests have been especially designed to model the conditions in industrial production. Application of the tests for evaluating new lubricants before introducing them in production has......Sheet metal forming of tribologically difficult materials such as stainless steel, Al-alloys and Ti-alloys or forming in tribologically difficult operations like ironing, punching or deep drawing of thick plate requires often use of environmentally hazardous lubricants such as chlorinated paraffin...... oils in order to avoid galling. The present paper describes a systematic research in the development of new, environmentally harmless lubricants focusing on the lubricant testing aspects. A system of laboratory tests has been developed to study the lubricant performance under the very varied conditions...

  7. Structure of Complex Verb Forms in Meiteilon

    Lourembam Surjit Singh

    2016-12-01

    Full Text Available This piece of work proposes to descriptively investigate the structures of complex verbs in Meiteilon. The categorization of such verbs is based on the nature of semantic and syntactic functions of a lexeme or verbal lexeme. A lexeme or verbal lexeme in Meiteilon may have multifunctional properties in the nature of occurrence. Such lexical items can be co-occurred together in a phrase as single functional word. Specifically, in the co-occurrences of two lexical items, the first component of lexical items has different semantic and syntactic functions in comparison to semantic and syntactic functions of the second component of lexical items. Such co-occurrences of two lexical items are the forms of complex verb that are covered with the term complex predicate in this work. The investigation in constructing complex predicate is thoroughly presenting in this work. Keywords: Structures, complex verb, conjunct verb, compound verb, complex predicate

  8. Metallic complexes with glyphosate: a review

    Coutinho, Cláudia F. B.; Mazo, Luiz Henrique

    2005-01-01

    We present studies involving metallic ions and the herbicide glyphosate. The metallic complexes of Cu(II), Zn(II), Mn(II), Ni(II), Cd(II), Pb(II), Cr(III), Fe(III), Co(III), ammonium, sodium, Ag(I), alkaline earth metals and of some lanthanides ions are described. The complexes are discussed in terms of their synthesis, identification, stability and structural properties, based on data from the current literature.

  9. Metallic complexes with glyphosate: a review

    Coutinho, Claudia F.B.; Mazo, Luiz Henrique

    2005-01-01

    We present studies involving metallic ions and the herbicide glyphosate. The metallic complexes of Cu(II), Zn(II), Mn(II), Ni(II), Cd(II), Pb(II), Cr(III), Fe(III), Co(III), ammonium, sodium, Ag(I), alkaline earth metals and of some lanthanides ions are described. The complexes are discussed in terms of their synthesis, identification, stability and structural properties, based on data from the current literature. (author)

  10. Damage Prediction in Sheet Metal Forming

    Saanouni, Khemais; Badreddine, Houssem

    2007-01-01

    Ductile (or plastic) damage often occurs during sheet metal forming processes due to the large plastic flow localization. Accordingly, it is crucial for numerical tools, used in the simulation of that processes, to use fully coupled constitutive equations accounting for both hardening and damage. This can be used in both cases, namely to overcome the damage initiation during some sheet metal forming processes as deep drawing, ... or to enhance the damage initiation and growth as in sheet metal cutting. In this paper, a fully coupled constitutive equations accounting for combined isotropic and kinematic hardening as well as the ductile damage is implemented into the general purpose Finite Element code for metal forming simulation. First, the fully coupled anisotropic constitutive equations in the framework of Continuum Damage Mechanics are presented. Attention is paid to the strong coupling between the main mechanical fields as elasto-viscoplasticity, mixed hardening, ductile isotropic damage and contact with friction. The anisotropy of the plastic flow is taken into account using various kinds of quadratic or non quadratic yield criteria in the framework of non associative finite plasticity theory with two types of normality rules. The associated numerical aspects concerning both the local integration of the coupled constitutive equations as well as the (global) equilibrium integration schemes are presented. The local integration is outlined thanks to the Newton iterative scheme applied to a reduced system of 2 equations. For the global resolution of the initial and boundary value problem, the classical dynamic explicit (DE) scheme with an adaptive time step control is used. The numerical implementation of the damage is made in such a manner that calculations can be executed with or without damage effect, i.e. fully coupled or uncoupled calculations. For the 2D processes an advanced adaptive meshing procedure is used in order to enhance the numerical solution and

  11. Trends and Visions in Metal Forming Tribology

    Bay, Niels

    2011-01-01

    operations, which otherwise would require the use of environmentally hazardous lubricant systems. A methodology for prediction of limits of lubrication of new tribo-system for sheet forming production based on numerical modelling and off-line testing in dedicated simulative tribo-tests is proposed....... of structured work piece and tool surfaces to facilitate micro-hydro-dynamic lubrication. Increased knowledge on skin-pass rolling to establish structured sheet surfaces and new automatic polishing equipment to manufacture tailored tool surfaces are important means to improve tribo-conditions in severe forming......Research and development in metal forming tribology is characterized by intensified focus on new tribo-systems such as new lubricants, tool materials and tool coatings in order to substitute environmentally hazardous lubricant systems. Other means to solve these problems include the development...

  12. Tribo-systems for Sheet Metal Forming

    Bay, Niels

    2009-01-01

    The present paper gives an overview of more than 10 years work by the author’s research group through participation in national as well as international framework programmes on developing and testing environmentally friendly lubricants and tool materials and coatings inhibiting galling. Partners ......’s research group has especially been involved in the development of a system of tribo-tests for sheet metal forming and in testing and modelling of friction and limits of lubrication of new, environmentally friendly lubricants and tool materials....

  13. Complexes of natural carbohydrates with metal cations

    Alekseev, Yurii E; Garnovskii, Alexander D; Zhdanov, Yu A

    1998-01-01

    Data on the interaction of natural carbohydrates (mono-, oligo-, and poly-saccharides, amino sugars, and natural organic acids of carbohydrate origin) with metal cations are surveyed and described systematically. The structural diversity of carbohydrate metal complexes, caused by some specific features of carbohydrates as ligands, is demonstrated. The influence of complex formation on the chemical properties of carbohydrates is discussed. It is shown that the formation of metal complexes plays an important role in the configurational and conformational analysis of carbohydrates. The practical significance of the coordination interaction in the series of carbohydrate ligands is demonstrated. The bibliography includes 571 references.

  14. Experimental evaluation of coating delamination in vinyl coated metal forming

    Son, Young Ki; Lee, Chan Joo; Kim, Byung Min; Lee, Jung Min; Byoen, Sang Doek; Lee, Soen Bong

    2012-01-01

    In this paper, a new evaluation and prediction method for coating delamination during sheet metal forming is presented. On the basis of the forming limit diagram (FLD), the current study evaluates the delamination of PET coating by using a cross cut specimen, dome test, and rectangular cup drawing test. Dome test specimens were subjected to biaxial, plane strain, and uniaxial deformation modes. Rectangular cup drawing test specimens were subjected to the deep drawing deformation mode, and compression deformation mode. A vinyl coated metal (VCM) sheet consists of three layers of polymer on the sheet metals: a protective film, a PET layer and a PVC layer. The areas with coating delamination were identified, and the results of the evaluation were plotted according to major and minor strain values, depicting coating delamination. The constructed delamination limit diagram (DLD) can be used to determine the forming limit of VCM during the complex press forming process. ARGUS (GOM) was employed to identify the strain value and deformation mode of the delaminated surface after the press forming. After identifying the areas of delamination, the DLD of the PET coating can be constructed in a format similar to that of the FLD. The forming limit of the VCM sheet can be evaluated using the superimposition of the delamination limit strain of the coating onto the FLD of VCM sheet. The experimental results showed that the proposed test method will support the sheet metal forming process design for VCM sheets. The assessment method presented in this study can be used to determine the delamination limit strain under plastic deformation of other polymer coated metals. The experimental results suggested that the proposed testing method is effective in evaluating delamination for specific applications

  15. Experimental evaluation of coating delamination in vinyl coated metal forming

    Son, Young Ki; Lee, Chan Joo; Kim, Byung Min [Pusan National Univ., Busan (Korea, Republic of); Lee, Jung Min [Korea Institute of Industrial Technology, Busan (Korea, Republic of); Byoen, Sang Doek [HA Digital Engineering Gr., Seongsan Gu (Korea, Republic of); Lee, Soen Bong [Keimyung Univ., Daegu (Korea, Republic of)

    2012-10-15

    In this paper, a new evaluation and prediction method for coating delamination during sheet metal forming is presented. On the basis of the forming limit diagram (FLD), the current study evaluates the delamination of PET coating by using a cross cut specimen, dome test, and rectangular cup drawing test. Dome test specimens were subjected to biaxial, plane strain, and uniaxial deformation modes. Rectangular cup drawing test specimens were subjected to the deep drawing deformation mode, and compression deformation mode. A vinyl coated metal (VCM) sheet consists of three layers of polymer on the sheet metals: a protective film, a PET layer and a PVC layer. The areas with coating delamination were identified, and the results of the evaluation were plotted according to major and minor strain values, depicting coating delamination. The constructed delamination limit diagram (DLD) can be used to determine the forming limit of VCM during the complex press forming process. ARGUS (GOM) was employed to identify the strain value and deformation mode of the delaminated surface after the press forming. After identifying the areas of delamination, the DLD of the PET coating can be constructed in a format similar to that of the FLD. The forming limit of the VCM sheet can be evaluated using the superimposition of the delamination limit strain of the coating onto the FLD of VCM sheet. The experimental results showed that the proposed test method will support the sheet metal forming process design for VCM sheets. The assessment method presented in this study can be used to determine the delamination limit strain under plastic deformation of other polymer coated metals. The experimental results suggested that the proposed testing method is effective in evaluating delamination for specific applications.

  16. Pharmacologically significant tetraaza macrocyclic metal complexes ...

    MOHAMMAD SHAKIR

    2017-11-22

    Nov 22, 2017 ... structural biological models.6 Hence, biological prop- erties of ... poor water solubility, exhibits intrinsic resistance and ..... pdb). The metal complex files were drawn using. ChemDraw (MM2) and their energies were minimized.

  17. Synthesis, characterization and biological profile of metal and azo-metal complexes of embelin

    R. Aravindhan

    2014-12-01

    Full Text Available The present study emphasizes synthesis and bioprofiling of embelin, embelin-metal (EM and embelin-azo-metal (EAM complexes in detail. EM complexes were prepared using pure embelin and d-block transition elements, namely Mn, Fe, Co, Ni, Cu, and Zn. Similarly, EAM complexes were synthesized using phenyl azo-embelin with the said transition metals. Embelin, EM, and EAM complexes were subjected to ultra violet visible spectroscopy, Fourier transform infrared spectroscopy, nuclear magnetic resonance, electrospray ionization mass spectrometry, thermogravimetric analysis, carbon hydrogen nitrogen sulfur analysis. With regard to bioprofiling, the test complexes were studied for the antioxidant and antimicrobial activities. Results revealed that the prepared EM and EAM complexes form octahedral complexes with embelin with the yield in the range of 45–75%. All the instrumental analyses authenticate the interaction of metals with bidentate embelin through its enolic and quinonic oxygen atoms as [M(Emb2(H2O2]H2O and [M(Emb-Azo2(H2O2]. The antioxidant profile studies suggested that upon complexation with metals, the free radical scavenging activity of embelin reduced significantly. But, with regard to antimicrobial activity, cobalt and nickel embelin complexes displayed>80% growth inhibition in comparison with embelin alone. The hemolytic activity studies suggested that both embelin and the metal complexes are non-hemolytic. The reason for the reduction in antioxidant and an increase in antimicrobial activities were discussed in detail.

  18. Quinonoid metal complexes: toward molecular switches.

    Dei, Andrea; Gatteschi, Dante; Sangregorio, Claudio; Sorace, Lorenzo

    2004-11-01

    The peculiar redox-active character of quinonoid metal complexes makes them extremely appealing to design materials of potential technological interest. We show here how the tuning of the properties of these systems can be pursued by using appropriate molecular synthetic techniques. In particular, we focus our attention on metal polyoxolene complexes exhibiting intramolecular electron transfer processes involving either the ligand and the metal ion or the two dioxolene moieties of a properly designed ligand thus inducing electronic bistability. The transition between the two metastable electronic states can be induced by different external stimuli such as temperature, pressure, light, or pH suggesting the use of these systems for molecular switches.

  19. A Historical Review of High Speed Metal Forming

    Zittel, G.

    2010-01-01

    This paper will present a Historical Review of High Speed Metal Forming beginning with the first thought of forming metal by using an electromagnetic impulse to today, whereby High Speed Metal Forming is an accepted production process. Although this paper will briefly cover the basic physics of the process, it will not dwell on it. It will rather show how the industrial acceptance of High Speed Metal Forming is tightly connected to the knowledge acquired from many applications studies. These ...

  20. Forming and bending of metal foams

    Nebosky, Paul; Tyszka, Daniel; Niebur, Glen; Schmid, Steven

    2004-01-01

    This study examines the formability of a porous tantalum foam, known as trabecular metal (TM). Used as a bone ingrowth surface on orthopedic implants, TM is desirable due to its combination of high strength, low relative density, and excellent osteoconductive properties. This research aims to develop bend and stretch forming as a cost-effective alternative to net machining and EDM for manufacturing thin parts made of TM. Experimentally, bending about a single axis using a wiping die was studied by observing cracking and measuring springback. It was found that die radius and clearance strongly affect the springback properties of TM, while punch speed, embossings, die radius and clearance all influence cracking. Depending on the various combinations of die radius and clearance, springback factor ranged from .70-.91. To examine the affect of the foam microstructure, bending also was examined numerically using a horizontal hexagonal mesh. As the hexagonal cells were elongated along the sheet length, elastic springback decreased. This can be explained by the earlier onset of plastic hinging occurring at the vertices of the cells. While the numerical results matched the experimental results for the case of zero clearance, differences at higher clearances arose due to an imprecise characterization of the post-yield properties of tantalum. By changing the material properties of the struts, the models can be modified for use with other open-cell metallic foams

  1. Electrochemical corrosion testing of metal waste forms

    Abraham, D. P.; Peterson, J. J.; Katyal, H. K.; Keiser, D. D.; Hilton, B. A.

    1999-01-01

    Electrochemical corrosion tests have been conducted on simulated stainless steel-zirconium (SS-Zr) metal waste form (MWF) samples. The uniform aqueous corrosion behavior of the samples in various test solutions was measured by the polarization resistance technique. The data show that the MWF corrosion rates are very low in groundwaters representative of the proposed Yucca Mountain repository. Galvanic corrosion measurements were also conducted on MWF samples that were coupled to an alloy that has been proposed for the inner lining of the high-level nuclear waste container. The experiments show that the steady-state galvanic corrosion currents are small. Galvanic corrosion will, hence, not be an important mechanism of radionuclide release from the MWF alloys

  2. Lability of nanoparticulate metal complexes in electrochemical speciation analysis

    van Leeuwen, Herman P.; Town, Raewyn M.

    2016-01-01

    Lability concepts are elaborated for metal complexes with soft (3D) and hard (2D) aqueous nanoparticles. In the presence of a non-equilibrium sensor, e.g. a voltammetric electrode, the notion of lability for nanoparticulate metal complexes, M-NP, reflects the ability of the M-NP to maintain...... equilibrium with the reduced concentration of the electroactive free M2+ in its diffusion layer. Since the metal ion binding sites are confined to the NP body, the conventional reaction layer in the form of a layer adjacent to the electrode surface is immaterial. Instead an intraparticulate reaction zone may...... of the electrochemical technique is crucial in the lability towards the electrode surface. In contrast, for nanoparticulate complexes it is the dynamics of the exchange of the electroactive metal ion with the surrounding medium that governs the effective lability towards the electrode surface....

  3. RAPID FREEFORM SHEET METAL FORMING: TECHNOLOGY DEVELOPMENT AND SYSTEM VERIFICATION

    Kiridena, Vijitha [Ford Scientific Research Lab., Dearborn, MI (United States); Verma, Ravi [Boeing Research and Technology (BR& T), Seattle, WA (United States); Gutowski, Timothy [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Roth, John [Pennsylvania State Univ., University Park, PA (United States)

    2018-03-31

    The objective of this project is to develop a transformational RApid Freeform sheet metal Forming Technology (RAFFT) in an industrial environment, which has the potential to increase manufacturing energy efficiency up to ten times, at a fraction of the cost of conventional technologies. The RAFFT technology is a flexible and energy-efficient process that eliminates the need for having geometry-specific forming dies. The innovation lies in the idea of using the energy resource at the local deformation area which provides greater formability, process control, and process flexibility relative to traditional methods. Double-Sided Incremental Forming (DSIF), the core technology in RAFFT, is a new concept for sheet metal forming. A blank sheet is clamped around its periphery and gradually deformed into a complex 3D freeform part by two strategically aligned stylus-type tools that follow a pre-described toolpath. The two tools, one on each side of the blank, can form a part with sharp features for both concave and convex shapes. Since deformation happens locally, the forming force at any instant is significantly decreased when compared to traditional methods. The key advantages of DSIF are its high process flexibility, high energy-efficiency, low capital investment, and the elimination of the need for massive amounts of die casting and machining. Additionally, the enhanced formability and process flexibility of DSIF can open up design spaces and result in greater weight savings.

  4. A study of transformation water - soluble forms of hevy metals at waste incenerator for detoxicationof ash.

    Bilets'ka V. А.

    2011-11-01

    Full Text Available The complex research processes of transformation of soluble forms of heavy metals in sediment interaction with ash. Proved that the adsorption processes of immobilization lead to a significant decrease of soluble forms of heavy metals in the waste.

  5. Alkane Soluble Transition Metal Complexes.

    1983-10-01

    lCam ludoalNm’s W S. has aA F. . Hadley. uppokli *mvahs Capm amAe Hall. 1~i. 6. 08 o.. ILDuataA ulpmr. Cai. 1d. CAM 4. 111aII. lop C Themm. - hftupvtm of...phoahines.3 descrbed previously.’ In this analyuis a series of assumption . isre onadc Our reasons for doing this were twofold. in order to enable a lhoea...nalytical method to be used. It sii be w-me First, pfmospftane complexes have been widely used as be. apparent that the assumptions that must be made

  6. Self-organization in metal complexes

    Radecka-Paryzek, W.

    1999-01-01

    Inorganic self-organization involves the spontaneous generation of well-defined supramolecular architectures from metal ions and organic ligands. The basic concept of supramolecular chemistry is a molecular recognition. When the substrate are metal ions, recognition is expressed in the stability and selectivity of metal ion complexation by organic ligands and depends on the geometry of the ligand and on their binding sites that it contains. The combination of the geometric features of the ligand units and the coordination geometries of the metal ions provides very efficient tool for the synthesis of novel, intriguing and highly sophisticated species such as catenanes, box structures, double and triple helicates with a variety of interesting properties. The article will focus on the examples of inorganic self-organization involving the templating as a first step for the assembly of supramolecular structures of high complexity. (author)

  7. On monosubstituted cyanurate complexes of transition metals

    Sejfer, G.B.; Tarasova, Z.A.

    1995-01-01

    Complex monosubstituted cyanurates of transition metals K 2 [Eh(H 2 C 3 N 3 O 3 ) 4 ]x4H 2 ) where Eh = Mn, Co, Ni, Cu, Zn, Cd are synthesized and investigated by means of IR - spectroscopy and thermal analysis methods. It is shown that only thermal decomposition of a manganese complex leads to the production of this metal oxide. All other derivatives decompose with the production of a free metal, because decomposition of these substances in argon atmosphere occurs through an intermediate production of their nitrides. An assumption is made that nitroduction of yttrium or rare earth element salts (instead of transition or alkali metal derivatives) as accelerating additions will facilitate increase of polyisocyanurate resin thermal stability. 25 refs.; 2 figs.; 3 tabs

  8. Cationic rare-earth metal SALEN complexes.

    Liu, Qiancai; Meermann, Christian; Görlitzer, Hans W; Runte, Oliver; Herdtweck, Eberhardt; Sirsch, Peter; Törnroos, Karl W; Anwander, Reiner

    2008-11-28

    Complexes (Salpren(tBu,tBu))Y[N(SiHMe2)2](thf) and (SALEN(tBu,tBu))La[N(SiHMe2)2](thf) (SALEN(tBu,tBu) = Salcyc(tBu,tBu) and Salpren(tBu,tBu)) were prepared from Ln[N(SiHMe2)2]3(thf)2 and H2SALEN(tBu,tBu). The yttrium complex was characterized by X-ray crystallography revealing intrinsic solid-state structural features: the metal centre is displaced by 1.05 angstroms from the [N2O2] least squares plane of a highly bent Salpren(tBu,tBu) ligand (angle(Ph,Ph) dihedral angle of 80.4(1) degrees ) and is coordinated asymmetrically by the silylamide ligand exhibiting one significant Y---(HSi) beta-agostic interaction (Y-N1-Si1, 106.90(9) degrees; Y---Si1, 3.2317(6) angstroms). Complexes (SALEN(tBu,tBu))Ln[N(SiHMe2)2](thf)n (n = 1, Sc; n = 2, Y, La) react with ammonium tetraphenylborate to form the ion pairs [(SALEN(tBu,tBu))Ln(thf)n][BPh4]. The cationisation was proven by X-ray crystal structure analyses of [(Salpren(tBu,tBu))Sc(thf)2][B(C6H5)4].2(thf) and [(Salpren(tBu,tBu))Ln(thf)3][B(C6H5)4].4(thf) (Ln = Y, La), showing an octahedral and pentagonal-bipyramidal coordination geometry, respectively.

  9. Reaction mechanisms of metal complexes

    Hay, R W

    2000-01-01

    This text provides a general background as a course module in the area of inorganic reaction mechanisms, suitable for advanced undergraduate and postgraduate study and/or research. The topic has important research applications in the metallurgical industry and is of interest in the science of biochemistry, biology, organic, inorganic and bioinorganic chemistry. In addition to coverage of substitution reactions in four-, five- and six-coordinate complexes, the book contains further chapters devoted to isomerization and racemization reactions, to the general field of redox reactions, and to the reactions of coordinated ligands. It is relevant in other fields such as organic, bioinorganic and biological chemistry, providing a bridge to organic reaction mechanisms. The book also contains a chapter on the kinetic background to the subject with many illustrative examples which should prove useful to those beginning research. Provides a general background as a course module in the area of inorganic reaction mechanis...

  10. Production of metal waste forms from spent fuel treatment

    Westphal, B.R.; Keiser, D.D.; Rigg, R.H.; Laug, D.V.

    1995-01-01

    Treatment of spent nuclear fuel at Argonne National Laboratory consists of a pyroprocessing scheme in which the development of suitable waste forms is being advanced. Of the two waste forms being proposed, metal and mineral, the production of the metal waste form utilizes induction melting to stabilize the waste product. Alloying of metallic nuclear materials by induction melting has long been an Argonne strength and thus, the transition to metallic waste processing seems compatible. A test program is being initiated to coalesce the production of the metal waste forms with current induction melting capabilities

  11. Metal complex derivatives of hydrogen uranyl phosphate

    Grohol, D.; Blinn, E.L.

    1994-01-01

    Derivatives of hydrogen uranyl phosphate were prepared by incorporating transition metal complexes into the uranyl phosphate matrix. The transition metal complexes employed include bis(ethylenediamine)copper(II), bis(1,3-propanediamine)copper(II) chloride, (triethylenetetramine)copper(II), (1,4,8,11-tetraazacyclotetradecane)copper(II), (1,4,8,12-tetraazacyclopentadecane)copper(II), (1,4,8,11-tetraazacyclotetradecane)nickel(II) chloride, (triethylenetetramine)nickel(II) and others. The chemical analyses of these derivatives indicated that the incorporation of the transition metal complexes into the uranyl phosphate matrix via ion exchange was not stoichiometric. The extent of ion exchange is dependent on the size and structure of the transition metal complex. All complexes were characterized by X-ray powder diffractometry, electronic and infrared spectra, thermal analyses and chemical analysis. An attempt was made to correlate the degree of quenching of the luminescence of the uranyl ion to the spacing between the uranyl phosphate layers in the derivatives

  12. Complex Metal Hydrides for Hydrogen, Thermal and Electrochemical Energy Storage

    Moller, Kasper T.; Sheppard, Drew; Ravnsbaek, Dorthe B.

    2017-01-01

    Hydrogen has a very diverse chemistry and reacts with most other elements to form compounds, which have fascinating structures, compositions and properties. Complex metal hydrides are a rapidly expanding class of materials, approaching multi-functionality, in particular within the energy storage...... inspiration to solve the great challenge of our time: efficient conversion and large-scale storage of renewable energy....... field. This review illustrates that complex metal hydrides may store hydrogen in the solid state, act as novel battery materials, both as electrolytes and electrode materials, or store solar heat in a more efficient manner as compared to traditional heat storage materials. Furthermore, it is highlighted...

  13. Solution properties of metal ion complexes formed with the antiviral and cytostatic nucleotide analogue 9-[2-(phosphonomethoxy)ethyl]-2-amino-6-dimethylaminopurine (PME2A6DMAP)

    Gómez-Coca, R. B.; Sigel, A.; Operschall, B. P.; Holý, Antonín; Sigel, H.

    2014-01-01

    Roč. 92, č. 8 (2014), s. 771-780 ISSN 0008-4042 Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonates * antivirals * intramolecular equilibria * metal-ion complexes * nucleotide analogues * stability constants Subject RIV: CC - Organic Chemistry Impact factor: 1.061, year: 2014

  14. Forming processes and mechanics of sheet metal forming

    Burchitz, I.A.

    2004-01-01

    The report is dealing with the numerical analysis of forming processes. Forming processes is the large group of manufacturing processes used to obtain various product shapes by means of plastic deformations. The report is organized as follows. An overview of the deformation processes and the

  15. Complex forming properties of natural organic acids. Pt. 2

    Ephraim, J.H.; Mathuthu, A.S.; Marinsky, J.A.

    1990-07-01

    An ultrafiltration technique combined with ion-selective-electrode and atomic absorption methods have been employed to obtain information on the complex forming properties of fulvic acid with iron and calcium. A model for interpreting complexation of metal ions to fulvic acid at any pH, medium ionic strength and metal to fulvic acid ratio developed earlier has been used in an attempt to predict the nature of iron and calcium interaction to Armadale Horizon Bh fulvic acid. Binding of calcium to fulvic acid which is enhanced at pHs greater than 6.0 has reasonably been predicted by the model taking into consideration complications due to the polyelectrolyte nature and the heterogeneity of the fulvic acid. The lack of agreement observed between the model predicted binding behavior and the experimentally observed results for the fulvic acid-iron system has been attributed to the formation of metal-induced aggregation. Reduction of Fe(III) to Fe(II) by the fulvic acid as reported by other workers is corroborated. (orig.)

  16. Anharmonic Vibrational Spectroscopy on Metal Transition Complexes

    Latouche, Camille; Bloino, Julien; Barone, Vincenzo

    2014-06-01

    Advances in hardware performance and the availability of efficient and reliable computational models have made possible the application of computational spectroscopy to ever larger molecular systems. The systematic interpretation of experimental data and the full characterization of complex molecules can then be facilitated. Focusing on vibrational spectroscopy, several approaches have been proposed to simulate spectra beyond the double harmonic approximation, so that more details become available. However, a routine use of such tools requires the preliminary definition of a valid protocol with the most appropriate combination of electronic structure and nuclear calculation models. Several benchmark of anharmonic calculations frequency have been realized on organic molecules. Nevertheless, benchmarks of organometallics or inorganic metal complexes at this level are strongly lacking despite the interest of these systems due to their strong emission and vibrational properties. Herein we report the benchmark study realized with anharmonic calculations on simple metal complexes, along with some pilot applications on systems of direct technological or biological interest.

  17. Biotransformation of uranium and transition metal citrate complexes by clostridia

    Francis, A.J.; Joshi-Tope, G.A.; Dodge, C.J.; Gillow, J.B.

    2002-01-01

    Clostridium sphenoides, which uses citric acid as its sole carbon source, metabolized equimolar Fe(III)-citrate with the degradation of citric acid and the reduction of Fe(III) to Fe(II), but not the U(VI)-citrate complex. However, in the presence of excess citric acid or added glucose it was reduced to U(IV)-citrate. In contrast, Clostridium sp., which ferments glucose but not citrate, reduced Fe(III)-citrate to Fe(II)-citrate and U(VI)-citrate to U(IV)-citrate only when supplied with glucose. These results show that complexed uranium is readily accessible as an electron acceptor despite the bacterium's inability to metabolize the organic ligand complexed to the actinide. These results also show that the metabolism of the metal-citrate complex depends upon the type of complex formed between the metal and citric acid. Fe(III) forms a bidentate complex with citric acid and was metabolized, whereas U forms a binuclear complex with citric acid and was recalcitrant. (author)

  18. The role of metal complexes in nuclear reactor decontamination

    Prince, A.A.M.; Raghavan, P.S.; Gopalan, R. [Madras Christian College, Tambaram, Chennai (India); Velmurugan, S.; Narasimhan, S.V. [Bhabha Atomic Research Center (BARC) (IN). Water and Steam Chemistry Lab. (WSCL)

    2006-07-15

    Chemical decontamination is the process of removal of radioactivity from corrosion products formed on structural materials in the nuclear reactors. These corrosion products cause problems for the operation and maintenance of the plants. Removal of the radioactive contaminants can be achieved by dissolving the oxide from the system surface using organic complexing agents in low concentrations known as dilute chemical decontamination (DCD) formulations. These organic complexing agents attack the oxide surface and form metal complexes, which further accelerate the dissolution process. The stability of the complexes plays an important role in dissolving the radioactive contaminated oxides. In addition, the DCD process is operated through ion exchange resins for the removal of the dissolved metal ions and radioactive nuclides. In the present study, the kinetics of dissolution of various model corrosion products such as magnetite (Fe{sub 3}O{sub 4}), hematite ({alpha}-Fe{sub 2}O{sub 3}) and maghemite ({gamma}-Fe{sub 2}O{sub 3}) have been studied in the presence of complexing agents such as ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), hydroxyethylethylenediaminepentaacetic acid (HEEDTA), and 2,6 pyridinedicarboxylic acid (PDCA). The reductive roles of metal complexes and organic reducing agents are discussed. (orig.)

  19. Biodegradation of metal citrate complexes and implications for toxic-metal mobility

    Francis, A.J.; Dodge, C.J.; Gillow, J.B.

    1992-01-01

    The presence of synthetic and naturally occurring chelating agents in nuclear and toxic-metal wastes is a major concern because of their potential to enhance mobilization of metal ions away from the disposal sites. Of particular interest is citric acid, which is present in low-level and transuranic radioactive wastes and in domestic and industrial wastes (as washing fluids, for instance), as well as being found naturally. Citrate ions form multidentate, stable complexes with a variety of toxic metals and radionuclides; but biodegradation of these complexes, precipitating the metal ions as insoluble hydroxides, oxides or other salts, may retard migration. Here we report a study of the biodegradation of citrate complexes of Ca, Fe(II), Fe(III), Cd, Cu, Ni, Pb and U. Several of these complexes were not readily degraded by bacteria, and the biodegradability depended on the chemical nature of the complex, not on the toxicity of the metal to the bacteria. This resistance to biodegradation implies that citrate complexation may play an important part in migration of these hazardous wastes. (author)

  20. TDPAC studies on metal-complex ferrimagnets

    Ohkubo, Yoshitaka [Kyoto Univ., Kumatori, Osaka (Japan). Research Reactor Inst.; Abe, Shizuko; Okada, Takuya [and others

    1997-03-01

    TDPAC spectra of {sup 117}In (left-arrow {sup 117}Cd) and {sup 111}Cd (left-arrow {sup 111m}Cd) in the mixed metal complex N(C{sub 4}H{sub 9}){sub 4}(M(II)Fe(III)(C{sub 2}O{sub 4}){sub 3})(M=Fe,Ni), the related substraces and LiNbO{sub 3} have been studied. In this paper, pure potassium iron (III) oxalate was prepared and mixed metal complexes were synthesized by changing amount of reagents and the order added, then observed by TDPAC. 2 mol%Cd was dispersed throughout potassium iron oxalate and potassium nickel oxalate, formulating M(II){sub 0.98}Cd(II){sub 0.02}C{sub 2}O{sub 4}{center_dot}2H{sub 2}O (M=Fe, Ni) with the same crystal structure. The formation reaction of mixed metal complex-Fe(II) was faster than that of iron oxalate. Its mixed metal complex-Ni(II) was slower than that of iron oxalate. The rate of quadrupole oscillation was obtained by {omega}{sub Q}({sup 117}In)=67.3 Mrad/s and {omega}{sub Q}({sup 111}Cd)=29.7 Mrad/s of which values were determined by TDPAC spectra of {sup 117}In and {sup 111}Cd in LiNbO{sub 3} at 4K. The value showed pure ion bond of oxygen coordinated with {sup 117}In and {sup 111}Cd. 0.08 {eta} was determined by TDPAC spectrum of {sup 111}Cd(left-arrow {sup 111m}Cd). The rate of {omega}{sub Q} of mixed metal oxalate complex was larger than 2.3, indicating 5s and 5p orbital electron took part in bond of oxygen of oxalic acid or approaching oxygen ion to In nucleus depend on the structual relaxation in decaying of {sup 117}In(left-arrow {sup 117}Cd). (S.Y.)

  1. Knowledge Based Cloud FE Simulation of Sheet Metal Forming Processes.

    Zhou, Du; Yuan, Xi; Gao, Haoxiang; Wang, Ailing; Liu, Jun; El Fakir, Omer; Politis, Denis J; Wang, Liliang; Lin, Jianguo

    2016-12-13

    The use of Finite Element (FE) simulation software to adequately predict the outcome of sheet metal forming processes is crucial to enhancing the efficiency and lowering the development time of such processes, whilst reducing costs involved in trial-and-error prototyping. Recent focus on the substitution of steel components with aluminum alloy alternatives in the automotive and aerospace sectors has increased the need to simulate the forming behavior of such alloys for ever more complex component geometries. However these alloys, and in particular their high strength variants, exhibit limited formability at room temperature, and high temperature manufacturing technologies have been developed to form them. Consequently, advanced constitutive models are required to reflect the associated temperature and strain rate effects. Simulating such behavior is computationally very expensive using conventional FE simulation techniques. This paper presents a novel Knowledge Based Cloud FE (KBC-FE) simulation technique that combines advanced material and friction models with conventional FE simulations in an efficient manner thus enhancing the capability of commercial simulation software packages. The application of these methods is demonstrated through two example case studies, namely: the prediction of a material's forming limit under hot stamping conditions, and the tool life prediction under multi-cycle loading conditions.

  2. Biological activities of some Fluoroquinolones-metal complexes

    McRoy

    DNA cleavage studies of some synthesized metal complexes of fluoroquinolone ... Although the FQs are generally characterized by a broad antimicrobial spectrum ..... six Coordinate 3rd metal complexes with N- (5 –Phenyl-3,4- thiadiazol-2-yl).

  3. Ibandronate metal complexes: solution behavior and antiparasitic activity.

    Demoro, Bruno; Rostán, Santiago; Moncada, Mauricio; Li, Zhu-Hong; Docampo, Roberto; Olea Azar, Claudio; Maya, Juan Diego; Torres, Julia; Gambino, Dinorah; Otero, Lucía

    2018-03-01

    To face the high costs of developing new drugs, researchers in both industry and academy are looking for ways to repurpose old drugs for new uses. In this sense, bisphosphonates that are clinically used for bone diseases have been studied as agents against Trypanosoma cruzi, causative parasite of Chagas disease. In this work, the development of first row transition metal complexes (M = Co 2+ , Mn 2+ , Ni 2+ ) with the bisphosphonate ibandronate (iba, H 4 iba representing the neutral form) is presented. The in-solution behavior of the systems containing iba and the selected 3d metal ions was studied by potentiometry. Mononuclear complexes [M(H x iba)] (2-x)- (x = 0-3) and [M(Hiba) 2 ] 4- together with the formation of the neutral polynuclear species [M 2 iba] and [M 3 (Hiba) 2 ] were detected for all studied systems. In the solid state, complexes of the formula [M 3 (Hiba) 2 (H 2 O) 4 ]·6H 2 O were obtained and characterized. All obtained complexes, forming [M(Hiba)] - species under the conditions of the biological studies, were more active against the amastigote form of T. cruzi than the free iba, showing no toxicity in mammalian Vero cells. In addition, the same complexes were selective inhibitors of the parasitic farnesyl diphosphate synthase (FPPS) enzyme showing poor inhibition of the human one. However, the increase of the anti-T. cruzi activity upon coordination could not be explained neither through the inhibition of TcFPPS nor through the inhibition of TcSPPS (T. cruzi solanesyl-diphosphate synthase). The ability of the obtained metal complexes of catalyzing the generation of free radical species in the parasite could explain the observed anti-T. cruzi activity.

  4. Migraine genetics : from monogenic to complex forms

    Vanmolkot, Kaate Raymond Josepha

    2008-01-01

    Migraine has a strong genetic component, but the identification of these factors has proven difficult mainly because of the complex interaction of multiple loci and environmental factors. Unraveling its molecular basis and deciphering pathways leading to migraine attacks will help identifying novel

  5. Interaction of Cr (III), Ni (II), Pb (II) with DTPA complexes of essential metal ions

    Gulzar, S.; Zahida; Maqsood, T.; Naqvi, R.R.

    2002-01-01

    With the increase of anthropogenic activities in the environment, heavy metal toxicity (Chromium, Nickel and Lead) is more common now. DTPA (diethylene triamine pentaacetic acid) a polyamino carboxylic acid is widely used to form hydrophilic and stable complexes with most of the metal ions. In this spectrophotometric study, concentration of Cr(III), Ni(II) and Pb(II) (toxic metal ions) exchanged with Fe(III), Zn(II) and Ca(II) from their DTPA complexes were estimated at pH 4,7 and 9. Concentration of added metal was varied from 1-4 times to that of complexed metal. (author)

  6. Evaluation of heavy metal complex phytotoxicity

    Vita Vasilyevna Datsenko

    2016-07-01

    Full Text Available The experimental data dealing with the effect of heavy metals contained in the technogenic contaminated soils on plant objects under controlled conditions was discussed. The aim of this work is to define the quantitative indicators of copper and zinc potential phytotoxicity, namely germination energy, simultaneous germination and duration of the test plants. It was found that the activity of the test plant growth is linked with copper and zinc complex action. Joint effect of copper and zinc is manifested both in inhibition of lettuce growth and determined, above all, by the nature contamination, soil properties and biological specificity of the test plants.

  7. FILAMENTARY STRUCTURE OF STAR-FORMING COMPLEXES

    Myers, Philip C.

    2009-01-01

    The nearest young stellar groups are associated with 'hubs' of column density exceeding 10 22 cm -2 , according to recent observations. These hubs radiate multiple 'filaments' of parsec length, having lower column density and fewer stars. Systems with many filaments tend to have parallel filaments with similar spacing. Such 'hub-filament structure' is associated with all of the nine young stellar groups within 300 pc, forming low-mass stars. Similar properties are seen in infrared dark clouds forming more massive stars. In a new model, an initial clump in a uniform medium is compressed into a self-gravitating, modulated layer. The outer layer resembles the modulated equilibrium of Schmid-Burgk with nearly parallel filaments. The filaments converge onto the compressed clump, which collapses to form stars with high efficiency. The initial medium and condensations have densities similar to those in nearby star-forming clouds and clumps. The predicted structures resemble observed hub-filament systems in their size, shape, and column density, and in the appearance of their filaments. These results suggest that HFS associated with young stellar groups may arise from compression of clumpy gas in molecular clouds.

  8. Simulation of the ductile damage under the metal forming

    Bogatov, A. A.

    2003-01-01

    Potentiality of metal forming is limited by ductile damage. The damage degree is estimated by the scalar value ω, that is equal to 0(ω=0) before plastic strain and is equal to 1(ω=1) at the macro cracks moment. There are two criteria that describe micro damage. The value ω=ω * corresponds to the generation of micro voids that couldn't be recovered by recrystallization but do not reduce the metal strength. The value ω=ω ** corresponds to the generation of micro voids that reduce the metal strength and material long life. The models of metal damage accumulation under pure and alternate strain also the model of metal damage recovery under the recrystallization are developed. The specimen testing at high loading parameters gives the basic equations of the ductile damage mechanics. All of that gives the method to study ductile damage under the metal forming. The methodology damage nucleation and growing is shown on various examples: the void and crack development in the areas ductile damage and unlimited ductility; mathematical simulation of the metal damage under the sheet and wire drawing and others. The problems of physical simulating at the ductile damage under metal forming are shown too in this paper. The method and equipment of metal damage physical simulation are proposed. (Original)

  9. Explosive force of primacord grid forms large sheet metal parts

    1966-01-01

    Primacord which is woven through fish netting in a grid pattern is used for explosive forming of large sheet metal parts. The explosive force generated by the primacord detonation is uniformly distributed over the entire surface of the sheet metal workpiece.

  10. Primary hafnium metal sponge and other forms, approved standard 1973

    Anon.

    1975-01-01

    A specification is presented covering virgin hafnium metal commonly designated as sponge because of its porous, sponge-like texture; it may also be in other forms such as chunklets. The specification does not cover crystal bar

  11. Environmentally Benign Tribo-systems for Metal Forming

    Bay, Niels; Azushima, A.; Groche, P.

    2010-01-01

    The growing awareness of environmental issues and the requirements to establish solutions diminishing the impact on working environment as well as external environment has initiated ever increasing efforts to develop new, environmentally benign tribological systems for metal forming. The present ...

  12. Overview of friction modelling in metal forming processes

    Nielsen, Chris Valentin; Bay, Niels Oluf

    2017-01-01

    In metal forming processes, friction between tool and workpiece is an important parameter influencing the material flow, surface quality and tool life. Theoretical models of friction in metal forming are based on analysis of the real contact area in tool-workpiece interfaces. Several research...... groups have studied and modelled the asperity flattening of workpiece material against tool surface in dry contact or in contact interfaces with only thin layers of lubrication with the aim to improve understanding of friction in metal forming. This paper aims at giving a review of the most important...... future work in order to advance further in modelling of real contact area in relation to implementation of frictional conditions existing finite element codes for simulation of metal forming processes. © 2017 The Authors. Published by Elsevier Ltd....

  13. Complexes in polyvalent metal - Alkali halide melts

    Akdeniz, Z.; Tosi, M.P.

    1991-03-01

    Experimental evidence is available in the literature on the local coordination of divalent and trivalent metal ions by halogens in some 140 liquid mixtures of their halides with alkali halides. After brief reference to classification criteria for main types of local coordination, we focus on statistical mechanical models that we are developing for Al-alkali halide mixtures. Specifically, we discuss theoretically the equilibrium between (AlF 6 ) 3- and (AlF 4 ) - complexes in mixtures of AlF 3 and NaF as a function of composition in the NaF-rich region, the effect of the alkali counterion on this equilibrium, the possible role of (AlF 5 ) 2- as an intermediate species in molten cryolite, and the origin of the different complexing behaviours of Al-alkali fluorides and chlorides. We also present a theoretical scenario for processes of structure breaking and electron localization in molten cryolite under addition of sodium metal. (author). 26 refs, 2 tabs

  14. Studies on micro plasto hydrodymic lubrication in metal forming

    Bay, Niels; Bech, Jakob Ilsted; Andreasen, Jan Lasson

    2002-01-01

    The influence of work piece surface topography on friction and lubrication and final surface quality in metal forming operations is well known and has been pointed out by many researchers, see Schey (1983) and Bay and Wanheim (1990). This is especially the case when liquid lubrication is applied...... characterization models the potential entrapment of a lubricant in closed reservoirs is used as a parameter to predetermine the formability of a sheet metal, Steinhoff et al. (1996), Geiger et al. (1997) and Schmoeckel et al. (1997). In experimental studies on friction in metal forming applying the strip drawing...

  15. Automobile sheet metal part production with incremental sheet forming

    İsmail DURGUN

    2016-02-01

    Full Text Available Nowadays, effect of global warming is increasing drastically so it leads to increased interest on energy efficiency and sustainable production methods. As a result of adverse conditions, national and international project platforms, OEMs (Original Equipment Manufacturers, SMEs (Small and Mid-size Manufacturers perform many studies or improve existing methodologies in scope of advanced manufacturing techniques. In this study, advanced manufacturing and sustainable production method "Incremental Sheet Metal Forming (ISF" was used for sheet metal forming process. A vehicle fender was manufactured with or without die by using different toolpath strategies and die sets. At the end of the study, Results have been investigated under the influence of method and parameters used.Keywords: Template incremental sheet metal, Metal forming

  16. Infrared Spectroscopy of Metal Ion Complexes: Models for Metal Ligand Interactions and Solvation

    Duncan, Michael

    2006-03-01

    Weakly bound complexes of the form M^+-Lx (M=Fe, Ni, Co, etc.; L=CO2, C2H2, H2O, benzene, N2) are prepared in supersonic molecular beams by laser vaporization in a pulsed-nozzle cluster source. These species are mass analyzed and size-selected in a reflectron time-of-flight mass spectrometer. Clusters are photodissociated at infrared wavelengths with a Nd:YAG pumped infrared optical parametric oscillator/amplifier (OPO/OPA) laser or with a tunable infrared free-electron laser. M^+-(CO2)x complexes absorb near the free CO2 asymmetric stretch near 2349 cm-1 but with an interesting size dependent variation in the resonances. Small clusters have blue-shifted resonances, while larger complexes have additional bands due to surface CO2 molecules not attached to the metal. M^+(C2H2)n complexes absorb near the C-H stretches in acetylene, but resonances in metal complexes are red-shifted with repect to the isolated molecule. Ni^+ and Co^+ complexes with acetylene undergo intracluster cyclization reactions to form cyclobutadiene. Transition metal water complexes are studied in the O-H stretch region, and partial rotational structure can be measured. M^+(benzene) and M^+(benzene)2 ions (M=V, Ti, Al) represent half-sandwich and sandwich species, whose spectra are measured near the free benzene modes. These new IR spectra and their assignments will be discussed as well as other new IR spectra for similar complexes.

  17. Operation of a capacitor bank for plasma metal forming

    pulse@svel.plasma.ernet.in (Pulse Expt.)

    Here we will be presenting a different technique for metal forming. ... Supply. Power. Input. Figure 1. Schematic diagram of the process. the work piece and a rigid conductor forms the electrode (in a ... in series with a 1000 MΩresistor chain. 4.

  18. Novel Metals and Metal Complexes as Platforms for Cancer Therapy

    Frezza, Michael; Hindo, Sarmad; Chen, Di; Davenport, Andrew; Schmitt, Sara; Tomco, Dajena; Dou, Q. Ping

    2010-01-01

    Metals are essential cellular components selected by nature to function in several indispensable biochemical processes for living organisms. Metals are endowed with unique characteristics that include redox activity, variable coordination modes, and reactivity towards organic substrates. Due to their reactivity, metals are tightly regulated under normal conditions and aberrant metal ion concentrations are associated with various pathological disorders, including cancer. For these reasons, coo...

  19. Extraction of fluoride metal complexes by octanols

    Baklanova, I.V.; Nikolaev, A.I.; Il'in, E.G.; Majorov, V.G.

    2005-01-01

    The extraction of niobium(V) and tantalum(V) by octanols, including 1-octanol, 2-octanol, and iso-octanol (2-ethylhexanol), was studied. The composition of the octanols and their solubility in various aqueous solutions were evaluated. The capacity of the octanols for tantalum(V) and niobium(V), the extraction properties of the octanols, the viscosity of extracts under conditions of metal fluoride extraction, and the temperature dependence of the viscosity of the octanols were studied. The composition of the extracted complexes was studied by IR and NMR spectroscopy and chemical analysis, and the hydration-solvation mechanism of the extraction of tantalum(V) and niobium(V) was supported [ru

  20. Literature survey on metal waste form for metallic waste from electrorefiners for the electrometallurgical treatment of spent metallic fuels

    Nishimura, Tomohiro

    2003-01-01

    This report summarizes the recent results of the metal waste form development activities at the Argonne National Laboratory in the USA for high-level radioactive metallic waste (stainless-steel (SS) cladding hulls, zirconium (Zr), noble-metal fission products (NMFPs), etc.) from electrorefiners for the electrometallurgical treatment of spent metallic fuels. Their main results are as follows: (1) SS- 15 wt.% Zr- ∼4 wt.% NMFPs alloy was selected as the metal waste form, (2) metallurgical data, properties, long-term corrosion data, etc. of the alloy have been collected, (3) 10-kg ingots have been produced in hot tests and a 60-kg production machine is under development. The following research should be made to show the feasibility of the metal waste form in Japan: (1) degradation assessment of the metal waste form in Japanese geological repository environments, and (2) clarification of the maximum allowable contents of NMFPs. (author)

  1. Protection of metal artefacts with the formation of metal-oxalates complexes by Beauveria bassiana.

    Edith eJoseph

    2012-01-01

    Full Text Available Several fungi present high tolerance to toxic metals and some are able to transform metals into metal-oxalate complexes. In this study, the ability of Beauveria bassiana to produce copper oxalates was evaluated in vitro. Growth performance was tested on various copper-containing media. B. bassiana proved highly resistant to copper, tolerating concentrations of up to 20 g.L-1, and precipitating copper oxalates on all media tested. Chromatographic analyses showed that this species produced oxalic acid as sole metal chelator. The production of metal-oxalates can be used in the restoration and conservation of archaeological and modern metal artefacts. The production of copper-oxalates was confirmed directly using metallic pieces (both archaeological and modern. The conversion of corrosion products into copper oxalates was demonstrated as well. In order to assess whether the capability of B. bassiana to produce metal-oxalates could be applied to other metals, iron and silver were tested as well. Iron appears to be directly sequestered in the wall of the fungal hyphae forming oxalates and probably goethite. However, the formation of a homogeneous layer on the object is not yet optimal. Silver nitrate was extracellularly reduced into nanoparticles of elemental silver by an unknown mechanism. The production of copper oxalates is immediately applicable for the conservation of copper-based artefacts. For iron and silver this is not yet the case. However, the vast ability of B. bassiana to transform toxic metals using different immobilization mechanisms seems to offer considerable possibilities for industrial applications, such as the bioremediation of contaminated soils or the green synthesis of chemicals.

  2. Incremental electrohydraulic forming - A new approach for the manufacture of structured multifunctional sheet metal blanks

    Djakow, Eugen; Springer, Robert; Homberg, Werner; Piper, Mark; Tran, Julian; Zibart, Alexander; Kenig, Eugeny

    2017-10-01

    Electrohydraulic Forming (EHF) processes permit the production of complex, sharp-edged geometries even when high-strength materials are used. Unfortunately, the forming zone is often limited as compared to other sheet metal forming processes. The use of a special industrial-robot-based tool setup and an incremental process strategy could provide a promising solution for this problem. This paper describes such an innovative approach using an electrohydraulic incremental forming machine, which can be employed to manufacture the large multifunctional and complex part geometries in steel, aluminium, magnesium and reinforced plastic that are employed in lightweight constructions or heating elements.

  3. Structural disorder in metallic glass-forming liquids.

    Pan, Shao-Peng; Feng, Shi-Dong; Wang, Li-Min; Qiao, Jun-Wei; Niu, Xiao-Feng; Dong, Bang-Shao; Wang, Wei-Min; Qin, Jing-Yu

    2016-06-09

    We investigated structural disorder by a new structural parameter, quasi-nearest atom (QNA), in atomistic configurations of eight metallic glass-forming systems generated through molecular dynamics simulations at various temperatures. Structural analysis reveals that the scaled distribution of the number of QNA appears to be an universal property of metallic liquids and the spatial distribution of the number of QNA displays to be clearly heterogeneous. Furthermore, the new parameter can be directly correlated with potential energy and structural relaxation at the atomic level. Some straightforward relationships between QNA and other properties (per-atom potential energy and α-relaxation time) are introduced to reflect structure-property relationship in metallic liquids. We believe that the new structural parameter can well reflect structure disorder in metallic liquids and play an important role in understanding various properties in metallic liquids.

  4. Theoretical studies of transition metal complexes with nitriles and isocyanides

    Kuznetsov, Maksim L

    2002-01-01

    Theoretical studies of transition metal complexes with nitriles and isocyanides are reviewed. The electronic structures and the nature of coordination bonds in these complexes are discussed. The correlation between the electronic structures of transition metal complexes with nitriles and isocyanides and their structural properties, spectroscopic characteristics, and reactivities are considered. The bibliography includes 121 references.

  5. Metal complexation capacity of Antarctic lacustrine sediments.

    Alberti, Giancarla; Mussi, Matteo; Quattrini, Federico; Pesavento, Maria; Biesuz, Raffaela

    2018-04-01

    The purpose of this study is to implement a work that is a part of a project funded by the Italian National Antarctic Research Program (PNRA, Piano Nazionale di Ricerche in Antartide) within the main thematic focus "Chemical Contamination-Global Change". This research was devoted to detect and characterize micro and nano components with strong complexing capability towards metal ions at trace level in sea water, lakes and lacustrine sediments, sampled during the XXII expedition of PNRA. In particular, in the present work, the sorption complexation capacity of an Antarctic lacustrine sediments toward Cu(II) and Pb(II) is described. The characterization of the sorption was undertaken, studying kinetics and isotherm profiles. The lake here considered is Tarn Flat in the area of Terra Nova Bay. The sorption equilibria of Cu(II) and Pb(II) on the lacustrine sediments were reached in about 10 h, and they were best modelled by the Langmuir equation. Preliminary, to establish if the data here obtained were consistent with those reported for the same area in other expeditions, a common multivariate techniques, namely the principal component analysis (PCA), was applied and finally the consistency of the data has been confirmed. Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. Measuring the Complexity of Urban Form and Design

    Boeing, Geoff

    2017-01-01

    Complex systems have become a popular lens for conceptualizing cities, and complexity has substantial implications for urban performance and resilience. This paper develops a typology of methods and measures for assessing the complexity of the built form at the scale of urban design. It extends quantitative methods from urban planning, network science, ecosystems studies, fractal geometry, and information theory to the physical urban form and the analysis of qualitative human experience. Metr...

  7. Review of friction modeling in metal forming processes

    Nielsen, C.V.; Bay, N.

    2018-01-01

    Abstract In metal forming processes, friction between tool and workpiece is an important parameter influencing the material flow, surface quality and tool life. Theoretical models of friction in metal forming are based on analysis of the real contact area in tool-workpiece interfaces. Several...... research groups have studied and modeled the asperity flattening of workpiece material against tool surface in dry contact or in contact interfaces with only thin layers of lubrication with the aim to improve understanding of friction in metal forming. This paper aims at giving a review of the most...... conditions, normal pressure, sliding length and speed, temperature changes, friction on the flattened plateaus and deformation of the underlying material. The review illustrates the development in the understanding of asperity flattening and the methods of analysis....

  8. Complex metal hydrides for hydrogen, thermal and electrochemical energy storage

    Møller, Kasper T.; Sheppard, Drew; Ravnsbæk, Dorthe B.

    2017-01-01

    field. This review illustrates that complex metal hydrides may store hydrogen in the solid state, act as novel battery materials, both as electrolytes and electrode materials, or store solar heat in a more efficient manner as compared to traditional heat storage materials. Furthermore, it is highlighted...... how complex metal hydrides may act in an integrated setup with a fuel cell. This review focuses on the unique properties of light element complex metal hydrides mainly based on boron, nitrogen and aluminum, e.g., metal borohydrides and metal alanates. Our hope is that this review can provide new...

  9. Process and equipment qualification of the ceramic and metal waste forms for spent fuel treatment

    Marsden, Ken; Knight, Collin; Bateman, Kenneth; Westphal, Brian; Lind, Paul

    2005-01-01

    The electrometallurgical process for treating sodium-bonded spent metallic fuel at the Materials and Fuels Complex of the Idaho National Laboratory separates actinides and partitions fission products into two waste forms. The first is the metal waste form, which is primarily composed of stainless steel from the fuel cladding. This stainless steel is alloyed with 15w% zirconium to produce a very corrosion-resistant metal which binds noble metal fission products and residual actinides. The second is the ceramic waste form which stabilizes fission product-loaded chloride salts in a sodalite and glass composite. These two waste forms will be packaged together for disposal at the Yucca Mountain repository. Two production-scale metal waste furnaces have been constructed. The first is in a large argon-atmosphere glovebox and has been used for equipment qualification, process development, and process qualification - the demonstration of process reliability for production of the DOE-qualified metal waste form. The second furnace will be transferred into a hot cell for production of metal waste. Prototype production-scale ceramic waste equipment has been constructed or procured; some equipment has been qualified with fission product-loaded salt in the hot cell. Qualification of the remaining equipment with surrogate materials is underway. (author)

  10. Scale effects in metal-forming friction and lubrication

    Nielsen, Peter Søe; Paldan, Nikolas Aulin; Calaon, Matteo

    2011-01-01

    Downscaling of metal-forming operations from macro-to microscale implies significant changes caused by size effects. Among these, the friction increases as reported by researchers using indirect test methods such as the ring-compression test and double-cup-extrusion test. In this study, a new test...... equipment is developed for studies of the size effect in metal-forming friction in the range from macro-to microscale. Investigations confirm a significant friction increase when downscaling. Visual inspection of the workpieces shows this to be explained by the amount of open and closed lubricant pockets....

  11. Electrochemical Corrosion Studies for Modeling Metallic Waste Form Release Rates

    Poineau, Frederic; Tamalis, Dimitri

    2016-01-01

    The isotope 99 Tc is an important fission product generated from nuclear power production. Because of its long half-life (t 1/2 = 2.13 ∙ 105 years) and beta-radiotoxicity (β - = 292 keV), it is a major concern in the long-term management of spent nuclear fuel. In the spent nuclear fuel, Tc is present as an alloy with Mo, Ru, Rh, and Pd called the epsilon-phase, the relative amount of which increases with fuel burn-up. In some separation schemes for spent nuclear fuel, Tc would be separated from the spent fuel and disposed of in a durable waste form. Technetium waste forms under consideration include metallic alloys, oxide ceramics and borosilicate glass. In the development of a metallic waste form, after separation from the spent fuel, Tc would be converted to the metal, incorporated into an alloy and the resulting waste form stored in a repository. Metallic alloys under consideration include Tc–Zr alloys, Tc–stainless steel alloys and Tc–Inconel alloys (Inconel is an alloy of Ni, Cr and iron which is resistant to corrosion). To predict the long-term behavior of the metallic Tc waste form, understanding the corrosion properties of Tc metal and Tc alloys in various chemical environments is needed, but efforts to model the behavior of Tc metallic alloys are limited. One parameter that should also be considered in predicting the long-term behavior of the Tc waste form is the ingrowth of stable Ru that occurs from the radioactive decay of 99 Tc ( 99 Tc → 99 Ru + β - ). After a geological period of time, significant amounts of Ru will be present in the Tc and may affect its corrosion properties. Studying the effect of Ru on the corrosion behavior of Tc is also of importance. In this context, we studied the electrochemical behavior of Tc metal, Tc-Ni alloys (to model Tc-Inconel alloy) and Tc-Ru alloys in acidic media. The study of Tc-U alloys has also been performed in order to better understand the nature of Tc in metallic spent fuel. Computational modeling

  12. Electrochemical Corrosion Studies for Modeling Metallic Waste Form Release Rates

    Poineau, Frederic [Univ. of Nevada, Las Vegas, NV (United States); Tamalis, Dimitri [Florida Memorial Univ., Miami Gardens, FL (United States)

    2016-08-01

    The isotope 99Tc is an important fission product generated from nuclear power production. Because of its long half-life (t1/2 = 2.13 ∙ 105 years) and beta-radiotoxicity (β⁻ = 292 keV), it is a major concern in the long-term management of spent nuclear fuel. In the spent nuclear fuel, Tc is present as an alloy with Mo, Ru, Rh, and Pd called the epsilon-phase, the relative amount of which increases with fuel burn-up. In some separation schemes for spent nuclear fuel, Tc would be separated from the spent fuel and disposed of in a durable waste form. Technetium waste forms under consideration include metallic alloys, oxide ceramics and borosilicate glass. In the development of a metallic waste form, after separation from the spent fuel, Tc would be converted to the metal, incorporated into an alloy and the resulting waste form stored in a repository. Metallic alloys under consideration include Tc–Zr alloys, Tc–stainless steel alloys and Tc–Inconel alloys (Inconel is an alloy of Ni, Cr and iron which is resistant to corrosion). To predict the long-term behavior of the metallic Tc waste form, understanding the corrosion properties of Tc metal and Tc alloys in various chemical environments is needed, but efforts to model the behavior of Tc metallic alloys are limited. One parameter that should also be considered in predicting the long-term behavior of the Tc waste form is the ingrowth of stable Ru that occurs from the radioactive decay of 99Tc (99Tc → 99Ru + β⁻). After a geological period of time, significant amounts of Ru will be present in the Tc and may affect its corrosion properties. Studying the effect of Ru on the corrosion behavior of Tc is also of importance. In this context, we studied the electrochemical behavior of Tc metal, Tc-Ni alloys (to model Tc-Inconel alloy) and Tc-Ru alloys in acidic media. The study of Tc-U alloys has also been performed in order to better understand the

  13. EXPERIMENTAL TESTING OF DRAW-BEAD RESTRAINING FORCE IN SHEET METAL FORMING

    J.H. Yang; J. Chen; D.N. He; X. Y. Ruan

    2003-01-01

    Due to complexities of draw-bead restraining force calculated according to theory anddepending on sheet metal forming properties experiment testing system, a simplifiedmethod to calculate draw-bead restraining force is put forward by experimental methodin cup-shaped drawing process. The experimental results were compared with numer-ical results and proved agreement. It shows the method is effective.

  14. Metal oxalate complexes as novel inorganic dopants: Studies on ...

    Unknown

    UV-visible and IR spectral features not only confirmed the polyaniline doping by complex anions but also substantiated ... MoS3 dopant. Although inorganic metal complexes bear- ... distilled water and then with methanol and acetone until.

  15. Synthesis, characterization, anti-microbial, DNA binding and cleavage studies of Schiff base metal complexes

    Poomalai Jayaseelan

    2016-09-01

    Full Text Available A novel Schiff base ligand has been prepared by the condensation between butanedione monoxime with 3,3′-diaminobenzidine. The ligand and metal complexes have been characterized by elemental analysis, UV, IR, 1H NMR, conductivity measurements, EPR and magnetic studies. The molar conductance studies of Cu(II, Ni(II, Co(II and Mn(II complexes showed non-electrolyte in nature. The ligand acts as dibasic with two N4-tetradentate sites and can coordinate with two metal ions to form binuclear complexes. The spectroscopic data of metal complexes indicated that the metal ions are complexed with azomethine nitrogen and oxyimino nitrogen atoms. The binuclear metal complexes exhibit octahedral arrangements. DNA binding properties of copper(II metal complex have been investigated by electronic absorption spectroscopy. Results suggest that the copper(II complex bind to DNA via an intercalation binding mode. The nucleolytic cleavage activities of the ligand and their complexes were assayed on CT-DNA using gel electrophoresis in the presence and absence of H2O2. The ligand showed increased nuclease activity when administered as copper complex and copper(II complex behave as efficient chemical nucleases with hydrogen peroxide activation. The anti-microbial activities and thermal studies have also been studied. In anti-microbial activity all complexes showed good anti-microbial activity higher than ligand against gram positive, gram negative bacteria and fungi.

  16. Testing of environmentally friendly lubricants for sheet metal forming

    Bay, Niels; Olsson, David Dam; Andreasen, Jan Lasson

    2005-01-01

    the authors have especially been involved in the development of a system of test methods for sheet metal forming and in testing of friction and limits of lubrication of new, environmentally friendly lubricants. An overview of the developed tests is presented together with selected results....

  17. Lability of Nanoparticulate Metal Complexes at a Macroscopic Metal Responsive (Bio)interface

    Duval, Jérôme F.L.; Town, Raewyn M.; Leeuwen, Van Herman P.

    2018-01-01

    The lability of metal complexes expresses the extent of the dissociative contribution of the complex species to the flux of metal ions toward a macroscopic metal-responsive (bio)interface, for example, an electrodic sensor or an organism. While the case of molecular ligands is well-established, it

  18. Metal Complexation with Chitosan and its Grafted Copolymer

    Abo-Hussen, A.A.; Elkholy, S.S.; Elsabee, M.Z.

    2005-01-01

    The adsorption of M (II); Co (II), Ni (If), Cu (II), Zn (II) and Cd (II) from aqueous solutions by chitosan flakes and beads have been studied. The maximum up-take of M (II) ions on chitosan beads was greater than on flakes. Batch adsorption experiments were carried out as a function of ph, agitation period and initial concentration of the metal ions. A ph of 6.0 was found to be optimum for M (II) adsorption on chitosan flakes and beads. The uptake of the ions was determined from the changes in its concentration, as measured by ultraviolet and visible spectroscopy. The metal ions uptake of chitosan grafted with vinyl pyridine (VP) is higher than that of the chitosan. The experimental data of the adsorption equilibrium from M (II)-solutions correlated well with the Langmuir and Freundlich equations. Several spectroscopic methods have been used to study the formation of the polymer/metal cation complex. The cation coordination is accompanied by proton displacement off the polymer or by fixation of a hydroxide ion in aqueous solutions. The largest ionic displacement is observed with Cu (II) and Zn (II) demonstrating the largest affinity of chitosan for these ions. The FT-IR spectral of the complexes show that both the amino and hydroxyl groups of chitosan participated in the chelation process. The ESR spectra of Cu-complex show an absorption at gi 2.06, g// = 2.23, A// x 10-4 (cm-1) = 160 and G = 3.8 indicating the formation of square planar structure. The adsorption of M (II) ions followed the sequence Cu (II) > Zn (II) > Cd (II) > Ni (II) > Co (II), this order seems to be independent on the size and the physical form of chitosan. SEM shows small membranous structure on the surface of chitosan flakes as compared to Cu (Il)- chitosan complex. EDTA was used for the desorption studies

  19. Plasmon hybridization in complex metallic nanostructures

    Hao, Feng

    With Plasmon Hybridization (PH) and Finite-Difference Time-Domain (FDTD) method, we theoretically investigated the optical properties of some complex metallic nanostructures (coupled nanoparticle/wire, nanostars, nanorings and combined ring/disk nanocavity systems). We applied the analytical formulism of PH studying the plasmonic coupling of a spherical metallic nanoparticle and an infinite long cylindrical nanowire. The plasmon resonance of the coupled system is shown shifted in frequency, which highly depends on the polarization of incident light relative to the geometry of the structure. We also showed the nanoparticle serves as an efficient antenna coupling the electromagnetic radiation into the low-energy propagating wire plasmons. We performed an experimental and theoretical analysis of the optical properties of gold nanorings with different sizes and cross sections. For light polarized parallel to the ring, the optical spectrum sensitively depends on the incident angle. When light incidence is normal to the ring, two dipolar resonance is observed. As the incident light is titled, some previously dark mulipolar plasmon resonances will be excited as a consequence of the retardation. The concept of plasmon hybridization is combined with the power of brute-force numerical methods to understand the plasmonic properties of some very complicated nanostructures. We showed the plasmons of a gold nanostar are a result of hybridization of the plasmons of the core and the tips of the particle. The core serves as a nanoantenna, dramatically enhanced the optical spectrum and the field enhancement of the nanostar. We also applied this method analyzing the plasmonic modes of a nanocavity structure composed of a nanodisk with a surrounding minoring. For the concentric combination, we showed the nature of the plasmon modes can be understood as the plasmon hybrization of an individual ring and disk. The interation results in a blueshifted and broadened superradiant antibonding

  20. Cell complexes of transition metals in biochemistry and medicine

    Voloshin, Ya.Z.; Varzatskij, O.A.; Bubnov, Yu.N.

    2007-01-01

    Basic directions and prospects of use of cell complexes of transition metals in medicine and biochemistry are considered: incapsulation of radioactive metal ions for radiotherapy and diagnostics; preparation of contrast compounds for magnetic resonance tomography, antidotes and pharmaceutical preparation of prolonged effect, preparations for boron-neutron-capture therapy of neoplasms, antioxidants; membrane transport of metal ions; study of interaction of cell metal complexes with nucleic acids; possibility of use of self-assembly of cell complexes for imitation of ligases and use of clathrochelates as linkers; design of inhibitors of viruses for AIDS therapy [ru

  1. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Diazo substituted carbomonocyclic... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting under...

  2. Tris-diamine-derived transition metal complexes of flurbiprofen as ...

    admin

    butyrylcholinesterase (BChE) inhibitory activities. Method: Tris-diamine-derived transition metal complexes of Co(II), Ni(II), and Mn(II) were synthesized and characterized ... Conductance measurements indicated that diamine-derived metal complexes of ..... contributes to enhanced biological activity, and provides novel ...

  3. Mixed Metal Complexes of Isoniazid and Ascorbic Acid: Chelation ...

    HP

    these ligands and their metal complexes have revealed the bi-dentate coordination of isoniazid ligand to ... of the drugs on coordination with a metal is enhanced ..... James, O.O., Nwinyi, C.O. and. Allensela, M.A. (2008). Cobalt(II) complexes of mixed antibiotics: Synthesis,. Characterization, antimicrobial potential and their.

  4. Advanced Wear Simulation for Bulk Metal Forming Processes

    Behrens Bernd-Arno

    2016-01-01

    Full Text Available In the recent decades the finite element method has become an essential tool for the cost-efficient virtual process design in the metal forming sector in order to counter the constantly increasing quality standards, particularly from the automotive industry as well as intensified international competition in the forging industry. An optimized process design taking precise tool wear prediction into account is a way to increase the cost-efficiency of the bulk metal forming processes. The main objective of the work presented in this paper is a modelling algorithm, which allows predicting die wear with respect to a geometry update during the forming simulation. Changes in the contact area caused by geometry update lead to the different die wear distribution. It primarily concerns the die areas, which undergo high thermal and mechanical loads.

  5. Precision analysis in billet preparation for micro bulk metal forming

    Mahshid, Rasoul; Hansen, Hans N.

    2015-01-01

    The purpose of this research is to fabricate billets for an automated transfer press for micro forming. High performance transfer presses are wellknown in conventional metal forming and distinguished from their automation and mass production. The press used in this research is a vertical mechanical...... press. When using a vertical mechanical press, the material is fed as billets into the forming zone. Therefore, a large number of highly uniform billets are required to run mass production in such a setup. Shearing technique was used for manufacturing the billets. The efficiency of the shearing tool...

  6. Metallacyclopentadienes: structural features and coordination in transition metal complexes

    Dolgushin, Fedor M; Yanovsky, Aleksandr I; Antipin, Mikhail Yu

    2004-01-01

    Results of structural studies of polynuclear transition metal complexes containing the metallacyclopentadiene fragment are overviewed. The structural features of the complexes in relation to the nature of the substituents in the organic moiety of the metallacycles, the nature of the transition metals and their ligand environment are analysed. The main structural characteristics corresponding to different modes of coordination of metallacyclopentadienes to one or two additional metal centres are revealed.

  7. Secondary Teachers' Conception of Various Forms of Complex Numbers

    Karakok, Gulden; Soto-Johnson, Hortensia; Dyben, Stephenie Anderson

    2015-01-01

    This study explores in-service high school mathematics teachers' conception of various forms of complex numbers and ways in which they transition between different representations of these forms. One 90-min interview was conducted with three high school mathematics teachers after they completed three professional development sessions, each 4 h, on…

  8. Dynamical complexity changes during two forms of meditation

    Li, Jin; Hu, Jing; Zhang, Yinhong; Zhang, Xiaofeng

    2011-06-01

    Detection of dynamical complexity changes in natural and man-made systems has deep scientific and practical meaning. We use the base-scale entropy method to analyze dynamical complexity changes for heart rate variability (HRV) series during specific traditional forms of Chinese Chi and Kundalini Yoga meditation techniques in healthy young adults. The results show that dynamical complexity decreases in meditation states for two forms of meditation. Meanwhile, we detected changes in probability distribution of m-words during meditation and explained this changes using probability distribution of sine function. The base-scale entropy method may be used on a wider range of physiologic signals.

  9. Formability models for warm sheet metal forming analysis

    Jiang, Sen

    Several closed form models for the prediction of strain space sheet metal formability as a function of temperature and strain rate are proposed. The proposed models require only failure strain information from the uniaxial tension test at an elevated temperature setting and failure strain information from the traditionally defined strain space forming limit diagram at room temperature, thereby featuring the advantage of offering a full forming limit description without having to carry out expensive experimental studies for multiple modes of deformation under the elevated temperature. The Power law, Voce, and Johnson-Cook hardening models are considered along with the yield criterions of Hill's 48 and Logan-Hosford yield criteria. Acceptable correlations between the theory and experiment are reported for all the models under a plane strain condition. Among all the proposed models, the model featuring Johnson-Cook hardening model and Logan-Hosford yield behavior (LHJC model) was shown to best correlate with experiment. The sensitivity of the model with respect to various forming parameters is discussed. This work is significant to those aiming to incorporate closed-form formability models directly into numerical simulation programs for the purpose of design and analysis of products manufactured through the warm sheet metal forming process. An improvement based upon Swift's diffuse necking theory, is suggested in order to enhance the reliability of the model for biaxial stretch conditions. Theory relating to this improvement is provided in Appendix B.

  10. Complexes formed by cadmium and chelating agents in plants

    Strasdeit, H.; Duhme, A.K.; Johanning, J.

    1993-01-01

    Measurements of X-ray absorption spectrums and potentiometric titrations yield some information on the basic complexforming properties of phytochelates. Cadmium-phytochelate complexes are extremely variable as regards composition and structure. This is evident from the fact that the metal's coordination environment (sulphur or oxygen coordination) is dependent uopn pH values. At pH values of about 7 it is normal to find Cd(SCys) 4 units. Given the availability of an adequate number of ligands, these are seen to occur as solitary units even in multinucleate complexes. (orig.) [de

  11. Preparation and characterisation of some transition metal complexes of niacinamide (vitamin b3)

    Hasan, M.M.; Hossain, M.E.; Halim, M.E.

    2015-01-01

    Niacinamide forms metal complexes of general formula (M(C/sub 6/H/sub 6/N/sub 2/O)2)Cl/sub 2/; where M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) in the aqueous medium. The complexes were formulated by comparing the experimental and calculated data for C, H, N and metal. The prepared complexes were characterized by different physicochemical methods. The UV-vis, FTIR spectral analysis and thermo gravimetric analysis (TGA). TGA of these complexes have been discussed. Magnetic susceptibility values indicate that all complexes except Zn complex are paramagnetic in nature. The redox properties of the metal ions in the Mn, Cu and Zn complexes have been discussed from the cyclic voltammetric studies. In all cases the systems are quasi reversible. (author)

  12. Observation of metallic sphere–complex plasma interactions in microgravity

    Schwabe, M; Zhdanov, S; Hagl, T; Huber, P; Rubin-Zuzic, M; Zaehringer, E; Thomas, H M; Lipaev, A M; Molotkov, V I; Naumkin, V N; Fortov, V E; Vinogradov, P V

    2017-01-01

    The PK-3 Plus laboratory on board the International Space Station is used to study the interaction between metallic spheres and a complex plasma. We show that the metallic spheres significantly affect both the local plasma environment and the microparticle dynamics. The spheres charge under the influence of the plasma and repel the microparticles, forming cavities surrounding the spheres. The size of the cavity around a sphere is used to study the force balance acting on microparticles at the cavity edge. We show that the ion drag force and pressure force from other microparticles balances with the electric force acting from the sphere to within 20%. At intermediate distances from the sphere surface, the interaction between the microparticles and the metallic spheres is attractive due to the drag force stemming from the ions which are moving towards the highly charged spheres. The spheres thus strongly affect the plasma fluxes. This modification of the plasma flux can lead to an effective surface tension acting on the microparticles, and to the excitation of dust-density waves near the spheres, as the local electric field crosses a threshold. (paper)

  13. Hydrogen storage and evolution catalysed by metal hydride complexes.

    Fukuzumi, Shunichi; Suenobu, Tomoyoshi

    2013-01-07

    The storage and evolution of hydrogen are catalysed by appropriate metal hydride complexes. Hydrogenation of carbon dioxide by hydrogen is catalysed by a [C,N] cyclometalated organoiridium complex, [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))benzoic acid-κC(3))(OH(2))](2)SO(4) [Ir-OH(2)](2)SO(4), under atmospheric pressure of H(2) and CO(2) in weakly basic water (pH 7.5) at room temperature. The reverse reaction, i.e., hydrogen evolution from formate, is also catalysed by [Ir-OH(2)](+) in acidic water (pH 2.8) at room temperature. Thus, interconversion between hydrogen and formic acid in water at ambient temperature and pressure has been achieved by using [Ir-OH(2)](+) as an efficient catalyst in both directions depending on pH. The Ir complex [Ir-OH(2)](+) also catalyses regioselective hydrogenation of the oxidised form of β-nicotinamide adenine dinucleotide (NAD(+)) to produce the 1,4-reduced form (NADH) under atmospheric pressure of H(2) at room temperature in weakly basic water. In weakly acidic water, the complex [Ir-OH(2)](+) also catalyses the reverse reaction, i.e., hydrogen evolution from NADH to produce NAD(+) at room temperature. Thus, interconversion between NADH (and H(+)) and NAD(+) (and H(2)) has also been achieved by using [Ir-OH(2)](+) as an efficient catalyst and by changing pH. The iridium hydride complex formed by the reduction of [Ir-OH(2)](+) by H(2) and NADH is responsible for the hydrogen evolution. Photoirradiation (λ > 330 nm) of an aqueous solution of the Ir-hydride complex produced by the reduction of [Ir-OH(2)](+) with alcohols resulted in the quantitative conversion to a unique [C,C] cyclometalated Ir-hydride complex, which can catalyse hydrogen evolution from alcohols in a basic aqueous solution (pH 11.9). The catalytic mechanisms of the hydrogen storage and evolution are discussed by focusing on the reactivity of Ir-hydride complexes.

  14. Testing of Lubricant Performance in Sheet Metal Forming

    Bay, Niels; Olsson, David Dam; Friis, Kasper Leth

    2008-01-01

    Increasing focus on environmental issues in industrial production has urged a number of sheet metal forming companies to look for new tribo-systems in order to substitute hazardous lubricants such as chlorinated paraffin oils. The problems are especially pronounced, when forming tribologically...... of the lubricant film causing pick-up of work piece material on the tool surface and scoring of subsequent work piece surfaces. The present paper gives an overview of more than 10 years work by the authors’ research group through participation in national as well as international framework programmes on developing...

  15. Forming Limits in Sheet Metal Forming for Non-Proportional Loading Conditions - Experimental and Theoretical Approach

    Ofenheimer, Aldo; Buchmayr, Bruno; Kolleck, Ralf; Merklein, Marion

    2005-01-01

    The influence of strain paths (loading history) on material formability is well known in sheet forming processes. Sophisticated experimental methods are used to determine the entire shape of strain paths of forming limits for aluminum AA6016-T4 alloy. Forming limits for sheet metal in as-received condition as well as for different pre-deformation are presented. A theoretical approach based on Arrieux's intrinsic Forming Limit Stress Curve (FLSC) concept is employed to numerically predict the influence of loading history on forming severity. The detailed experimental strain paths are used in the theoretical study instead of any linear or bilinear simplified loading histories to demonstrate the predictive quality of forming limits in the state of stress

  16. Distribution of metals between particulate and gaseous forms in a volcanic plume

    Hinkley, T.K.

    1991-01-01

    In order to gain information on the distribution of metals between particles and gaseous forms in the plume of Kilauea volcano, a filter designed to collect metals associated with particles was followed in series by two other collectors intended to trap metals present in gaseous (atomic, molecular, or complexed) form: first an acid-bubbler bath and then a cold trap. Of the six metals measured, all of the In, Tl and Bi, and almost all of the Cd, Pb and Cu were found on the filter. None of any of the metals was detected in the acid-bubbler bath. Masses equivalent to 0.3% of the amount of Cd on the filter, 0.4% of the amount of Pb, and 9.3% of the Cu, were measured in the cold trap. The results indicate that all or nearly all of the six metals were partitioned to the particulate portion of the physical mixture of gases and particles that constitutes a volcanic plume, but that there may be systematic differences between chalcophile metals in the ways they are partitioned between particulate and gaseous phases in a cooled plume, and possibly differences in the acidity or other chemical properties of the molecular phases. ?? 1991 Springer-Verlag.

  17. 48 CFR 53.301-1427 - Standard Form 1427, Inventory Schedule A-Construction Sheet (Metals in Mill Product Form).

    2010-10-01

    ... 48 Federal Acquisition Regulations System 2 2010-10-01 2010-10-01 false Standard Form 1427, Inventory Schedule A-Construction Sheet (Metals in Mill Product Form). 53.301-1427 Section 53.301-1427... Illustrations of Forms 53.301-1427 Standard Form 1427, Inventory Schedule A—Construction Sheet (Metals in Mill...

  18. Complex-forming capacity of some biologically active imidazoles

    Lenarcik, B; Wisniewski, M

    1983-01-01

    By using the potentiometric and spectrophotometric methods, formation of Co(2), Cu(2), Zn(2), Ni(2) and Cd(2) complexes of (3S-cis)-3-ethyl-dihydro-4-((1-methyl-1H-imidazol-5-yl)-methyl)-2(3H)-furanone (pilocarpine, PLC), 4,5-dihydro-2-(phenylmethyl)-1H-imidazole (tolazoline, TLZ), 2-methyl-5-nitro-1H-imidazole-1-ethanol (metronidazole, MET) and 1H-imidazole-4-ethanamine (histamine, HIST) was investigated. The stability constants, ..beta../sub n/, of these complexes were determined. It was shown that the electron-donor strength of the ligands was controlled by the heterocyclic nitrogen atom, and that the formation of the Zn(2)-PLC complex was accompanied by the change in the structure of the coordination sphere of the metal. With Cu(2), the PLC and TLZ ligands were shown to enhance the Jahn-Teller deformation.

  19. Reactivity of monoolefin ligand in transition metal complexes

    Rybinskaya, M.I.

    1978-01-01

    The main tendencies in the coordinated olefin ligand property changes are discussed in the transition metal complexes in comparison with free olefins. The review includes the papers published from 1951 up to 1976. It has been shown that in complexes with transition metal cations olefin π-base acquires the ability to react with nucleophylic reagents. Olefin π-acids in complexes with zero valent metals are easily subjected to electrophylic reagent action. At coordination with transition metal cations the olefin properties are generally preserved, while in the zero-valent metal complexes the nonsaturated ligand acquires the properties of a saturated compounds. The ability of transition metal cations in complexes to intensify reactions of nucleophylic bimolecular substitution of vinyl halogen is clearly detected in contrast to the zero valent metal complexes. It has been shown that investigations of the coordinated olefin ligand reactivity give large possibilities in the further development of the organic synthesis. Some reactions are taken as the basis of important industrial processes

  20. N-acyl thioureas - selective ligands for complexing of heavy metals and noble metals

    Schuster, M.

    1992-01-01

    Acyl thioureas are complexing agents for heavy metals that are easily produced and very stable. Their favourable toxicological data make them particularly suitable for industrial applications, e.g. detoxification of metallic process solutions or solvent extraction of metals. (orig.) [de

  1. Gas-phase complexes formed between amidoxime ligands and vanadium or iron investigated using electrospray ionization mass spectrometry.

    Mustapha, Adetayo M; Pasilis, Sofie P

    2016-08-15

    Amidoxime-functionalized sorbents can be used to extract uranium from seawater. Iron(III) and vanadium(V) may compete with uranium for adsorption sites. We use 2,6-dihydroxyiminopiperidine (DHIP) and N(1) ,N(5) -dihydroxypentanediimidamide (DHPD) to model amidoxime functional groups and characterize the vanadium(V) and iron(III) complexes with these ligands. We also examine the effect of iron(III) and vanadium(V) on uranyl(VI) complexation by DHIP and DHPD. The experiments were carried out in positive ion mode using a quadrupole ion trap mass spectrometer equipped with an electrospray ionization source. The effect on the mass spectra of changes in ligand, metal:ligand mole ratio, and pH was examined. Iron(III) formed a 1:2 metal:ligand complex with DHIP at all metal:ligand mole ratios and pH values investigated; it formed both 1:2 and 1:3 metal:ligand complexes with DHPD. Vanadium(V) formed 1:1 and 1:2 metal:ligand complexes with DHIP. A 1:2 metal:ligand complex was formed with DHPD at all vanadium(V):DHPD mole ratios investigated. Changes in solution pH did not affect the ions observed. The relative binding affinities of the metal ions towards DHIP followed the order iron(III) > vanadium(V) > uranyl(VI). This study presents a first look at the gas-phase vanadium(V)- and iron(III)-DHIP and -DHPD complexes using electrospray ionization mass spectrometry. These metals form stronger complexes with amidoxime ligands than uranyl(VI), and will affect uranyl(VI) adsorption to amidoxime-based sorbents. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  2. Energetic Surface Smoothing of Complex Metal-Oxide Thin Films

    Willmott, P.R.; Herger, R.; Schlepuetz, C.M.; Martoccia, D.; Patterson, B.D.

    2006-01-01

    A novel energetic smoothing mechanism in the growth of complex metal-oxide thin films is reported from in situ kinetic studies of pulsed laser deposition of La 1-x Sr x MnO 3 on SrTiO 3 , using x-ray reflectivity. Below 50% monolayer coverage, prompt insertion of energetic impinging species into small-diameter islands causes them to break up to form daughter islands. This smoothing mechanism therefore inhibits the formation of large-diameter 2D islands and the seeding of 3D growth. Above 50% coverage, islands begin to coalesce and their breakup is thereby suppressed. The energy of the incident flux is instead rechanneled into enhanced surface diffusion, which leads to an increase in the effective surface temperature of ΔT≅500 K. These results have important implications on optimal conditions for nanoscale device fabrication using these materials

  3. Alkylation and arylation of alkenes by transition metal complexes

    Volkova, L.G.; Levitin, I.Ya.; Vol'pin, M.E.

    1975-01-01

    In this paper are reviewed methods of alkylation and irylation of unsaturated compounds with complexes of transition metals (Rh, Pd). Analysis of alkylation and arylation of olefines with organic derivatives of transition metals, obtained as a result of exchange reactions between organic compounds of transition metals and salts of metals of the 8th group of the periodic system, allows a conclusion as to the wide possibilities of these reactions in the synthesis of various derivatives of unsaturated compounds. In all the reactions under consideration, intermediate formation of sigma-complexes is assumed. Also considered are alkylation and arylation of olefines with organic derivatives of halogens in the presence of compounds of metals of the 8th group of the periodic system, as well as arylation of olefines with aromatic compounds in the presence of salts of transition metals

  4. Kinetics of the reactions of hydrated electrons with metal complexes

    Korsse, J.

    1983-01-01

    The reactivity of the hydrated electron towards metal complexes is considered. Experiments are described involving metal EDTA and similar complexes. The metal ions studied are mainly Ni 2+ , Co 2+ and Cu 2+ . Rates of the reactions of the complexes with e - (aq) were measured using the pulse radiolysis technique. It is shown that the reactions of e - (aq) with the copper complexes display unusually small kinetic salt effects. The results suggest long-range electron transfer by tunneling. A tunneling model is presented and the experimental results are discussed in terms of this model. Results of approximate molecular orbital calculations of some redox potentials are given, for EDTA chelates as well as for series of hexacyano and hexaquo complexes. Finally, equilibrium constants for the formation of ternary complexes are reported. (Auth./G.J.P.)

  5. A System of Test Methods for Sheet Metal Forming Tribology

    Bay, Niels; Olsson, David Dam; Andreasen, Jan Lasson

    2007-01-01

    Sheet metal forming of tribologically difficult materials such as stainless steel, Al-alloys and Ti-alloys or forming in tribologically difficult operations like ironing, punching or deep drawing of thick plate requires often use of environmentally hazardous lubricants such as chlorinated paraffin...... oils in order to avoid galling. The present paper describes a systematic research in the development of new, environmentally harmless lubricants focusing on the lubricant testing aspects. A system of laboratory tests has been developed to study the lubricant performance under the very varied conditions...... appearing in different sheet forming operations such as stamping, deep drawing, ironing and punching. The laboratory tests have been especially designed to model the conditions in industrial production....

  6. Radial-rotation profile forming: A new processing technology of incremental sheet metal forming

    Laue, Robert; Härtel, Sebastian; Awiszus, Birgit

    2018-05-01

    Incremental forming processes (i.e., spinning) of sheet metal blanks into cylindrical cups are suitable for lower lot sizes. The produced cups were frequently used as preforms to produce workpieces in further forming steps with additional functions like profiled hollow parts [1]. The incremental forming process radial-rotation profile forming has been developed to enable the production of profiled hollow parts with low sheet thinning and good geometrical accuracy. The two principal forming steps are the production of the preform by rotational swing-folding [2] and the subsequent radial profiling of the hollow part in one clamping position. The rotational swing-folding process is based on a combination of conventional spinning and swing-folding. Therefore, a round blank rotates on a profiled mandrel and due to the swinging of a cylindrical forming tool, the blank is formed to a cup with low sheet thinning. In addition, thickening results at the edge of the blank and wrinkling occurs. However, the wrinkles are formed into the indentation of the profiled mandrel and can be reshaped as an advantage in the second process step, the radial profiling. Due to the rotation and continuous radial feed of a profiled forming tool to the profiled mandrel, the axial profile is formed in the second process step. Because of the minor relative movement in axial direction between tool and blank, low sheet thinning occurs. This is an advantage of the principle of the process.

  7. Basic deuteroexchange in complexes of transition metals with nitrogen-containing aromatic heterocycles

    Tupitsyn, I.F.

    1986-01-01

    A study was made of the kinetics of deuteroexchange in the methyl group in complexes of one metal [nickel(II)] with different methyl-substituted aromatic heterocycles and in isostructural complexes of one ligand (2-methylquinoline) with different central metal atoms (Mn 2+ , Ni 2+ , Cu 2+ , Zn 2+ ). The order in which the structures of the ligands influence the rate of deuteroexchange in the complexes does not correspond qualitatively with the order of increase in the rate of deuteroexchange in the noncoordinated ligands. The rate of deuteroexchange is only weakly influenced by change in the identity of the metal complex former. A deuteroexchange mechanism is proposed and discussed. A structure arising in the course of the exchange process with transfer of electron density from the heterocyclic ligand to the metal ion forms the transition state of the reaction

  8. Thiosemicarbazone complexes of the platinum metals. A story of ...

    Unknown

    Thiosemicarbazone complexes; platinum metals; variable coordination; ... carbonylic carbon via one or two intervening atoms, D,N,S tricoordination usually takes .... modelling studies show that in this coordination mode, the phenyl ring of the.

  9. 3d-METAL COMPLEXES WITH BARBITURIC ACID DERIVATIVES

    T. V. Koksharova

    2015-04-01

    Full Text Available The various aspects of the 3d-metal complexes with barbiturates and uric acid chemistry such as composition, structure, physicochemical properties, possible fields of application – have been illustrated in this review

  10. Structural systematics of some metal complexes with 4,5 ...

    study reveals that each metal(II) centre in the four complexes adopts distorted octahedral geometry with MN6 ... potassium permanganate (E Merck, India), potassium. 717 ... The final reaction solu- ..... ble in water, methanol, acetonitrile, etc.

  11. Sub-chronic toxicological studies of transition metal complexes of ...

    Md. Sharif Hasan

    2017-01-18

    Jan 18, 2017 ... naproxen showed more side effects than metal complexes which ..... Fosslein E. Adverse effects of nonsteroidal anti-inflammatory drugs on the ... association increases the anti-inflammatory and analgesic activity of ibuprofen.

  12. Synthesis and characterization of some metal complexes of a Schiff ...

    KEY WORDS: Metal complexes, Schiff base, Ninhydrin, α,L-Alanine, .... Buck Scientific Infrared Spectrophotometer Model 500 in the range of 4000 .... Assignments based on Nakamoto [35], ν - stretching vibration, δ - bending or deformation.

  13. Self-Assembly of Discrete Metal Complexes in Aqueous Solution via Block Copolypeptide Amphiphiles

    Timothy J. Deming

    2013-01-01

    Full Text Available The integration of discrete metal complexes has been attracting significant interest due to the potential of these materials for soft metal-metal interactions and supramolecular assembly. Additionally, block copolypeptide amphiphiles have been investigated concerning their capacity for self-assembly into structures such as nanoparticles, nanosheets and nanofibers. In this study, we combined these two concepts by investigating the self-assembly of discrete metal complexes in aqueous solution using block copolypeptides. Normally, discrete metal complexes such as [Au(CN2]−, when molecularly dispersed in water, cannot interact with one another. Our results demonstrated, however, that the addition of block copolypeptide amphiphiles such as K183L19 to [Au(CN2]− solutions induced one-dimensional integration of the discrete metal complex, resulting in photoluminescence originating from multinuclear complexes with metal-metal interactions. Transmission electron microscopy (TEM showed a fibrous nanostructure with lengths and widths of approximately 100 and 20 nm, respectively, which grew to form advanced nanoarchitectures, including those resembling the weave patterns of Waraji (traditional Japanese straw sandals. This concept of combining block copolypeptide amphiphiles with discrete coordination compounds allows the design of flexible and functional supramolecular coordination systems in water.

  14. Bovine Serum Albumin Metal Complexes for Mimic of SOD

    Key Lab. Eco-Environment-Related Polymer Materials of Ministry of Education, Key Lab. ... scaffold and the metal complex functioned as the catalytic active center. ... small molecule.22 It is found that the antioxidative ... and absence, respectively, of the measured compound. ... monitor the interaction of metal ions with BSA.

  15. Inkjet Printing of 3D Metallic Silver Complex Microstructures

    Wits, Wessel Willems; Sridhar, Ashok; Dimitrov, D.

    2010-01-01

    To broaden the scope of inkjet printing, this paper focuses on printing of an organic silver complex ink on glass substrates towards the fabrication of metallic 3D microstructures. The droplet formation sequence of the inkjet printer is optimised to print continuous layers of metal. A brief

  16. Revisited: the conception of lability of metal complexes

    Leeuwen, van H.P.

    2001-01-01

    Starting from the original reaction layer concept, the voltammetric properties of electroinactive metal complexes are critically reviewed in terms of their finite rates of dissociation into electroactive free metal ions. The limiting conditions for the reaction layer-based flux expressions are made

  17. Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms

    Steinberg, Simon; Zimmermann, Sina; Brühmann, Matthias; Meyer, Eva; Rustige, Christian; Wolberg, Marike; Daub, Kathrin; Bell, Thomas; Meyer, Gerd, E-mail: gerd.meyer@uni-koeln.de

    2014-11-15

    Comproportionation reactions of rare-earth metal trihalides (RX{sub 3}) with the respective rare-earth metals (R) and transition metals (T) led to the formation of 22 oligomeric R cluster halides encapsulating T, in 19 cases for the first time. The structures of these compounds were determined by single-crystal X-ray diffraction and are composed of trimers ((T{sub 3}R{sub 11})X{sub 15}-type, P6{sub 3}/m), tetramers ((T{sub 4}R{sub 16})X{sub 28}(R{sub 4}) (P-43m), (T{sub 4}R{sub 16})X{sub 20} (P4{sub 2}/nnm), (T{sub 4}R{sub 16})X{sub 24}(RX{sub 3}){sub 4} (I4{sub 1}/a) and (T{sub 4}R{sub 16})X{sub 23} (C2/m) types of structure) and pentamers ((Ru{sub 5}La{sub 14}){sub 2}Br{sub 39}, Cc) of (TR{sub r}){sub n} (n=2–5) clusters. These oligomers are further enveloped by inner (X{sup i}) as well as outer (X{sup a}) halido ligands, which possess diverse functionalities and interconnect like oligomers through i–i, i–a and/or a–i bridges. The general features of the crystal structures for these new compounds are discussed and compared to literature entries as well as different structure types with oligomeric T centered R clusters. Dimers and tetramers originating from the aggregation of (TR{sub 6}) octahedra via common edges are more frequent than trimers and pentamers, in which the (TR{sub r}) clusters share common faces. - Graphical abstract: Rare earth-metal cluster complexes with endohedral transition metal atoms (TR{sub 6}) may connect via common edges or faces to form dimers, trimers, tetramers and pentamers of which the tetramers are the most prolific. Packing effects and electron counts play an important role. - Highlights: • Rare-earth metal cluster complexes encapsulate transition metal atoms. • Oligomers are built via connection of octahedral clusters via common edges or faces. • Dimers through pentamers with closed structures are known. • Tetramers including a tetrahedron of endohedral atoms are the most prolific.

  18. Compartmentation and complexation of metals in hyperaccumulator plants

    Barbara eLeitenmaier

    2013-09-01

    Full Text Available Hyperaccumulators are being intensely investigated. They are not only interesting in scientific context due to their strange behaviour in terms of dealing with high concentrations of metals, but also because of their use in phytoremediation and phytomining, for which understanding the mechanisms of hyperaccumulation is crucial. Hyperaccumulators naturally use metal accumulation as a defence against herbivores and pathogens, and therefore deal with accumulated metals in very specific ways of complexation and compartmentation, different from non-hyperaccumulator plants and also non-hyperaccumulated metals. For example, in contrast to non-hyperaccumulators, in hyperaccumulators even the classical phytochelatin-inducing metal, cadmium, is predominantly not bound by such sulfur ligands, but only by weak oxygen ligands. This applies to all hyperaccumulated metals investigated so far, as well as hyperaccumulation of the metalloid arsenic. Stronger ligands, as they have been shown to complex metals in non-hyperaccumulators, are in hyperaccumulators used for transient binding during transport to the storage sites. This confirmed that enhanced active metal transport, and not metal complexation, is the key mechanism of hyperaccumulation. Hyperaccumulators tolerate the high amount of accumulated heavy metals by sequestering them into vacuoles, usually in large storage cells of the epidermis. This is mediated by strongly elevated expression of specific transport proteins in various tissues from metal uptake in the shoots up to the storage sites in the leaf epidermis. However, this mechanism seems to be very metal specific. Non-hyperaccumulated metals in hyperaccumulators seem to be dealt with like in non-hyperaccumulator plants, i.e. detoxified by binding to strong ligands such as metallothioneins.

  19. Solubility of hydrogen isotopes in stressed hydride-forming metals

    Coleman, C.E.; Ambler, J.F.R.

    1983-01-01

    Components made from hydride-forming metals can be brittle when particles of hydride are present. The solid solubility limit of hydrogen in these metals needs to be known so that fracture resistance can be properly assessed. Stress affects the solubility of hydrogen in metals. As hydrogen dissolves the metal volume increases, an applied hydrostatic tensile stress supplies work to increase the solubility. Precipitation of hydrides increases the volume further. A hydrostatic tensile stress promotes the formation of hydrides and tends to reduce the terminal solubility. For materials containing hydrogen in solution in equilibrium with hydrides, the effect of stress on the terminal solubility is given. Hydrogen migrates up tensile stress gradients because of the effect of stress on the solubility and solubility limit. Consequently, hydrogen concentrates at flaws. When hydrides are present in the metal matrix, those remote from the flaw tip will preferentially dissolve in favor of those precipitated at the flaw. If the stress is large enough, at some critical condition the hydrides at the flaw will crack. This is delayed hydrogen cracking. Notched and fatigue-cracked cantilever beam specimens (6) (38 x 4 x 3 mm) were machined from the circumferential direction of several cold-worked Zr-2.5 at. % Nb pressure tubes. The chemical compositions had the ranges (in atomic %) Nb - 2.5 to 2.7; O - 0.58 to 0.71; H - 0.018 to 0.18. The effect of test temperature is for a specimen containing 0.13 at. % protium and 0.29 at .% deuterium. Between 505 K and 530 K was less than 1 hr, between 530 K and 537 K it increased to 25.8 h, while at 538 K no cracking was observed up to the 54 h

  20. High capacity hydrogen absorption in transition-metal ethylene complexes: consequences of nanoclustering

    Phillips, A B; Shivaram, B S

    2009-01-01

    We have recently shown that organo-metallic complexes formed by laser ablating transition metals in ethylene are high hydrogen absorbers at room temperature (Phillips and Shivaram 2008 Phys. Rev. Lett. 100 105505). Here we show that the absorption percentage depends strongly on the ethylene pressure. High ethylene pressures (>100 mTorr) result in a lowered hydrogen uptake. Transmission electron microscopy measurements reveal that while low pressure ablations result in metal atoms dispersed uniformly on a near atomic scale, high pressure ones yield distinct nanoparticles with electron energy-loss spectroscopy demonstrating that the metal atoms are confined solely to the nanoparticles.

  1. Potentiometric study of complexes formed between (s)-&alpha

    isoxazole ring. The first complex [CuHL], which is fully formed by pH 4 is proposed to be with {N,O} bonding which results in the formation of a stable five membered chelate ring. The [CuL] species has some enhanced stability which suggest ...

  2. Spatial structure of transition metal complexes in solution determined by EXAFS spectroscopy

    Erenburg, S.B. E-mail: simon@che.nsk.su; Bausk, N.V.; Zemskova, S.M.; Mazalov, L.N

    2000-06-21

    CdK EXAFS, ZnK and CuK EXAFS and XANES spectra were measured for solutions of cadmium, zinc and copper dialkyldithiocarbamates in organic solvents with varying donating abilities: tributylphosphine, methylene chloride, benzene, dibutylsulfide, pyridine, dimethylsulfoxide and for some model compounds. The parameters of the local surroundings of the Cd, Zn and Cu atoms for complex forms in solutions were determined using EXAFS spectroscopy. Spatial structure models of the complex forms in a metal chelate - nonaqueous solvent system are suggested.

  3. Spatial structure of transition metal complexes in solution determined by EXAFS spectroscopy

    Erenburg, S.B.; Bausk, N.V.; Zemskova, S.M.; Mazalov, L.N.

    2000-01-01

    CdK EXAFS, ZnK and CuK EXAFS and XANES spectra were measured for solutions of cadmium, zinc and copper dialkyldithiocarbamates in organic solvents with varying donating abilities: tributylphosphine, methylene chloride, benzene, dibutylsulfide, pyridine, dimethylsulfoxide and for some model compounds. The parameters of the local surroundings of the Cd, Zn and Cu atoms for complex forms in solutions were determined using EXAFS spectroscopy. Spatial structure models of the complex forms in a metal chelate - nonaqueous solvent system are suggested

  4. Tool-life prediction under multi-cycle loading during metal forming: a feasibility study

    Hu Yiran

    2015-01-01

    Full Text Available In the present research, the friction and wear behaviour of a hard coating were studied by using ball-on-disc tests to simulate the wear process of the coated tools for sheet metal forming process. The evolution of the friction coefficient followed a typical dual-plateau pattern, i.e. at the initial stage of sliding, the friction coefficient was relatively low, followed by a sharp increase due to the breakdown of the coatings after a certain number of cyclic dynamic loadings. This phenomenon was caused by the interactive response between the friction and wear from a coating tribo-system, which is often neglected by metal forming researchers, and constant friction coefficient values are normally used in the finite element (FE simulations to represent the complex tribological nature at the contact interfaces. Meanwhile, most of the current FE simulations consider single-cycle loading processes, whereas many metal-forming operations are conducted in a form of multi-cycle loading. Therefore, a novel friction/wear interactive friction model was developed to, simultaneously, characterise the evolutions of friction coefficient and the remaining thickness of the coating layer, to enable the wear life of coated tooling to be predicted. The friction model was then implemented into the FE simulation of a sheet metal forming process for feasibility study.

  5. 4. Seminar on efficient metal forming and machining: papers

    1982-01-01

    The 4th seminar on efficient metal forming and machining was held at the CSIR conference centre in Pretoria on 16 November 1982. This conference basically discussed the forming, fabrication and machining of metals which included the different methods used as well as new developments on tools manufacturing and their applications. The topics that were discussed cover subjects such as the creep feed grinding, thermal properties of coating materials and their effect on the efficiency of coated cutting tools, economic rough and finish milling, the design and application of high speed steel cutting tools, aluminium extrusion, the manufacturing and finishing of extrusion dies, broaching techniques, cold forming in the fastener industry, finishing methods for spiral, bevel and hypoid gears, laser cutting, press tool design, and productivity in the forging industry. Another topic that were discussed, is the current status of diamond and cubic boron nitride composites, their synthesis and roll in the production of a new range of ultra hard ceramic-type materials

  6. Application of Six Sigma Robust Optimization in Sheet Metal Forming

    Li, Y.Q.; Cui, Z.S.; Ruan, X.Y.; Zhang, D.J.

    2005-01-01

    Numerical simulation technology and optimization method have been applied in sheet metal forming process to improve design quality and shorten design cycle. While the existence of fluctuation in design variables or operation condition has great influence on the quality. In addition to that, iterative solution in numerical simulation and optimization usually take huge computational time or endure expensive experiment cost In order to eliminate effect of perturbations in design and improve design efficiency, a CAE-based six sigma robust design method is developed in this paper. In the six sigma procedure for sheet metal forming, statistical technology and dual response surface approximate model as well as algorithm of 'Design for Six Sigma (DFSS)' are integrated together to perform reliability optimization and robust improvement. A deep drawing process of a rectangular cup is taken as an example to illustrate the method. The optimization solutions show that the proposed optimization procedure not only improves significantly the reliability and robustness of the forming quality, but also increases optimization efficiency with approximate model

  7. EXPERIMENTAL TESTING OF DRAW—BEAD RESTRAINING FORCE IN SHEET METAL FORMING

    J.H.Yang; J.Chen; 等

    2003-01-01

    Due to complexities of draw-bead restraining force calculated according to theory and depending on sheet metal forming properties experiment testing system,a simplified method to calculate draw-bead restraining force is put forward by experimental method in cup-shaped drawing process.The experimental results were compared with numer-ical results and proved agreement.It shows the method is effective.

  8. In-situ ductile metal/bulk metallic glass matrix composites formed by chemical partitioning

    Kim, Choong Paul; Hays, Charles C.; Johnson, William L.

    2004-03-23

    A composite metal object comprises ductile crystalline metal particles in an amorphous metal matrix. An alloy is heated above its liquidus temperature. Upon cooling from the high temperature melt, the alloy chemically partitions, forming dendrites in the melt. Upon cooling the remaining liquid below the glass transition temperature it freezes to the amorphous state, producing a two-phase microstructure containing crystalline particles in an amorphous metal matrix. The ductile metal particles have a size in the range of from 0.1 to 15 micrometers and spacing in the range of from 0.1 to 20 micrometers. Preferably, the particle size is in the range of from 0.5 to 8 micrometers and spacing is in the range of from 1 to 10 micrometers. The volume proportion of particles is in the range of from 5 to 50% and preferably 15 to 35%. Differential cooling can produce oriented dendrites of ductile metal phase in an amorphous matrix. Examples are given in the Zr--Ti--Cu--Ni--Be alloy bulk glass forming system with added niobium.

  9. Multi-objective optimization under uncertainty for sheet metal forming

    Lafon Pascal

    2016-01-01

    Full Text Available Aleatory uncertainties in material properties, blank thickness and friction condition are inherent and irreducible variabilities in sheet metal forming. Optimal design configurations, which are obtained by conventional design optimization methods, are not always able to meet the desired targets due to the effect of uncertainties. This paper proposes a multi-objective robust design optimization that aims to tackle this problem. Results obtained on a U shape draw bending benchmark show that spring-back effect can be controlled by optimizing process parameters.

  10. Features of proteolytic properties of tetraphenylporphyrin complex with lanthanide group metals

    Tobolkina, Elena A.; Skripnikova, Tatiana A.; Starikova, Anna A.; Shumilova, Galina I.; Pendin, Andrey A.

    2018-01-01

    Demetallation of metalloporphyrin molecules is one of the essential degradation reactions in photosynthesis. The effect of metalloporphyrin nature on removal of central metals from tetraphenylporphyrin complexes based on lanthanide group metals (Dy, Er, Lu, Ho) has been studied. pH values, at which the metal ions leave the metalloporphyrin complex were established using two-phase spectrophotometric titration with potentiometric pH-control. The pH values decrease with the increase of atomic numbers of lanthanide groups, as well as with increase of 4f-electrons. The reaction of an extra ligand exchange for the hydroxide ion was studied. For Dy-, Er- and Ho-tetraphenylporphyrin complexes one particle of extra ligand coordinates with one porphyrin complex. A complex with dimeric particles can be formed for the system of Lu-tetraphenylporphyrin. Constants of the ion exchange reactions were calculated.

  11. Humic substances in natural waters and their complexation with trace metals and radionuclides: a review

    Boggs, S. Jr.; Livermore, D.; Seitz, M.G.

    1985-07-01

    Dissolved humic substances (humic and fulvic acids) occur in surface waters and groundwaters in concentrations ranging from less than 1 mg(C)/L to more than 100 mg(C)/L. Humic substances are strong complexing agents for many trace metals in the environment and are also capable of forming stable soluble complexes or chelates with radionuclides. Concentrations of humic materials as low as 1 mg(C)/L can produce a detectable increase in the mobility of some actinide elements by forming soluble complexes that inhibit sorption of the radionuclides onto rock materials. The stability of trace metal- or radionuclide-organic complexes is commonly measured by an empirically determined conditional stability constant (K'), which is based on the ratio of complexed metal (radionuclide) in solution to the product concentration of uncomplexed metal and humic complexant. Larger values of stability constants indicate greater complex stability. The stability of radionuclide-organic complexes is affected both by concentration variables and envionmental factors. In general, complexing is favored by increased of radionuclide, increased pH, and decreased ionic strength. Actinide elements are generally most soluble in their higher oxidation states. Radionuclides can also form stable, insoluble complexes with humic materials that tend to reduce radionuclide mobility. These insoluble complexes may be radionuclide-humate colloids that subsequently precipitate from solution, or complexes of radionuclides and humic substances that sorb to clay minerals or other soil particulates strongly enough to immobilize the radionuclides. Colloid formation appears to be favored by increased radionuclide concentration and lowered pH; however, the conditions that favor formation of insoluble complexes that sorb to particulates are still poorly understood. 129 refs., 25 figs., 19 tabs

  12. Strategic directions of personnel potential forming of a building complex

    Simonova Marina

    2016-01-01

    Full Text Available The analysis of directions of strategic approach forming of labor potential management of a building complex is carried out in this paper. On the basis of this analysis the system of actions for strategy forming divided into consecutive stages is offered. The development of the personnel forecast is a strategic planning basis. One of personnel forecast variants is the correlation of needs estimates in personnel of a building complex with available allowances. On the basis of the personnel forecast strategic analysis it is possible to compose working programs for the stated goals of implementation. Operational assessment of personnel requirements of a building complex is proved to be combined with strategic objectives. Some assessment approaches to qualitative and quantitative need for specialists of a building complex are offered. The fact that high-quality labor power supply system of a building complex with should be based on industry development forecast and increase in construction products competitiveness is revealed in the article. Strategic management priority will allow to react immediately to the current situation changes, to introduce amendments both into tactical, and operational management.

  13. Variations in Canonical Star-Forming Laws at Low Metallicity

    Monkiewicz, Jacqueline; Bowman, Judd D.; Scowen, Paul

    2018-01-01

    Empirically-determined star formation relations link observed galaxy luminosities to extrapolated star formation rates at almost every observable wavelength range. These laws are a cornerstone of extragalactic astronomy, and will be critically important for interpreting upcoming observations of early high-redshift protogalaxies with JWST and WFIRST. There are indications at a variety of wavelengths that these canonical relations may become unreliable at the lowest metallicities observed. This potentially complicates interpretation of the earliest protogalaxies, which are expected to be pristine and largely unenriched by stellar nucleosynthesis. Using a sample of 15 local dwarf galaxies with 12+[O/H] dwarf galaxies 1 Zw 18 and SBS 0335-052E suggest that the far-IR/radio relation probably deviates at low metallicities, but the low luminosity end of the relation is not well sampled. The upgraded Jansky Very Large Array has the sensitivity to fill in this gap. I have obtained 45 hours of L- and C-band continuum data of my dwarf galaxy sample. I present radio continuum imaging of an initial sub-sample of Local Group dwarfs, some of which have never before been detected in radio continuum. The H-alpha/UV relationship is likewise known to become unreliable for dwarf galaxies, though this has been attributed to dwarf galaxy "bursty-ness" rather than metallicity effects. I have conducted a parallel survey of emission line imaging to study the underlying astrophysics of the H-alpha/UV relation. Using Balmer decrement imaging, I map out the pixel-to-pixel dust distribution and geometry within the nearest galaxies in my sample. I compare this to GALEX UV imaging. I discuss implications for UV escape fraction, and present initial results of the canonical star-forming relations at low galaxy luminosity and metallicity. THIS IS A POSTER AND WILL BE LOCATED IN THE AAS BOOTH.

  14. Metal plasmon enhanced europium complex luminescence

    Liu Feng; Aldea, Gabriela; Nunzi, Jean-Michel

    2010-01-01

    The plasmon enhanced luminescence of a rare-earth complex Tris(6, 6, 7, 7, 8, 8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionato) europium (Eu(fod) 3 ) was investigated. A polyvinyl alcohol (PVA) thin film was successfully adopted as a spacer to separate the Eu complex from the silver island film (SIF), and five-fold enhancement of the radiative decay rate of the Eu complex on SIF was demonstrated based on the luminescence intensity and lifetime measurement. Investigation of the distance dependent luminescence indicates that 7 nm is an optimal distance for SIF enhanced Eu luminescence. Plasmon enhanced rare-earth luminescence based on an organic film spacer would find potential applications in plasmon enhanced organic light emitting diode (OLED) devices.

  15. Mixed metal complexes of isoniazid and ascorbic acid: chelation ...

    Novel mixed complexes of isoniazid and ascorbic acid have been synthesized and characterized using infrared, electronic absorption data, elemental analysis, molar conductivity, melting point, thin layer chromatography and solubility. The metal ions involved in the complex formation are Cu2+, Zn2+ and Cd2+. The melting ...

  16. Metal complex catalysis in the synthesis of organoaluminium compounds

    Dzhemilev, Usein M; Ibragimov, Askhat G

    2000-01-01

    The published data on the synthesis of organoaluminium compounds involving metal complex catalysts are generalised and systematised. Hydro-, carbo- and cycloalumination reactions of alkenes, conjugated dienes and alkynes catalysed by Ti and Zr complexes are considered in detail. The use of organoaluminium reagents in organic synthesis and novel reactions involving these compounds are discussed. The bibliography includes 240 references.

  17. An Experiment on Isomerism in Metal-Amino Acid Complexes.

    Harrison, R. Graeme; Nolan, Kevin B.

    1982-01-01

    Background information, laboratory procedures, and discussion of results are provided for syntheses of cobalt (III) complexes, I-III, illustrating three possible bonding modes of glycine to a metal ion (the complex cations II and III being linkage/geometric isomers). Includes spectrophotometric and potentiometric methods to distinguish among the…

  18. Preconcentration of metallic elements by complexation with ammonium pyrrolidine dithiocarbamate (APDC) for atomic absorption analysis

    Santos Coelho, Ricardo dos; Dantas, Elizabeth S.K.

    1997-01-01

    Ammonium pyrrolidine dithiocarbamate (APDC) forms stable chelates with many metals being therefore, used in systems of preconcentration for determination of heavy metals in water. In this work, the metals were complexed with APDC and extracted with methyl isobutyl ketone (MIBK). The results showed that the studied metals (Co, Cu, Fe, Ni, Pb, Cr and Cd), in the range of 2 to 5 μg, in 100 ml of sample, were quantitatively extracted in only one stage using 10 ml of MIBK and 5 ml of 4% APDC. The pH must be between 4 and 5. The complexes stability was also studied. The proposed method can be applied to pre concentrate heavy metals in natural waters. (author). 4 refs., 1 fig., 3 tabs

  19. N-heterocyclic carbene metal complexes as bio-organometallic antimicrobial and anticancer drugs.

    Patil, Siddappa A; Patil, Shivaputra A; Patil, Renukadevi; Keri, Rangappa S; Budagumpi, Srinivasa; Balakrishna, Geetha R; Tacke, Matthias

    2015-01-01

    Late transition metal complexes that bear N-heterocyclic carbene (NHC) ligands have seen a speedy growth in their use as both, metal-based drug candidates and potentially active homogeneous catalysts in a plethora of C-C and C-N bond forming reactions. This review article focuses on the recent developments and advances in preparation and characterization of NHC-metal complexes (metal: silver, gold, copper, palladium, nickel and ruthenium) and their biomedical applications. Their design, syntheses and characterization have been reviewed and correlated to their antimicrobial and anticancer efficacies. All these initial discoveries help validate the great potential of NHC-metal derivatives as a class of effective antimicrobial and anticancer agents.

  20. Metallic nanomaterials formed by exerting large plastic strains

    Richert, M; Richert, J.; Zasadzinski, J.; Hawrylkiewicz, S.

    2002-01-01

    The investigations included pure Al and Cu single crystals, AlMg5 alloy and AlCuZr alloy have been presented. The materials were deformed by the cyclic extrusion compression method (CEC) within the range of true strains φ = 0.4-59.8 (1 to 67 deformation cycles by the CEC method). In all examined materials a strong tendency to form banded was observed. Within the range of very large plastic strains there was observed intensive rebuilding of the banded microstructure into subgrains, at first of rhombic shape, and next into equiaxial subgrains. A characteristic feature of the newly formed subgrains, not encountered in the range of conventional deformations, was the occurrence of large misorientation angles between the newly formed subgrains. The proportion of large misorientation angles in the microstructure varied, and it increased with increasing deformation. Reduction of the recovery process in AlMg5 and AlCuZr alloys preserved the growth of the newly formed nanograins, favoring the retaining of the nanomeric dimensions. This results show that there is the effective possibility of production of metallic nanomaterials by exerting of very large nonconventional plastic strains. (author)

  1. DFT study on metal-mediated uracil base pair complexes

    Ayhan Üngördü

    2017-11-01

    Full Text Available The most stable of metal-mediated uracil base pair complexes were determined. Method was used density functional theory, B3LYP. The calculations of systems containing C, H, N, O were described by 6-311++G(d,p and cc-PVTZ basis sets and LANL2DZ and SDD basis sets was used for transition metals. Then Egap values of complexes were calculated and the electrical conductivity of the complexes for single nanowires was studied by band theory. Metal-mediated uracil base pair complexes which will be used as conductive wires in nanotechnology were predicted. In nanoworld, this study is expected to show a way for practical applications.

  2. Synchronization of complex chaotic systems in series expansion form

    Ge Zhengming; Yang Chenghsiung

    2007-01-01

    This paper studies the synchronization of complex chaotic systems in series expansion form by Lyapunov asymptotical stability theorem. A sufficient condition is given for the asymptotical stability of an error dynamics, and is applied to guiding the design of the secure communication. Finally, numerical results are studied for the Quantum-CNN oscillators synchronizing with unidirectional/bidirectional linear coupling to show the effectiveness of the proposed synchronization strategy

  3. Solvation Effect on Complexation of Alkali Metal Cations by a Calix[4]arene Ketone Derivative.

    Požar, Josip; Nikšić-Franjić, Ivana; Cvetnić, Marija; Leko, Katarina; Cindro, Nikola; Pičuljan, Katarina; Borilović, Ivana; Frkanec, Leo; Tomišić, Vladislav

    2017-09-14

    The medium effect on the complexation of alkali metal cations with a calix[4]arene ketone derivative (L) was systematically examined in methanol, ethanol, N-methylformamide, N,N-dimethylformamide, dimethyl sulfoxide, and acetonitrile. In all solvents the binding of Na + cation by L was rather efficient, whereas the complexation of other alkali metal cations was observed only in methanol and acetonitrile. Complexation reactions were enthalpically controlled, while ligand dissolution was endothermic in all cases. A notable influence of the solvent on NaL + complex stability could be mainly attributed to the differences in complexation entropies. The higher NaL + stability in comparison to complexes with other alkali metal cations in acetonitrile was predominantly due to a more favorable complexation enthalpy. The 1 H NMR investigations revealed a relatively low affinity of the calixarene sodium complex for inclusion of the solvent molecule in the calixarene hydrophobic cavity, with the exception of acetonitrile. Differences in complex stabilities in the explored solvents, apart from N,N-dimethylformamide and acetonitrile, could be mostly explained by taking into account solely the cation and complex solvation. A considerable solvent effect on the complexation equilibria was proven to be due to an interesting interplay between the transfer enthalpies and entropies of the reactants and the complexes formed.

  4. Surface Structures Formed by a Copper(II Complex of Alkyl-Derivatized Indigo

    Akinori Honda

    2016-10-01

    Full Text Available Assembled structures of dyes have great influence on their coloring function. For example, metal ions added in the dyeing process are known to prevent fading of color. Thus, we have investigated the influence of an addition of copper(II ion on the surface structure of alkyl-derivatized indigo. Scanning tunneling microscope (STM analysis revealed that the copper(II complexes of indigo formed orderly lamellar structures on a HOPG substrate. These lamellar structures of the complexes are found to be more stable than those of alkyl-derivatized indigos alone. Furthermore, 2D chirality was observed.

  5. Preparation and Characterization of Double Metal Cyanide Complex Catalysts

    Weilin Guo

    2003-01-01

    Full Text Available A series of double metal cyanide (DMC complex catalysts were prepared in two different methods by using ß-cyclodextrin, PEG-1000 and Tween-60 as an additional complex ligands respectively. It was showed that a mixture of crystalline and amorphous DMC was synthesized by using traditional method in which the additional complex ligand was added after the precipitation of DMC. Amorphous and dispersed DMC with higher activity could be obtained when the additional complex ligand was added in the reactant solution before reaction. The effect of additional complex ligand and preparation method on the crystalline state and catalytic property of DMC were also investigated.

  6. Preparation of Palladium-Impregnated Ceria by Metal Complex Decomposition for Methane Steam Reforming Catalysis

    Worawat Wattanathana

    2017-01-01

    Full Text Available Palladium-impregnated ceria materials were successfully prepared via an integrated procedure between a metal complex decomposition method and a microwave-assisted wetness impregnation. Firstly, ceria (CeO2 powders were synthesized by thermal decomposition of cerium(III complexes prepared by using cerium(III nitrate or cerium(III chloride as a metal source to form a metal complex precursor with triethanolamine or benzoxazine dimer as an organic ligand. Palladium(II nitrate was consequently introduced to the preformed ceria materials using wetness impregnation while applying microwave irradiation to assist dispersion of the dopant. The palladium-impregnated ceria materials were obtained by calcination under reduced atmosphere of 10% H2 in He stream at 700°C for 2 h. Characterization of the palladium-impregnated ceria materials reveals the influences of the metal complex precursors on the properties of the obtained materials. Interestingly, the palladium-impregnated ceria prepared from the cerium(III-benzoxazine dimer complex revealed significantly higher BET specific surface area and higher content of the more active Pdδ+ (δ > 2 species than the materials prepared from cerium(III-triethanolamine complexes. Consequently, it exhibited the most efficient catalytic activity in the methane steam reforming reaction. By optimization of the metal complex precursors, characteristics of the obtained palladium-impregnated ceria catalysts can be modified and hence influence the catalytic activity.

  7. Computation of 3D form factors in complex environments

    Coulon, N.

    1989-01-01

    The calculation of radiant interchange among opaque surfaces in a complex environment poses the general problem of determining the visible and hidden parts of the environment. In many thermal engineering applications, surfaces are separated by radiatively non-participating media and may be idealized as diffuse emitters and reflectors. Consenquently the net radiant energy fluxes are intimately related to purely geometrical quantities called form factors, that take into account hidden parts: the problem is reduced to the form factor evaluation. This paper presents the method developed for the computation of 3D form factors in the finite-element module of the system TRIO, which is a general computer code for thermal and fluid flow analysis. The method is derived from an algorithm devised for synthetic image generation. A comparison is performed with the standard contour integration method also implemented and suited to convex geometries. Several illustrative examples of finite-element thermal calculations in radiating enclosures are given

  8. Metal Complexes for Organic Optoelectronic Applications

    Huang, Liang

    Organic optoelectronic devices have drawn extensive attention by over the past two decades. Two major applications for Organic optoelectronic devices are efficient organic photovoltaic devices(OPV) and organic light emitting diodes (OLED). Organic Solar cell has been proven to be compatible with the low cost, large area bulk processing technology and processed high absorption efficiencies compared to inorganic solar cells. Organic light emitting diodes are a promising approach for display and solid state lighting applications. To improve the efficiency, stability, and materials variety for organic optoelectronic devices, several emissive materials, absorber-type materials, and charge transporting materials were developed and employed in various device settings. Optical, electrical, and photophysical studies of the organic materials and their corresponding devices were thoroughly carried out. In this thesis, Chapter 1 provides an introduction to the background knowledge of OPV and OLED research fields presented. Chapter 2 discusses new porphyrin derivatives- azatetrabenzylporphyrins for OPV and near infrared OLED applications. A modified synthetic method is utilized to increase the reaction yield of the azatetrabenzylporphyrin materials and their photophysical properties, electrochemical properties are studied. OPV devices are also fabricated using Zinc azatetrabenzylporphyrin as donor materials. Pt(II) azatetrabenzylporphyrin were also synthesized and used in near infra-red OLED to achieve an emission over 800 nm with reasonable external quantum efficiencies. Chapter 3, discusses the synthesis, characterization, and device evaluation of a series of tetradentate platinum and palladium complexesfor single doped white OLED applications and RGB white OLED applications. Devices employing some of the developed emitters demonstrated impressively high external quantum efficiencies within the range of 22%-27% for various emitter concentrations. And the palladium complex, i

  9. Fine Coining of Bulk Metal Formed Parts in Digital Environment

    Pepelnjak, T.; Kuzman, K.; Krusic, V.

    2007-01-01

    At present the production of bulk metal formed parts in the automotive industry must increasingly fulfil demands for narrow tolerance fields. The final goal of the million parts production series is oriented towards zero defect production. This is possible by achieving production tolerances which are even tighter than the prescribed ones. Different approaches are used to meet this demanding objective affected by many process parameters. Fine coining as a final forming operation is one of the processes which enables the production of good manufacturing tolerances and high process stability. The paper presents the analyses of the production of the inner race and a digital evaluation of manufacturing tolerances caused by different material parameters of the workpiece. Digital optimisation of the fine coining with FEM simulations was performed in two phases. Firstly, fine coining of the inner racer in a digital environment was comparatively analysed with the experimental work in order to verify the accuracy and reliability of digitally calculated data. Secondly, based on the geometrical data of a digitally fine coined part, tool redesign was proposed in order to tighten production tolerances and increase the process stability of the near-net-shaped cold formed part

  10. Advanced Gradient Based Optimization Techniques Applied on Sheet Metal Forming

    Endelt, Benny; Nielsen, Karl Brian

    2005-01-01

    The computational-costs for finite element simulations of general sheet metal forming processes are considerable, especially measured in time. In combination with optimization, the performance of the optimization algorithm is crucial for the overall performance of the system, i.e. the optimization algorithm should gain as much information about the system in each iteration as possible. Least-square formulation of the object function is widely applied for solution of inverse problems, due to the superior performance of this formulation.In this work focus will be on small problems which are defined as problems with less than 1000 design parameters; as the majority of real life optimization and inverse problems, represented in literature, can be characterized as small problems, typically with less than 20 design parameters.We will show that the least square formulation is well suited for two classes of inverse problems; identification of constitutive parameters and process optimization.The scalability and robustness of the approach are illustrated through a number of process optimizations and inverse material characterization problems; tube hydro forming, two step hydro forming, flexible aluminum tubes, inverse identification of material parameters

  11. Towards Industrial Application of Damage Models for Sheet Metal Forming

    Doig, M.; Roll, K.

    2011-05-01

    Due to global warming and financial situation the demand to reduce the CO2-emission and the production costs leads to the permanent development of new materials. In the automotive industry the occupant safety is an additional condition. Bringing these arguments together the preferable approach for lightweight design of car components, especially for body-in-white, is the use of modern steels. Such steel grades, also called advanced high strength steels (AHSS), exhibit a high strength as well as a high formability. Not only their material behavior but also the damage behavior of AHSS is different compared to the performances of standard steels. Conventional methods for the damage prediction in the industry like the forming limit curve (FLC) are not reliable for AHSS. Physically based damage models are often used in crash and bulk forming simulations. The still open question is the industrial application of these models for sheet metal forming. This paper evaluates the Gurson-Tvergaard-Needleman (GTN) model and the model of Lemaitre within commercial codes with a goal of industrial application.

  12. Porous silicon based anode material formed using metal reduction

    Anguchamy, Yogesh Kumar; Masarapu, Charan; Deng, Haixia; Han, Yongbong; Venkatachalam, Subramanian; Kumar, Sujeet; Lopez, Herman A.

    2015-09-22

    A porous silicon based material comprising porous crystalline elemental silicon formed by reducing silicon dioxide with a reducing metal in a heating process followed by acid etching is used to construct negative electrode used in lithium ion batteries. Gradual temperature heating ramp(s) with optional temperature steps can be used to perform the heating process. The porous silicon formed has a high surface area from about 10 m.sup.2/g to about 200 m.sup.2/g and is substantially free of carbon. The negative electrode formed can have a discharge specific capacity of at least 1800 mAh/g at rate of C/3 discharged from 1.5V to 0.005V against lithium with in some embodiments loading levels ranging from about 1.4 mg/cm.sup.2 to about 3.5 mg/cm.sup.2. In some embodiments, the porous silicon can be coated with a carbon coating or blended with carbon nanofibers or other conductive carbon material.

  13. Surface modification by metal ion implantation forming metallic nanoparticles in an insulating matrix

    Salvadori, M.C.; Teixeira, F.S.; Sgubin, L.G.; Cattani, M.; Brown, I.G.

    2014-01-01

    Highlights: • Metal nanoparticles can be produced through metallic ion implantation in insulating substrate, where the implanted metal self-assembles into nanoparticles. • The nanoparticles nucleate near the maximum of the implantation depth profile, that can be estimated by computer simulation using the TRIDYN. • Nanocomposites, obtained by this way, can be produced in different insulator materials. More specifically we have studied Au/PMMA (polymethylmethacrylate), Pt/PMMA, Ti/alumina and Au/alumina systems. • The nanocomposites were characterized by measuring the resistivity of the composite layer as function of the dose implanted, reaching the percolation threshold. • Excellent agreement was found between the experimental results and the predictions of the theory. - Abstract: There is special interest in the incorporation of metallic nanoparticles in a surrounding dielectric matrix for obtaining composites with desirable characteristics such as for surface plasmon resonance, which can be used in photonics and sensing, and controlled surface electrical conductivity. We have investigated nanocomposites produced by metal ion implantation into insulating substrates, where the implanted metal self-assembles into nanoparticles. The nanoparticles nucleate near the maximum of the implantation depth profile (projected range), which can be estimated by computer simulation using the TRIDYN code. TRIDYN is a Monte Carlo simulation program based on the TRIM (Transport and Range of Ions in Matter) code that takes into account compositional changes in the substrate due to two factors: previously implanted dopant atoms, and sputtering of the substrate surface. Our study show that the nanoparticles form a bidimentional array buried a few nanometers below the substrate surface. We have studied Au/PMMA (polymethylmethacrylate), Pt/PMMA, Ti/alumina and Au/alumina systems. Transmission electron microscopy of the implanted samples show that metallic nanoparticles form in

  14. Compressive deformation of in situ formed bulk metallic glass composites

    Clausen, B. [Lujan Neutron Science Center, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Lee, S.Y. [Department of Materials Science and Engineering, Iowa State University, Ames, IA 50011 (United States); Ustuendag, E. [Department of Materials Science and Engineering, Iowa State University, Ames, IA 50011 (United States)]. E-mail: ustundag@iastate.edu; Kim, C.P. [Liquidmetal Technologies, Lake Forest, CA 92630 (United States); Brown, D.W. [Materials Science and Technology Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Bourke, M.A.M. [Materials Science and Technology Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)

    2006-02-15

    A bulk metallic glass matrix composite with dendc second phase precipitates was investigated using neutron diffraction and self-consistent modeling (SCM) to ascertain its deformation mechanisms. The compressive behavior of both the composite and the second phase (in its monolithic form) were investigated. The diffraction data were compared to the predictions of a new SCM resulting in good agreement. For the first time, this model considered both amorphous and crystalline phases and allowed the calculation of single crystal elastic constants from polycrystalline diffraction data. It was shown that the ductile second phase yielded first upon loading, and this was followed by multiple shear band formation in the matrix, a process which enhanced the ductility of the composite.

  15. Compressive deformation of in situ formed bulk metallic glass composites

    Clausen, B.; Lee, S.Y.; Ustuendag, E.; Kim, C.P.; Brown, D.W.; Bourke, M.A.M.

    2006-01-01

    A bulk metallic glass matrix composite with dendritic second phase precipitates was investigated using neutron diffraction and self-consistent modeling (SCM) to ascertain its deformation mechanisms. The compressive behavior of both the composite and the second phase (in its monolithic form) were investigated. The diffraction data were compared to the predictions of a new SCM resulting in good agreement. For the first time, this model considered both amorphous and crystalline phases and allowed the calculation of single crystal elastic constants from polycrystalline diffraction data. It was shown that the ductile second phase yielded first upon loading, and this was followed by multiple shear band formation in the matrix, a process which enhanced the ductility of the composite

  16. Homogeneous Catalysis with Metal Complexes Fundamentals and Applications

    Duca, Gheorghe

    2012-01-01

    The book about homogeneous catalysis with metal complexes deals with the description of the reductive-oxidative, metal complexes  in a liquid phase (in polar solvents, mainly in water, and less in nonpolar solvents). The exceptional importance of the redox processes in chemical systems, in the reactions occuring in living organisms, the environmental processes, atmosphere, water, soil, and in industrial technologies (especially in food-processing industries) is discussed. The detailed practical aspects of the established regularities are explained for solving the specific practical tasks in various fields of industrial chemistry, biochemistry, medicine, analytical chemistry and ecological chemistry. The main scope of the book is the survey and systematization of the latest advances in homogeneous catalysis with metal complexes. It gives an overview of the research results and practical experience accumulated by the author during the last decade.

  17. Characterization of tannin-metal complexes by UV-visible spectrophotometry

    Tannins enter soils by plant decay and rain throughfall, but little is known of their effects on soils. Tannins may influence bioavailability and toxicity of metals by forming complexes and by mediating redox reactions. We evaluated the affinity and stoichiometry of Al(III) for a gallotannin, pent...

  18. Complexation-induced supramolecular assembly drives metal-ion extraction.

    Ellis, Ross J; Meridiano, Yannick; Muller, Julie; Berthon, Laurence; Guilbaud, Philippe; Zorz, Nicole; Antonio, Mark R; Demars, Thomas; Zemb, Thomas

    2014-09-26

    Combining experiment with theory reveals the role of self-assembly and complexation in metal-ion transfer through the water-oil interface. The coordinating metal salt Eu(NO3)3 was extracted from water into oil by a lipophilic neutral amphiphile. Molecular dynamics simulations were coupled to experimental spectroscopic and X-ray scattering techniques to investigate how local coordination interactions between the metal ion and ligands in the organic phase combine with long-range interactions to produce spontaneous changes in the solvent microstructure. Extraction of the Eu(3+)-3(NO3(-)) ion pairs involves incorporation of the "hard" metal complex into the core of "soft" aggregates. This seeds the formation of reverse micelles that draw the water and "free" amphiphile into nanoscale hydrophilic domains. The reverse micelles interact through attractive van der Waals interactions and coalesce into rod-shaped polynuclear Eu(III) -containing aggregates with metal centers bridged by nitrate. These preorganized hydrophilic domains, containing high densities of O-donor ligands and anions, provide improved Eu(III) solvation environments that help drive interfacial transfer, as is reflected by the increasing Eu(III) partitioning ratios (oil/aqueous) despite the organic phase approaching saturation. For the first time, this multiscale approach links metal-ion coordination with nanoscale structure to reveal the free-energy balance that drives the phase transfer of neutral metal salts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Wastewater treatment from heavy metal ions using nanoactivated complexes of natural zeolite and diatomite

    Malkin Polad

    2018-04-01

    Full Text Available Despite the wide practical use of sorption methods and complexones in treatment of industrial wastewater, some problems are still to be solved in this field. These are the most significant: insufficient sorption capacity of materials, lack of reliable methods for regenerating sorbents and resource-saving ecology friendly treatment technologies with the use of sorbents as well as methods of utilization of heavy metals from waste by complex formation. An important factor affecting the behavior of heavy metals in the soil is the medium acidity. With a neutral and slightly alkaline reaction of the medium, hardly soluble compounds are formed: hydroxides, sulphides, phosphates, carbonates, and oxalates of heavy metals. When acidity increases the reverse process runs in the soil: hardly soluble compounds become more mobile, while mobility of many heavy metals increases. However, the effect of soil acidity on mobility of heavy metals is ambiguous. Although mobility of many heavy metals decreases with increasing pH of the medium (for example, Fe, Mn, Zn, Co, etc., there are a number of metals whose mobility increases with soil neutralization. These include molybdenum and chromium, which are able to form soluble salts in a weak ly acidic and alkaline medium. In addition, heavy metals such as mercury and cadmium are able to maintain mobility in an alkaline medium through formation of complex compounds with organic matter in soils. Heavy metals interact with a solid phase of the soil by mechanisms of specific and nonspecific adsorption. In this article, a technique of wastewater treatment from heavy metal ions using nanoactivated complexes of natural zeolite and diatomite is proposed. This technique can reduce significant costs in preparation of raw materials and subsequent chemical modification of them. Technological solutions aimed at disposal and recycling of industrial wastewater have been proposed. These solutions make it possible to obtain the water

  20. Physicochemical and biological properties of new steroid metal complexes

    Huber, R.

    1980-04-01

    The aim of this investigation was to prepare stable steroid metal chelates by chemical conversion of the natural steroid hormones testerone, 5α-dihydrotestosterone (5α-DHT) and estradiol and to characterize these by means of their spectroscopic and other physico-chemical properties. In addition, various measuring techniques for the qualitative and quantitative study of complex stabilities and hydrolytic properties were employed. The distribution of some tritiated steroid metal complexes in the tissues of rats was tested using whole animal autoradiography, mainly with a view to identifying whether selective concentration occurs in certain organs. (orig.) [de

  1. THE THEORY OF DEVELOPMENT OF SUPPORTED METAL-COMPLEX CATALYSTS

    T. L. Rakitskaya

    2015-06-01

    Full Text Available Some results of the investigations for the purpose of development of supported metal-complex catalysts for phosphine and carbon monoxide oxidation as well as for ozone decomposition are summarized. The activity of such catalysts has been found to depend not only on a nature of a central atom and ligands but also on a nature of supports. The theoretical model explaining mechanisms of surface complex formation taking into account the influence of physicochemical and structural-adsorption properties of the supports (SiO2, Al2O3, carbon materials, zeolites, dispersed silicas, lamellar aluminosilicates, etc. has been proposed. For quantitative description of the support effect, such a thermodynamic parameter as the adsorbed water activity assignable with the help of water vapor adsorption isotherms has been introduced. Successive stability constants of the surface metal complexes have been calculated by the kinetic method and, hence, compositions and partial catalytic activity of the latter have been determined. Taking into account the competitive adsorption of metal ions on the supports, some schemes of formation of surface bimetallic complexes have been suggested. The compositions of the supported metal-complex catalysts have been optimized to meet requirements of their use in respirators and plants for air purification from foregoing gaseous toxicants.

  2. Properties- and applications of quasicrystals and complex metallic alloys.

    Dubois, Jean-Marie

    2012-10-21

    This article aims at an account of what is known about the potential for applications of quasicrystals and related compounds, the so-called family of Complex Metallic Alloys (CMAs‡). Attention is focused at aluminium-based CMAs, which comprise a large number of crystalline compounds and quasicrystals made of aluminium alloyed with transition metals (like Fe or Cu) or normal metals like Mg. Depending on composition, the structural complexity varies from a few atoms per unit cell up to thousands of atoms. Quasicrystals appear then as CMAs of ultimate complexity and exhibit a lattice that shows no periodicity anymore in the usual 3-dimensional space. Properties change dramatically with lattice complexity and turn the metal-type behaviour of simple Al-based crystals into a far more complex behaviour, with a fingerprint of semi-conductors that may be exploited in various applications, potential or realised. An account of the ones known to the author is given in the light of the relevant properties, namely light absorption, reduced adhesion and friction, heat insulation, reinforcement of composites for mechanical devices, and few more exotic ones. The role played by the search for applications of quasicrystals in the development of the field is briefly addressed in the concluding section.

  3. High Molecular Weight Forms of Mammalian Respiratory Chain Complex II

    Kovářová, Nikola; Mráček, Tomáš; Nůsková, Hana; Holzerová, Eliška; Vrbacký, Marek; Pecina, Petr; Hejzlarová, Kateřina; Klučková, Katarína; Rohlena, Jakub; Neužil, Jiří; Houštěk, Josef

    2013-01-01

    Roč. 8, č. 8 (2013), e71869 E-ISSN 1932-6203 R&D Projects: GA ČR(CZ) GPP303/10/P227; GA MŠk(CZ) LL1204; GA MZd(CZ) NT12370; GA ČR(CZ) GAP301/10/1937 Institutional research plan: CEZ:AV0Z50520701 Institutional support: RVO:67985823 Keywords : supercomplexes * high molecular weihgt forms of complex II * native electrophoretic systems Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 3.534, year: 2013

  4. Synthesis and complex forming property of phosphor acid derivatives

    Babaev, B.N.

    2004-01-01

    Full text:With the aim to get new effective and selective extra gents of noble and non-ferrous metals from acid solution and industrial sewage, research of the dependence of 'structure effectiveness' the various phosphor acid derivatives with logical changeable structure (thio phosphor acids, derivatives of dialkoxythiophosphor, O-alkyl-methylphosphon, alkylphenylphosphon, diphenylphosphine acids also 4 methyl-1,3,2 dioxaphosphorinane) which contain different functional groups, the remains of heterocyclic amines and alkaloids, new derivatives of some analytical reagents were synthesized. The structure of synthesized compounds is approved by the results of IR-, PMR-, mass-spectrum analyze. Researching mass-spectrum decay of synthesized phosphor acid derivatives we defined that differing from O-dihexyl-S-propargyl-benzylthio phosphat, mass spectrum decay of O-dialkyl-S-(piperdynobutin-2-il)thio phosphat is characterized by the appearing [M-H] + ions and during the decay ions with high intensiveness are formed. Fragmentation of M + O-alkyl-O-(aminoalkyl)phenylphosphonate proceeds in various directions and characterized with the great number of phosphor containing ions, the possession of the second phenyl radical in the molecule of diphenylphosphon acid derivatives changes the fragmentation of molecular ion of diphenylphosphon acid derivatives. The process of extraction of noble (Au, Ag, Pt, Pd, Os) metals from hydrochloric-sulphur-nitrogen acid medium was analyzed by radioactive indicator's method. It was noticed that structure, strength, conformation of compounds, the temperature, of acid medium (0,1-10 M) and the nature of acids (HCL, H 2 SO 4 , HNO 3 ) could have strong influence to the effectiveness of metal extraction. During the research of metals extraction from pure solutions we can see the followings: 1) There are such substances, which can be used as effective group reagent towards the Au, Ag and Pd. 2) Derivatives with acetylene extract ions of gold from

  5. Paradigm Change: Alternate Approaches to Constitutive and Necking Models for Sheet Metal Forming

    Stoughton, Thomas B.; Yoon, Jeong Whan

    2011-01-01

    This paper reviews recent work proposing paradigm changes for the currently popular approach to constitutive and failure modeling, focusing on the use of non-associated flow rules to enable greater flexibility to capture the anisotropic yield and flow behavior of metals using less complex functions than those needed under associated flow to achieve that same level of fidelity to experiment, and on the use of stress-based metrics to more reliably predict necking limits under complex conditions of non-linear forming. The paper discusses motivating factors and benefits in favor of both associated and non-associated flow models for metal forming, including experimental, theoretical, and practical aspects. This review is followed by a discussion of the topic of the forming limits, the limitations of strain analysis, the evidence in favor of stress analysis, the effects of curvature, bending/unbending cycles, triaxial stress conditions, and the motivation for the development of a new type of forming limit diagram based on the effective plastic strain or equivalent plastic work in combination with a directional parameter that accounts for the current stress condition.

  6. THE COMPACT STAR-FORMING COMPLEX AT THE HEART OF NGC 253

    Davidge, T. J., E-mail: tim.davidge@nrc.ca [Dominion Astrophysical Observatory, National Research Council of Canada, 5071 West Saanich Road, Victoria, BC V9E 2E7 (Canada)

    2016-02-20

    We discuss integral field spectra of the compact star-forming complex that is the brightest near-infrared (NIR) source in the central regions of the starburst galaxy NGC 253. The spectra cover the H and K passbands and were recorded with the Gemini NIR Spectrograph during subarcsecond seeing conditions. Absorption features in the spectrum of the star-forming complex are weaker than in the surroundings. An absorption feature is found near 1.78 μm that coincides with the location of a C{sub 2} bandhead. If this feature is due to C{sub 2} then the star-forming complex has been in place for at least a few hundred Myr. Emission lines of Brγ, [Fe ii], and He i 2.06 μm do not track the NIR continuum light. Pockets of star-forming activity that do not have associated concentrations of red supergiants, and so likely have ages <8 Myr, are found along the western edge of the complex, and there is evidence that one such pocket contains a rich population of Wolf–Rayet stars. Unless the star-forming complex is significantly more metal-poor than the surroundings, then a significant fraction of its total mass is in stars with ages <8 Myr. If the present-day star formation rate is maintained then the timescale to double its stellar mass ranges from a few Myr to a few tens of Myr, depending on the contribution made by stars older than ∼8 Myr. If—as suggested by some studies—the star-forming complex is centered on the galaxy’s nucleus, which presumably contains a large population of old and intermediate-age stars, then the nucleus of NGC 253 is currently experiencing a phase of rapid growth in its stellar mass.

  7. Zeolites as supports for transition-metal complexes

    Le Van Mao, R

    1979-01-01

    The unique structural characteristics of the zeolites, including the presence of molecular-size cages and channels and of an internal electrostatic field, make them promising as supports for converting homogeneous to heterogeneous catalysts. The acidic sites on the zeolites may also contribute to catalysis of reactions, such as hydrocracking; may stabilize metal complexes in a highly disperse state; and may improve activity or selectivity. Recent studies on the synthesis of new types of zeolite-supported complexes of transition metals (TM), such as Co, Cu, Ag, Fe, Mo, Ru, Rh, Re, and Os, suggest the feasibility of the direct introduction of some TM complexes into the zeolitic cages during zeolite synthesis, especially during the crystallization phase. This method may considerably reduce the structural limitations associated with the incorporation of TM complexes into zeolites by conventional methods.

  8. New Transition metal assisted complex borohydrides for hydrogen storage

    Sesha Srinivasan; Elias Lee Stefanakos; Yogi Goswami

    2006-01-01

    High capacity hydrogen storage systems are indeed essential for the on-board vehicular application that leads to the pollution free environment. Apart from the various hydrogen storage systems explored in the past, complex hydrides involving light weight alkali/alkaline metals exhibits promising hydrogenation/ dehydrogenation characteristics. New transition metal assisted complex borohydrides [Zn(BH 4 ) 2 ] have been successfully synthesized by an inexpensive mechano-chemical process. These complex hydrides possesses gravimetric hydrogen storage capacity of ∼8.4 wt.% at around 120 C. We have determined the volumetric hydrogen absorption and desorption of these materials for a number of cycles. Another complex borohydride mixture LiBH 4 /MgH 2 catalyzed with ZnCl 2 has been synthesized and characterized using various analytical techniques. (authors)

  9. The metallic ratios as limits of complex valued transformations

    Falcon, Sergio; Plaza, Angel

    2009-01-01

    We study the presence of the metallic ratios as limits of two complex valued transformations. These complex variable functions are introduced and related with the two geometric antecedents for each triangle in a particular triangle partition, the four-triangle longest-edge (4TLE) partition. In this way, the fractality of a geometric diagram for the classes of dissimilar generated triangles is also explained.

  10. A Study of Deposition Coatings Formed by Electroformed Metallic Materials.

    Shoji Hayashi

    Full Text Available Major joining methods of dental casting metal include brazing and laser welding. However, brazing cannot be applied for electroformed metals since heat treatment could affect the fit, and, therefore, laser welding is used for such metals. New methods of joining metals that do not impair the characteristics of electroformed metals should be developed. When new coating is performed on the surface of the base metal, surface treatment is usually performed before re-coating. The effect of surface treatment is clinically evaluated by peeling and flex tests. However, these testing methods are not ideal for deposition coating strength measurement of electroformed metals. There have been no studies on the deposition coating strength and methods to test electroformed metals. We developed a new deposition coating strength test for electroformed metals. The influence of the negative electrolytic method, which is one of the electrochemical surface treatments, on the strength of the deposition coating of electroformed metals was investigated, and the following conclusions were drawn: 1. This process makes it possible to remove residual deposits on the electrodeposited metal surface layer. 2. Cathode electrolysis is a simple and safe method that is capable of improving the surface treatment by adjustments to the current supply method and current intensity. 3. Electrochemical treatment can improve the deposition coating strength compared to the physical or chemical treatment methods. 4. Electro-deposition coating is an innovative technique for the deposition coating of electroformed metal.

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

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

    2012-01-01

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

  12. Method for synthesizing metal bis(borano) hypophosphite complexes

    Cordaro, Joseph G.

    2013-06-18

    The present invention describes the synthesis of a family of metal bis(borano) hypophosphite complexes. One procedure described in detail is the syntheses of complexes beginning from phosphorus trichloride and sodium borohydride. Temperature, solvent, concentration, and atmosphere are all critical to ensure product formation. In the case of sodium bis(borano) hypophosphite, hydrogen gas was evolved upon heating at temperatures above 150.degree. C. Included in this family of materials are the salts of the alkali metals Li, Na and K, and those of the alkaline earth metals Mg and Ca. Hydrogen storage materials are possible. In particular the lithium salt, Li[PH.sub.2(BH.sub.3).sub.2], theoretically would contain nearly 12 wt % hydrogen. Analytical data for product characterization and thermal properties are given.

  13. Metathesis synthesis and characterization of complex metal fluoride ...

    Administrator

    V MANIVANNAN*, P PARHI and JONATHAN W KRAMER. Department of Mechanical Engineering, Campus Delivery 1374, Colorado State University, Fort Collins,. CO 80523, USA. MS received 30 April 2008. Abstract. Metathesis synthesis of complex metal fluorides using mechanochemical activation has been reported.

  14. DNA interactions and biocidal activity of metal complexes of ...

    Narendrula Vamsikrishna

    The Schiff bases and metal complexes were characterized by analytical and spectral methods like elemental analysis, ... cleavages.8–10 Cisplatin and its second generation com- ..... in DMSO. The test microorganisms were grown on nutrient agar medium in ...... effects on polymer characteristics Appl. Organomet. Chem.

  15. Dimeric Complexes of Tryptophan with M2+ Metal Ions

    Dunbar, R. C.; Steill, J. D.; Polfer, N. C.; Oomens, J.

    2009-01-01

    IRMPD spectroscopy using the FELIX free electron laser and a Fourier transform ICR mass spectrometer was used to characterize the structures of electrosprayed dimer complexes M(2+)Trp(2) of tryptophan with a series of eight doubly charged metal ions, including alkaline earths Ca, Sr, and Ba, and

  16. Sub-chronic toxicological studies of transition metal complexes of ...

    However, Naproxen metal complexes showed comparatively lower side effects than naproxen. Hematological report suggested that naproxen was in process of initiating inflammation which was justified by decreasing the mean value hemoglobin and hematocrit level and increasing the white blood cells level. There were ...

  17. Lability criteria for metal complexes in micro-electrode voltammetry

    Leeuwen, van H.P.; Pinheiro, J.P.

    1999-01-01

    Theoretical expressions are derived for the voltammetric lability criteria of metal complexes in the micro-electrode regime. The treatment includes three limiting situations: (i) the macro-electrode limit, where both the diffusion layer and the dissociation reaction layer are linear; (ii) an

  18. Schiff base transition metal complexes for Suzuki–Miyaura cross

    Schiff base ligand and its complex with iron (Fe), cobalt (Co), nickel (Ni) and copper (Cu) ions were synthesized using 4-aminoacetophenone and salicylaldehyde and characterized. FTIR spectrum shows that bidentate coordination of metal ions with ligand where O, N are electron donating sites of azomethine group.

  19. Group 4 Metal Complexes of Chelating Cyclopentadienyl-ketimide Ligands

    Večeřa, M.; Varga, Vojtěch; Císařová, I.; Pinkas, Jiří; Kucharczyk, P.; Sedlařík, V.; Lamač, Martin

    2016-01-01

    Roč. 35, č. 5 (2016), s. 785-798 ISSN 0276-7333 R&D Projects: GA ČR(CZ) GA14-08531S; GA MŠk(CZ) LO1504 Institutional support: RVO:61388955 Keywords : group 4 metal complexes * cyclopentadienyl-ketimide ligands * metallocenes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.862, year: 2016

  20. Metal-isonitrile adducts for preparing radionuclide complexes

    Carpenter, A.P.; Linder, K.E.; Maheu, L.J.; Patz, M.A.; Thompson, J.S.; Tulip, T.H.; Subramanyam, V.

    1988-01-01

    An method for preparing a coordination complex of isonitrile ligand and a radioisotope of Te, Ru, Co, Pt, Re, Os, Ir, W, Re, Cr, Mo, Mn, Ni, Rh, Nb and Ta from a non-radioactive metal adduct of the isonitrile

  1. Metal complexes in cancer therapy – an update from drug design perspective

    Ndagi U

    2017-03-01

    Full Text Available Umar Ndagi, Ndumiso Mhlongo, Mahmoud E Soliman Molecular Modelling and Drug Design Research Group, School of Health Sciences, University of KwaZulu-Natal, Westville, Durban, South Africa Abstract: In the past, metal-based compounds were widely used in the treatment of disease conditions, but the lack of clear distinction between the therapeutic and toxic doses was a major challenge. With the discovery of cisplatin by Barnett Rosenberg in 1960, a milestone in the history of metal-based compounds used in the treatment of cancers was witnessed. This forms the foundation for the modern era of the metal-based anticancer drugs. Platinum drugs, such as cisplatin, carboplatin and oxaliplatin, are the mainstay of the metal-based compounds in the treatment of cancer, but the delay in the therapeutic accomplishment of other metal-based compounds hampered the progress of research in this field. Recently, however, there has been an upsurge of activities relying on the structural information, aimed at improving and developing other forms of metal-based compounds and nonclassical platinum complexes whose mechanism of action is distinct from known drugs such as cisplatin. In line with this, many more metal-based compounds have been synthesized by redesigning the existing chemical structure through ligand substitution or building the entire new compound with enhanced safety and cytotoxic profile. However, because of increased emphasis on the clinical relevance of metal-based complexes, a few of these drugs are currently on clinical trial and many more are awaiting ethical approval to join the trial. In this review, we seek to give an overview of previous reviews on the cytotoxic effect of metal-based complexes while focusing more on newly designed metal-based complexes and their cytotoxic effect on the cancer cell lines, as well as on new approach to metal-based drug design and molecular target in cancer therapy. We are optimistic that the concept of selective

  2. Modeling corrosion and constituent release from a metal waste form

    Bauer, T. H.; Fink, J. K.; Abraham, D. P.; Johnson, I.; Johnson, S. G.; Wigeland, R. A.

    2000-01-01

    Several ANL ongoing experimental programs have measured metal waste form (MWF) corrosion and constituent release. Analysis of this data has initiated development of a consistent and quantitative phenomenology of uniform aqueous MWF corrosion. The effort so far has produced a preliminary fission product and actinide release model based on measured corrosion rates and calibrated by immersion test data for a 90 C J-13 and concentrated J-13 solution environment over 1-2 year exposure times. Ongoing immersion tests of irradiated and unirradiated MWF samples using more aggressive test conditions and improved tracking of actinides will serve to further validate, modify, and expand the application base of the preliminary model-including effects of other corrosion mechanisms. Sample examination using both mechanical and spectrographic techniques will better define both the nature and durability of the protective barrier layer. It is particularly important to assess whether the observations made with J-13 solution at 900 C persist under more aggressive conditions. For example, all the multiplicative factors in Table 1 implicitly assume the presence of protective barriers. Under sufficiently aggressive test conditions, such protective barriers may very well be altered or even eliminated

  3. Micromechanical simulation of frictional behaviour in metal forming

    Zhang, S.; Hodgson, P.D.; Cardew-Hall, M.J.; Kalyanasundaram, S.

    2000-01-01

    Friction is a critical factor for Sheet Metal Forming (SMF). The Coulomb friction model is usually used in most Finite Element (FE) simulation for SMF. However, friction is a function of the local contact deformation conditions, such as local pressure, roughness and relative velocity. This paper will present a micromechanical model that accounts for the local frictional behaviour through finite element simulations performed at the micromechanical level. Frictional behaviour between contact surfaces can be based on three cases: boundary, hydrodynamic and mixed lubrication. In our microscopic friction model based on FEM, the case of boundary lubrication contact between sheet and tool has been considered. In the view of microscopic geometry, roughness depends upon amplitude and wavelength of surface asperities of sheet and tool. The mean pressure applied on the surface differs from the pressure over the actual contact area. The effect of roughness (microscopic geometric condition) and relative speed of contact surfaces on friction coefficient was examined in the FE model for the microscopic friction behaviour. The analysis was performed using an explicit finite element formulation. In this study, it was found that the roughness of deformable sheet decreases during sliding and the coefficient of friction increases with increasing roughness of contact surfaces. The coefficient of friction increases with the increase of relative velocity and adhesive friction coefficient between contact surfaces. (author)

  4. Metal distributions in complexes with Chlorella vulgaris in seawater and wastewater

    Pascucci, P.R.; Kowalak, A.D.

    1999-10-01

    Divalent cadmium (Cd), copper (Cu), iron (Fe), nickel (Ni), lead (Pb), and zinc (Zn) simultaneous complexes with an algal biomass Chlorella vulgaris were studied for bioremediation purposes in various aqueous media: distilled-deionized water (DDIW), seawater, nuclear-reactor pool water, and process wastewater. Reactions were monitored using various dry masses of algae at constant temperature and constant metal concentrations for reaction times ranging from 0 to 150 minutes. Complexes occurred within 30 minutes and reached a steady state after 80 to 120 minutes. Distribution constants (K{prime}{sub d}) were calculated for the complexes and relative orders of K{prime}{sub d} were reported. The K{prime}{sub d} are used to evaluate relative efficiency of metal remediation from waters. Lead, Cu, and Ni complexes had the greatest K{prime}{sub d} values and those metals were most efficiently removed from these waters. Zinc and Fe formed the most labile complexes. The order of K{prime}{sub d} values for complexes in DDIW was Pb > Cu > Cd > Zn, then Cu > Cd > Zn in seawater, Cd > Cu > Zn in reactor pool water, and Ni > Cd > Cu > Zn > Fe in wastewater. C. vulgaris biomass may potentially be used as an alternative to traditional water treatment methods for simultaneous extraction of metals from seawater, process wastewater, or drinking water.

  5. Synthesis, Characterization and Biological Evaluation of Transition Metal Complexes Derived from N, S Bidentate Ligands

    Enis Nadia Md Yusof

    2015-05-01

    Full Text Available Two bidentate NS ligands were synthesized by the condensation reaction of S-2-methylbenzyldithiocarbazate (S2MBDTC with 2-methoxybenzaldehyde (2MB and 3-methoxybenzaldehyde (3MB. The ligands were reacted separately with acetates of Cu(II, Ni(II and Zn(II yielding 1:2 (metal:ligand complexes. The metal complexes formed were expected to have a general formula of [M(NS2] where M = Cu2+, Ni2+, and Zn2+. These compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility and various spectroscopic techniques. The magnetic susceptibility measurements and spectral results supported the predicted coordination geometry in which the Schiff bases behaved as bidentate NS donor ligands coordinating via the azomethine nitrogen and thiolate sulfur. The molecular structures of the isomeric S2M2MBH (1 and S2M3MBH (2 were established by X-ray crystallography to have very similar l-shaped structures. The Schiff bases and their metal complexes were evaluated for their biological activities against estrogen receptor-positive (MCF-7 and estrogen receptor-negative (MDA-MB-231 breast cancer cell lines. Only the Cu(II complexes showed marked cytotoxicity against the cancer cell lines. Both Schiff bases and other metal complexes were found to be inactive. In concordance with the cytotoxicity studies, the DNA binding studies indicated that Cu(II complexes have a strong DNA binding affinity.

  6. Segregation and persistence of form in the lateral occipital complex.

    Ferber, Susanne; Humphrey, G Keith; Vilis, Tutis

    2005-01-01

    While the lateral occipital complex (LOC) has been shown to be implicated in object recognition, it is unclear whether this brain area is responsive to low-level stimulus-driven features or high-level representational processes. We used scrambled shape-from-motion displays to disambiguate the presence of contours from figure-ground segregation and to measure the strength of the binding process for shapes without contours. We found persisting brain activation in the LOC for scrambled displays after the motion stopped indicating that this brain area subserves and maintains figure-ground segregation processes, a low-level function in the object processing hierarchy. In our second experiment, we found that the figure-ground segregation process has some form of spatial constancy indicating top-down influences. The persisting activation after the motion stops suggests an intermediate role in object recognition processes for this brain area and might provide further evidence for the idea that the lateral occipital complex subserves mnemonic functions mediating between iconic and short-term memory.

  7. The preparation and use of metal salen complexes derived from cyclobutane diamine

    Patil, Smita

    The helix is an important chiral motif in nature, there is increasing development in field of helical transition metal complexes and related supramolecular structures. Hence, the goals of this work are to apply the principles of helicity in order to produce metal complexes with predictable molecular shapes and to study their properties as asymmetric catalysts. Computational studies suggest that the (1R,2 R)-cyclobutyldiamine unit can produce highly twisted salen complexes with a large energy barrier between the M and P helical forms. To test this prediction, the tartrate salt of (1R,2R)-cyclobutyldiamine was synthesized and condensed with a series of saliclaldehydes to produce novel salen ligands. The salicylaldehydes chosen have extended phenanthryl or benz[a]anthryl sidearms to encourage formation of helical coordination complexes. These ligands were metallated with zinc, iron and manganese salts to produce salen metal complexes which were characterized by NMR analysis, high-resolution mass spectrometry, and IR spectroscopy. A second ligand type, neutral bis(pyridine-imine) has also been synthesized from (1R,2R)-cyclobutyldiamine and quinolylaldehydes. The synthesis of bis(pyridine-imine) ligands was conducted using greener method, solvent assisted grinding. These ligands, in-situ with nickel metal salts, showed good catalytic activity for asymmetric Diels-Alder reactions. The third ligand type studied was chiral acid-functionalized Schiff-base ligands. These were synthesized by the condensation of 3-formyl-5-methyl salicylic acid and (1R,2R)-cyclobutyldiamine. With this type of ligand, there is possibility of producing both mono and dinuclear metal complexes. In our studies, we were only able to synthesize mononuclear complexs. These were tested as catalysts for asymmetric direct Mannich-type reaction, but were found to be ineffective.

  8. Intraparticulate Metal Speciation Analysis of Soft Complexing Nanoparticles. The Intrinsic Chemical Heterogeneity of Metal-Humic Acid Complexes

    Town, R. M.; van Leeuwen, Herman P.

    2016-01-01

    ion condensation potential for higher valency counterions within the intraparticulate double layer zone of the soft NP. The approach offers new insights into the intrinsic heterogeneity of the HA. complexes, as revealed by the intraparticulate speciation as a function of the true degree of inner......-sphere complexation, theta(M). The ensuing intrinsic heterogeneity parameters, Gamma, for CdHA and CuHA complexes are in very good agreement with those obtained from dynamic electrochemical stripping chronopotentiometric measurements. The overall intraparticulate metal ion speciation is found to depend on theta...

  9. Research on Liquid Forming Process of Nickel Superalloys Thin Sheet Metals

    Hyrcza-Michalska M.

    2017-12-01

    Full Text Available The paper presents the study of drawability of thin sheet metals made of a nickel superalloy Inconel type. The manufacturing process of axisymmetric cup – cone and a closed section profile in the form of a circular tube were designed and analyzed. In both cases, working fluid-oil was used in place of the rigid tools. The process of forming liquid is currently the only alternative method for obtaining complex shapes, coatings, and especially if we do it with high-strength materials. In the case of nickel superalloys the search for efficient methods to manufacture of the shaped shell is one of the most considerable problems in aircraft industry [1-5]. However, the automotive industries have the same problem with so-called advanced high-strength steels (AHSS. Due to this, both industrial problems have been examined and the emphasis have been put on the process of liquid forming (hydroforming. The study includes physical tests and the corresponding numerical simulations performed, using the software Eta/Dynaform 5.9. Numerical analysis of the qualitative and quantitative forecasting enables the formability of materials with complex and unusual characteristics of the mechanical properties and forming technology. It has been found that only the computer aided design based on physical and numerical modeling, makes efficient plastic processing possible using a method of hydroforming. Drawability evaluation based on the determination of the mechanical properties of complex characteristics is an indispensable element of this design in the best practice of industrial manufacturing products made of thin sheet metals.

  10. Pesticides Curbing Soil Fertility: Effect of Complexation of Free Metal Ions

    Kaur, Sukhmanpreet

    2017-07-04

    Researchers have suggested that the reason behind infertility is pernicious effect of broad spectrum pesticides on non target, beneficial microorganism of soil. Here, studying the chelating effect of selective organophosphate and carbamate pesticides with essential metal ions, at all possible combinations of three different pH (4 ± 0.05, 7 ± 0.05 and 9 ± 0.05) and three different temperatures (15 ± 0.5°C, 30 ± 0.5°C and 45 ± 0.5°C), shows very fast rate of reaction which further increases with increase of pH and temperature. Carbonyl oxygen of carbamate and phosphate oxygen of organophosphate were found to be common ligating sites among all the complexes. Formed metal complexes were found to be highly stable and water insoluble on interaction with essential metal ions in solvent medium as well as over silica. Density functional theory (DFT) calculations not only reinforced the experimental observations, but, after a wide computational conformational analysis, unraveled the nature of the high stable undesired species that consist of pesticides complexed by metal ions from the soil. All in all, apart from the direct toxicity of pesticides, the indirect effect by means of complexation of free metal ions impoverishes the soil.

  11. Pesticides Curbing Soil Fertility: Effect of Complexation of Free Metal Ions

    Kaur, Sukhmanpreet; Kumar, Vijay; Chawla, Mohit; Cavallo, Luigi; Poater, Albert; Upadhyay, Niraj

    2017-07-01

    Researchers have suggested that the reason behind infertility is pernicious effect of broad spectrum pesticides on non target, beneficial microorganism of soil. Here, studying the chelating effect of selective organophosphate and carbamate pesticides with essential metal ions, at all possible combinations of three different pH (4±0.05, 7±0.05 and 9±0.05) and three different temperatures (15±0.5°C, 30±0.5°C and 45±0.5°C), shows very fast rate of reaction which further increases with increase of pH and temperature. Carbonyl oxygen of carbamate and phosphate oxygen of organophosphate were found to be common ligating sites among all the complexes. Formed metal complexes were found to be highly stable and water insoluble on interaction with essential metal ions in solvent medium as well as over silica. Density functional theory (DFT) calculations not only reinforced the experimental observations, but, after a wide computational conformational analysis, unraveled the nature of the high stable undesired species that consist of pesticides complexed by metal ions from the soil. All in all, apart from the direct toxicity of pesticides, the indirect effect by means of complexation of free metal ions impoverishes the soil.

  12. Pesticides Curbing Soil Fertility: Effect of Complexation of Free Metal Ions

    Kaur, Sukhmanpreet; Kumar, Vijay; Chawla, Mohit; Cavallo, Luigi; Poater, Albert; Upadhyay, Niraj

    2017-01-01

    Researchers have suggested that the reason behind infertility is pernicious effect of broad spectrum pesticides on non target, beneficial microorganism of soil. Here, studying the chelating effect of selective organophosphate and carbamate pesticides with essential metal ions, at all possible combinations of three different pH (4 ± 0.05, 7 ± 0.05 and 9 ± 0.05) and three different temperatures (15 ± 0.5°C, 30 ± 0.5°C and 45 ± 0.5°C), shows very fast rate of reaction which further increases with increase of pH and temperature. Carbonyl oxygen of carbamate and phosphate oxygen of organophosphate were found to be common ligating sites among all the complexes. Formed metal complexes were found to be highly stable and water insoluble on interaction with essential metal ions in solvent medium as well as over silica. Density functional theory (DFT) calculations not only reinforced the experimental observations, but, after a wide computational conformational analysis, unraveled the nature of the high stable undesired species that consist of pesticides complexed by metal ions from the soil. All in all, apart from the direct toxicity of pesticides, the indirect effect by means of complexation of free metal ions impoverishes the soil.

  13. Multi-scale contact modeling of coated steels for sheet metal forming applications

    Shisode, Meghshyam; Hazrati Marangalou, Javad; Mishra, Tanmaya; De Rooij, Matthijn; Van Den Boogaard, Ton; Bay, Niels; Nielsen, Chris V.

    2018-01-01

    Friction in sheet metal forming is a local phenomenon which depends on continuously evolving contact conditions during the forming process. This is mainly influenced by local contact pressure, surface textures of the sheet metal as well as the forming tool surface profile and material behavior. The

  14. Early stage crystallization kinetics in metallic glass-forming alloys

    Louzguine-Luzgin, Dmitri V.

    2014-01-01

    Highlights: • Heterogeneous nucleation may precede the homogeneous one in an alloy. • High kinetic constants and the nucleation rate at the initial stage. • Metallic glasses have heterogeneous nucleation sites which saturate later. -- Abstract: The crystallization kinetics and structural changes of a few metallic glassy alloys were monitored using X-ray diffraction, transmission electron microscopy, differential scanning and isothermal calorimetry methods. Microstructural observations were used to estimate the nucleation and growth rates. A clear comparison of the differences in the crystallization kinetics in the metallic glassy samples is observed at the early and later crystallization stages

  15. [Ultraviolet-visible spectrometry analysis of insoluble xanthate heavy metal complexes].

    Qiu, Bo; Liu, Jin-Feng; Liu, Yao-Chi; Yang, Zhao-Guang; Li, Hai-Pu

    2014-11-01

    A ultraviolet-visible spectrometry method of determining insoluble xanthate heavy metal complexes in flotation wastewater was the first time to be put forward. In this work, the changes of ultraviolet-visible spectra of xanthate solution after the addition of various heavy metal ions were investigated firstly. It was found that Pb2+ and Cu2+ can form insoluble complexes with xanthate, while Fe2+, Zn2+ and Mn2+ have little effect on the ultraviolet absorption of xanthate solution. Then the removal efficiencies of filter membrane with different pore sizes were compared, and the 0.22 μm membrane was found to be effective to separate copper xanthate or lead xanthate from the filtrate. Furthermore, the results of the study on the reaction of sodium sulfide and insoluble xanthate heavy metal complexes showed that S(2-) can release the xanthate ion quantitatively from insoluble complexes to solution. Based on the above research, it was concluded that the amount of insoluble xanthate heavy metal complexes in water samples can be obtained through the increase of free xanthate in the filtrate after the addition of sodium sulfide. Finally, the feasibility of this method was verified by the application to the analysis of flotation wastewater from three ore-dressing plants in the Thirty-six Coves in Chenzhou.

  16. Controlling Magnetism of a Complex Metallic System Using Atomic Individualism

    Mudryk, Y.; Paudyal, D.; Pecharsky, V. K.; Gschneidner, K. A., Jr.; Misra, S.; Miller, G. J.

    2010-08-01

    When the complexity of a metallic compound reaches a certain level, a specific location in the structure may be critically responsible for a given fundamental property of a material while other locations may not play as much of a role in determining such a property. The first-principles theory has pinpointed a critical location in the framework of a complex intermetallic compound—Gd5Ge4—that resulted in a controlled alteration of the magnetism of this compound using precise chemical tools.

  17. Charge transfers in complex transition metal alloys (Ti2Fe)

    Abramovici, G.

    1998-01-01

    We introduce a new non-orthogonal tight-binding model, for complex alloys, in which electronic structure is characterized by charge transfers. We give the analytic calculation of a charge transfer, in which overlapping two-center terms are rigorously taken into account. Then, we apply numerically this result to an approximant phase of a quasicrystal of Ti 2 Fe alloy. This model is more particularly adapted to transition metals, and gives realistic densities of states. (orig.)

  18. The dynamic behavior of the exohedral transition metal complexes ...

    Home; Journals; Journal of Chemical Sciences; Volume 129; Issue 7. The dynamic behavior of the exohedral transition metal complexes of B₄₀ : η⁶- and η⁷-B₄₀Cr(CO) ₃ and Cr(CO) ₃η⁷-B₄η₀-Cr(CO) ₃. NAIWRIT KARMODAK ELUVATHINGAL D JEMMIS. REGULAR ARTICLE Volume 129 Issue 7 July 2017 pp ...

  19. The impact of metal transport processes on bioavailability of free and complex metal ions in methanogenic granular sludge

    Bartacek, J.; Fermoso, F.G.; Vergeldt, F.; Gerkema, E.; Maca, J.; As, van H.; Lens, P.N.L.

    2012-01-01

    Bioavailability of metals in anaerobic granular sludge has been extensively studied, because it can have a major effect on metal limitation and metal toxicity to microorganisms present in the sludge. Bioavailability of metals can be manipulated by bonding to complexing molecules such as

  20. Mechanics of metal-catecholate complexes: The roles of coordination state and metal types

    Xu, Zhiping

    2013-01-01

    There have been growing evidences for the critical roles of metal-coordination complexes in defining structural and mechanical properties of unmineralized biological materials, including hardness, toughness, and abrasion resistance. Their dynamic (e.g. pH-responsive, self-healable, reversible) properties inspire promising applications of synthetic materials following this concept. However, mechanics of these coordination crosslinks, which lays the ground for predictive and rational material design, has not yet been well addressed. Here we present a first-principles study of representative coordination complexes between metals and catechols. The results show that these crosslinks offer stiffness and strength near a covalent bond, which strongly depend on the coordination state and type of metals. This dependence is discussed by analyzing the nature of bonding between metals and catechols. The responsive mechanics of metal-coordination is further mapped from the single-molecule level to a networked material. The results presented here provide fundamental understanding and principles for material selection in metal-coordination-based applications. PMID:24107799

  1. General Synthesis of Transition-Metal Oxide Hollow Nanospheres/Nitrogen-Doped Graphene Hybrids by Metal-Ammine Complex Chemistry for High-Performance Lithium-Ion Batteries.

    Chen, Jiayuan; Wu, Xiaofeng; Gong, Yan; Wang, Pengfei; Li, Wenhui; Mo, Shengpeng; Peng, Shengpan; Tan, Qiangqiang; Chen, Yunfa

    2018-02-09

    We present a general and facile synthesis strategy, on the basis of metal-ammine complex chemistry, for synthesizing hollow transition-metal oxides (Co 3 O 4 , NiO, CuO-Cu 2 O, and ZnO)/nitrogen-doped graphene hybrids, potentially applied in high-performance lithium-ion batteries. The oxygen-containing functional groups of graphene oxide play a prerequisite role in the formation of hollow transition-metal oxides on graphene nanosheets, and a significant hollowing process occurs only when forming metal (Co 2+ , Ni 2+ , Cu 2+ , or Zn 2+ )-ammine complex ions. Moreover, the hollowing process is well correlated with the complexing capacity between metal ions and NH 3 molecules. The significant hollowing process occurs for strong metal-ammine complex ions including Co 2+ , Ni 2+ , Cu 2+ , and Zn 2+ ions, and no hollow structures formed for weak and/or noncomplex Mn 2+ and Fe 3+ ions. Simultaneously, this novel strategy can also achieve the direct doping of nitrogen atoms into the graphene framework. The electrochemical performance of two typical hollow Co 3 O 4 or NiO/nitrogen-doped graphene hybrids was evaluated by their use as anodic materials. It was demonstrated that these unique nanostructured hybrids, in contrast with the bare counterparts, solid transition-metal oxides/nitrogen-doped graphene hybrids, perform with significantly improved specific capacity, superior rate capability, and excellent capacity retention. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Defining a metal-based waste form for IFR pyroprocessing wastes

    McDeavitt, S.M.; Park, J.Y.; Ackerman, J.P.

    1994-01-01

    Pyrochemical electrorefining to recover actinides from metal nuclear fuel is a key element of the Integral Fast Reactor (IFR) fuel cycle. The process separates the radioactive fission products from the long-lived actinides in a molten LiCl-KCl salt, and it generates a lower waste volume with significantly less long-term toxicity as compared to spent nuclear fuel. The process waste forms include a mineral-based waste form that will contain fission products removed from an electrolyte salt and a metal-based waste form that will contain metallic fission products and the fuel cladding and process materials. Two concepts for the metal-based waste form are being investigated: (1) encapsulating the metal constituents in a Cu-Al alloy and (2) alloying the metal constituents into a uniform stainless steel-based waste form. Results are given from our recent studies of these two concepts

  3. 40 CFR Appendix B to Part 414 - Complexed Metal-Bearing Waste Streams

    2010-07-01

    ... 414—Complexed Metal-Bearing Waste Streams Chromium Azo dye intermediates/Substituted diazonium salts + coupling compounds Vat dyes Acid dyes Azo dyes, metallized/Azo dye + metal acetate Acid dyes, Azo...

  4. Coordination diversity of new mononucleating hydrazone in 3d metal complexes: Synthesis, characterization and structural studies

    RAJESH S. BALIGAR

    2006-12-01

    Full Text Available The mononucleating hydrazone ligand LH3, a condensation product of salicyloylhydrazine and (2-formylphenoxyacetic acid, was synthesized and its coordination behavior with first row transition metal(II ions was investigated by isolating and elucidating the structure of the complexes using elemental analysis, conductivity and magnetic susceptibility measurements, as well as IR, 1H-NMR, electronic and EPR spectral techniques. The ligand forms mononuclear metal(II complexes of the type [CoLH(H2O2], [NiLH(H2O2, [CuLH] and [ZnLH]. The ligand field parameters, Dq, B and b values, in the case of the cobalt and nickel complexes support not only the octahedral geometry around the metal ion, but also imply the covalent nature of the bonding in the complexes. The EPR study revealed the presence of a spin exchange interaction in the solid copper complex and the covalent nature of the bonding. The 1H-NMR study of the zinc(II complex indicated the non-involvement of the COOH group in the coordination. The physico-chemical study supports for the presence of octahedral geometry around cobalt(II, nickel(II and tetrahedral geometry around copper(II and zinc(II ions.

  5. Late transition metal m-or chemistry and D6 metal complex photoeliminations

    Sharp, Paul [Univ. of Missouri, Columbia, MO (United States)

    2015-07-31

    With the goal of understanding and controlling photoreductive elimination reactions from d6 transition metal complexes as part of a solar energy storage cycle we have investigated the photochemistry of Pt(IV) bromo, chloro, hydroxo, and hydroperoxo complexes. Photoreductive elimination reactions occur for all of these complexes and appear to involve initial Pt-Br, Pt-Cl, or Pt-O bond fission. In the case of Pt-OH bond fission, the subsequent chemistry can be controlled through hydrogen bonding to the hydroxo group.

  6. Process of forming a sol-gel/metal hydride composite

    Congdon, James W [Aiken, SC

    2009-03-17

    An external gelation process is described which produces granules of metal hydride particles contained within a sol-gel matrix. The resulting granules are dimensionally stable and are useful for applications such as hydrogen separation and hydrogen purification. An additional coating technique for strengthening the granules is also provided.

  7. Recent developments in metal forming; Desenvolvimento na conformacao mecanica dos acos

    Schaeffer, Lirio [Rio Grande do Sul Univ., Porto Alegre, RS (Brazil)

    1990-12-31

    This work presents and discuss several processes concerning metal forming, specially steel forming. In the area of rolling, aspects related with liquid rolling and process simulation was analyzed. In the forging extrusion process, advances in cold and warm metal forming are reviewed. With regard to drawing of steel, a method for the evaluation of the lubrication efficiency through measurements of forces is presented. Finally, general considerations in forming of sintered products are also considered. 12 figs., 7 tabs., 10 refs.

  8. Organodioxygen complexes of some group 4B metal ions

    Tarafder, M.T.H.; Akhter Hossain; Gino Mariotto

    2003-09-01

    Organodioxygen complexes of some group 4B metal ions, viz., zirconium(IV), tin(IV) and lead(II) containing monodentate, bidentate and tridentate ligands were synthesized and characterized. The complexes have the compositions of [Zr(O)(O 2 )2C 5 H 5 N.H 2 O], [Zr(O)(O 2 - ) 2 .2OPPh 3 ], [Sn(O 2 )(C 9 H 6 NO) 2 ], [Sn(0 2 ) 2 .(CH 2 ) 2 (NH 2 ) 2 ], [Pb(O 2 - )(C 5 H 5 N) 2 NO 3 ], [Pb(O 2 )(C 8 H 6 NOH)], [Pb(O 2 - )(det)NO 3 ] and [PbO 2 - ) (C 5 H 4 NCOOH)NO 3 .H 2 O]. Because of apparent linearity of M- O 2 grouping, the V 1 (O-O) stretching modes were only Raman active, giving bands at 810- 841 cm 1 for the peroxo complexes (1, 3, ,4 and 6), while the bands in the superoxo complexes (2, 5, 7 and 8) appeared at 1020- 1100 cm -1 . The peroxo complex of Zr(IV) containing monodentate ligands were found to oxidize trans-stilbene to trans-stilbene oxide under stoichiometric conditions. The organoperoxo complexes of tin and lead were insensitive to oxidative processes. (author)

  9. Decoupled Simulation Method For Incremental Sheet Metal Forming

    Sebastiani, G.; Brosius, A.; Tekkaya, A. E.; Homberg, W.; Kleiner, M.

    2007-01-01

    Within the scope of this article a decoupling algorithm to reduce computing time in Finite Element Analyses of incremental forming processes will be investigated. Based on the given position of the small forming zone, the presented algorithm aims at separating a Finite Element Model in an elastic and an elasto-plastic deformation zone. Including the elastic response of the structure by means of model simplifications, the costly iteration in the elasto-plastic zone can be restricted to the small forming zone and to few supporting elements in order to reduce computation time. Since the forming zone moves along the specimen, an update of both, forming zone with elastic boundary and supporting structure, is needed after several increments.The presented paper discusses the algorithmic implementation of the approach and introduces several strategies to implement the denoted elastic boundary condition at the boundary of the plastic forming zone

  10. Chemical bonding of hydrogen molecules to transition metal complexes

    Kubas, G.J.

    1990-01-01

    The complex W(CO) 3 (PR 3 ) 2 (H 2 ) (CO = carbonyl; PR 3 = organophosphine) was prepared and was found to be a stable crystalline solid under ambient conditions from which the hydrogen can be reversibly removed in vacuum or under an inert atmosphere. The weakly bonded H 2 exchanges easily with D 2 . This complex represents the first stable compound containing intermolecular interaction of a sigma-bond (H-H) with a metal. The primary interaction is reported to be donation of electron density from the H 2 bonding electron pair to a vacant metal d-orbital. A series of complexes of molybdenum of the type Mo(CO)(H 2 )(R 2 PCH 2 CH 2 PR 2 ) 2 were prepared by varying the organophosphine substitutent to demonstrate that it is possible to bond either dihydrogen or dihydride by adjusting the electron-donating properties of the co-ligands. Results of infrared and NMR spectroscopic studies are reported. 20 refs., 5 fig

  11. Soil, climate and the environment - an indissociable threesome. Soil carbon and global changes: reciprocal impacts; Carbon in all its forms; Echomicadas, a new tool to analyse carbon 14; Biotransformation of metallic trace elements by soil micro-organisms; Absorption and distribution of metallic elements in plants; Dynamics of metallic contaminants in agricultural systems; Is photo-remediation for tomorrow? Hyper-accumulator plants; Sediments, tell me the Seine history... The complex history of plant feeding by the soil; The environmental analysis

    Hatte, Christine; Tisnerat-Laborde, Nadine; Ayrault, Sophie; Balesdent, Jerome; Chapon, Virginie; Bourguignon, Jacques; Alban, Claude; Ravanel, Stephane; Denaix, Laurence; Nguyen, Christophe; Vavasseur, Alain; Sarrobert, Catherine; Gasperi, Johnny; Latrille, Christelle; Savoye, Sebastien; Augusto, Laurent; Conan Labbe, Annie; Bernard Michel, Bruno; Douysset, Guilhem; Toqnelli, Antoine; Vailhen, Dominique; Moulin, Christophe

    2016-01-01

    The articles of this file on the relationships between soils, climate and the environment discuss the reciprocal impacts of soil carbon and global changes with the objective of reduction of greenhouse effect and of increase of carbon sequestration; the various forms of carbon are presented and their properties commented ; a compact radiocarbon system (ECHoMiCADAS) is presented, developed by the Laboratory of sciences of climate and environment (LSCE) and designed for the analysis of carbon 14; an article describes how micro-organisms can play a crucial role in the transformation of soil pollutants by modifying their chemical speciation and thus their toxicity; strategies based on the absorption of metallic trace elements present in the soil to control physiological processes in plants are discussed, with applications to agriculture, food supply and to the environment; researches related to the study of effects of metallic contaminants in agricultural systems are evoked, and the reasons for a slow development of phyto-technologies, notably phyto-remediation, for pollution control and decontamination of soils and liquid media, are explained. Other themes are presented : hyper-accumulator plants which present very high contents of non-essential (As, Cd, Hg, Pb, Se) or essential (Co, Cu, Fe, Mn, Mo, Ni) elements, are slowly growing, and display a limited biomass, but could be used for a phyto-extraction of metals from contaminated soils; how analysis and dating of sediments can reveal the presence of contaminants, and therefore give an insight into human activities and regulations, and into their impact on the river; how plants are able to develop strategies in their search for nutrients in different types of soils, even poor ones, and presentation of the various disciplines, methods and techniques used for environmental analysis with their applications to installation and site control, or to the study of pollutant migration

  12. FORMING TUBES AND RODS OF URANIUM METAL BY EXTRUSION

    Creutz, E.C.

    1959-01-27

    A method and apparatus are presented for the extrusion of uranium metal. Since uranium is very brittle if worked in the beta phase, it is desirable to extrude it in the gamma phase. However, in the gamma temperature range thc uranium will alloy with the metal of the extrusion dic, and is readily oxidized to a great degree. According to this patent, uranium extrusion in thc ganmma phase may be safely carried out by preheating a billet of uranium in an inert atmosphere to a trmperature between 780 C and 1100 C. The heated billet is then placed in an extrusion apparatus having dies which have been maintained at an elevated temperature for a sufficient length of time to produce an oxide film, and placing a copper disc between the uranium billet and the die.

  13. Chemistry and Properties of Complex Intermetallics from Metallic Fluxes

    Kanatzidis, Mercouri G. [Northwestern Univ., Evanston, IL (United States)

    2015-03-28

    This project investigated the reaction chemistry and synthesis of new intermetallic materials with complex compositions and structures using metallic fluxes as solvents. It was found that the metallic fluxes offer several key advantages in facilitating the formation and crystal growth of new materials. The fluxes mostly explored were liquid aluminum, gallium and indium. The main purpose of this project was to exploit the potential of metallic fluxes as high temperature solvent for materials discovery in the broad class of intermetallics. This work opened new paths to compound formation. We discovered many new Si (or Ge)-based compounds with novel structures, bonding and physicochemical properties. We created new insights about the reaction chemistry that is responsible for stabilizing the new materials. We also studied the structural and compositional relationships to understand their properties. We investigated the use of Group-13 metals Al, Ga and In as solvents and have generated a wide variety of new results including several new ternary and quaternary materials with fascinating structures and properties as well as new insights as to how these systems are stabilized in the fluxes. The project focused on reactions of metals from the rare earth element family in combination with transition metals with Si and Ge. For example molten gallium has serves both as a reactive and non-reactive solvent in the preparation and crystallization of intermetallics in the system RE/M/Ga/Ge(Si). Molten indium behaves similarly in that it too is an excellent reaction medium, but it gives compounds that are different from those obtained from gallium. Some of the new phase identified in the aluminide class are complex phases and may be present in many advanced Al-matrix alloys. Such phases play a key role in determining (either beneficially or detrimentally) the mechanical properties of advanced Al-matrix alloys. This project enhanced our basic knowledge of the solid state chemistry

  14. Synthesis of first row transition metal carboxylate complexes by ring ...

    tion of pyromellitic dianhydride with methanol and ring opening of pyromellitic dianhydride takes place. The corresponding carboxylate complex formed dur- ing the process can be crystallised by adding biden- tate nitrogen donor ligands such as 1,10-phenanthroline or 2,2 - bipyridine.20 From the reaction with 1,10-.

  15. Calculation of electromagnetic force in electromagnetic forming process of metal sheet

    Xu Da; Liu Xuesong; Fang Kun; Fang Hongyuan

    2010-01-01

    Electromagnetic forming (EMF) is a forming process that relies on the inductive electromagnetic force to deform metallic workpiece at high speed. Calculation of the electromagnetic force is essential to understand the EMF process. However, accurate calculation requires complex numerical solution, in which the coupling between the electromagnetic process and the deformation of workpiece needs be considered. In this paper, an appropriate formula has been developed to calculate the electromagnetic force in metal work-piece in the sheet EMF process. The effects of the geometric size of coil, the material properties, and the parameters of discharge circuit on electromagnetic force are taken into consideration. Through the formula, the electromagnetic force at different time and in different positions of the workpiece can be predicted. The calculated electromagnetic force and magnetic field are in good agreement with the numerical and experimental results. The accurate prediction of the electromagnetic force provides an insight into the physical process of the EMF and a powerful tool to design optimum EMF systems.

  16. Fixation of metallic sulfosalicylate complexes on an anionic exchange resin

    Cahuzac, S.

    1969-06-01

    Since sulfosalicylate ions have acid-base properties, sulfosalicylate complexes have an apparent stability which varies with the ph. As a result, the fixation of sulfo-salicylates on an anionic exchange resin depends on the ph of the solution in equilibrium with the resin. This research has been aimed at studying the influence of the ph on the fixation on an anionic exchange resin (Dowex 1 x 4) of sulfosalicylate anions on the one hand, and of metallic sulfosalicylate complexes on the other hand. In the first part of this work, a determination has been made, by frontal analysis of the distribution of sulfosalicylate ions in the resin according to the total sulfosalicylate I concentration in the aqueous solution in equilibrium with the resin. The exchange constants of these ions between the resin and the solution have been calculated. In the second part, a study has been made of the fixation of anionic sulfosalicylate complexes of Fe(III), Al(III), Cr(III), Cu(II), Ni(II), Co(II), Zn(II), Mn(II), Cd(II), Fe(II) and UO 2 2+ . By measuring the partition coefficients of these different elements between the resin and the solution it has been possible to give interpretation for the modes of fixation of the metallic ions, and to calculate their exchange constant between the resin and the solution. The relationship has been established for each metallic element studied, between its partition coefficient, the ph and the total concentration of the complexing agent in solution. Such a relationship makes it possible to predict, for given conditions, the nature of the species in solution and in the resin, as well as the partition coefficient of a metallic, element. Finally, in the third part of the work, use has been made of results obtained previously, to carry out some separations (Ni 2+ - Co 2+ ; Ni 2+ - Co 2+ - Cu 2+ ; UO 2 2+ - Fe 3+ ; UO 2 2+ - Cr 3+ ; UO 2 2+ - Cu 2+ ; UO 2 2+ - Ni 2+ ; UO 2 2+ - Co 2+ ; UO 2 2+ - Mn 2+ and UO 2 2+ - Cd 2+ ), as well as the purification

  17. Rapid Prototyping by Single Point Incremental Forming of Sheet Metal

    Skjødt, Martin

    2008-01-01

    . The process is incremental forming since plastic deformation takes place in a small local zone underneath the forming tool, i.e. the sheet is formed as a summation of the movement of the local plastic zone. The process is slow and therefore only suited for prototypes or small batch production. On the other...... in the plastic zone. Using these it is demonstrated that the growth rate of accumulated damage in SPIF is small compared to conventional sheet forming processes. This combined with an explanation why necking is suppressed is a new theory stating that SPIF is limited by fracture and not necking. The theory...... SPIF. A multi stage strategy is presented which allows forming of a cup with vertical sides in about half of the depth. It is demonstrated that this results in strain paths which are far from straight, but strains are still limited by a straight fracture line in the principal strain space. The multi...

  18. Quadruple metal-metal bonds with strong donor ligands. Ultraviolet photoelectron spectroscopy of M{sub 2}(form){sub 4} (M = Cr, Mo, W; form = N,N{prime}-diphenylformamidinate)

    Lichtenberger, D.L.; Lynn, M.A.; Chisholm, M.H.

    1999-12-29

    The He I photoelectron spectra of M{sub 2}(form){sub 4}(M = Cr, Mo, W; form - N,N{prime}-diphenylformamidinate) and Mo{sub 2}(cyform){sub 4} (cyform = N,N{prime}-dicyclohexylformamidinate) are presented. For comparison, the Ne I, He I, and He II photoelectron spectra of Mo{sub 2}(p-CH{sub 3}-form){sub 4} have also been obtained. The valence ionization features of these molecules are interpreted based on (1) the changes that occur with the metal and ligand substitutions, (2) the changes in photoelectron cross sections with excitation source, and (3) the changes from previously studied dimetal complexes. These photoelectron spectra are useful for revealing the effects that better electron donor ligands have on the valence electronic structure of M{sub 2}(L-L){sub 4} systems. Comparison with the He I spectra of the isoelectronic M{sub 2}(O{sub 2}CCH{sub 3}){sub 4} compounds is particularly revealing. Unlike with the more electron-withdrawing acetate ligand, several formamidinate-based ionizations derived from the nitrogen p{sub {pi}} orbitals occur among the metal-metal {sigma}, {pi}, and {delta} ionization bands. Although these formamidinate-based levels are close in energy to the occupied metal-metal bonds, they have little direct mixing interaction with them. The shift of the metal-metal bond ionizations to lower ionization energies for the formamidinate systems is primarily a consequence of the lower electronegativity of the ligand and the better {pi} donation into empty metal levels. The metal-metal {delta} orbital experiences some additional net bonding interaction with ligand orbitals of the same symmetry. Also, an additional bonding interaction from ligand-to-metal electron donation to the {delta}* orbital is identified. These spectra suggest a greater degree of metal-ligand covalency than in the related M{sub 2}(O{sub 2}CCH{sub 3}){sub 4} systems. Fenske-Hall molecular orbital and density functional (ADF) calculations agree with the assignment and

  19. Chemodynamics of metal ion complexation by charged nanoparticles: a dimensionless rationale for soft, core-shell and hard particle types.

    Duval, Jérôme F L

    2017-05-17

    Soft nanoparticulate complexants are defined by a spatial confinement of reactive sites and electric charges inside their 3D body. In turn, their reactivity with metal ions differs significantly from that of simple molecular ligands. A revisited form of the Eigen mechanism recently elucidated the processes leading to metal/soft particle pair formation. Depending on e.g. particle size and metal ion nature, chemodynamics of nanoparticulate metal complexes is controlled by metal conductive diffusion to/from the particles, by intraparticulate complex formation/dissociation kinetics, or by both. In this study, a formalism is elaborated to achieve a comprehensive and systematic identification of the rate-limiting step governing the overall formation and dissociation of nanoparticulate metal complexes. The theory covers the different types of spherical particulate complexants, i.e. 3D soft/permeable and core-shell particles, and hard particles with reactive sites at the surface. The nature of the rate-limiting step is formulated by a dynamical criterion involving a power law function of the ratio between particle radius and an intraparticulate reaction layer thickness defined by the key electrostatic, diffusional and kinetic components of metal complex formation/dissociation. The analysis clarifies the intertwined contributions of particle properties (size, soft or hard type, charge, density or number of reactive sites) and aqueous metal ion dehydration kinetics in defining the chemodynamic behavior of nanoparticulate metal complexes. For that purpose, fully parameterized chemodynamic portraits involving the defining features of particulate ligand and metal ion as well as the physicochemical conditions in the local intraparticulate environment, are constructed and thoroughly discussed under conditions of practical interest.

  20. Complex forming properties of natural occurring fulvic acids

    Marinsky, J.A.; Mathuthu, A.; Bicking, M.; Ephraim, J.

    1985-07-01

    The experimental program developed in our earlier investigations of the protonation equilibria encountered with Armadale Horizons Bh and Suwannee River fulvic-acid has been employed in the present investigation of a Swedish fulvic acid source. Complications introduced by the polyelectrolyte nature and the degree of heterogeneity in the functional unit content of this natural organic acid molecule have been resolved as they were with the previous fulvic acid samples. The physical chemical properties of this fulvic acid have been compared with those resolved for the Armadale Horizons Bh and the Suwannee River fulvic acid as well. The insight gained from these protonation studies and metal ion binding studies, also carried out in the course of this investigation, has led to the development of a model for interpretation of the binding of metal ions to fulvic acid at any fulvic acid concentration level. With 12 refs. (Author)

  1. Complexation of metal ions with humic acid: charge neutralization model

    Kim, J.I.; Czerwinski, K.R.

    1995-01-01

    A number of different approaches are being used for describing the complexation equilibrium of actinide ions with humic or fulvic acid. The approach chosen and verified experimentally by Tu Muenchen will be discussed with notable examples from experiment. This approach is based on the conception that a given actinide ion is neutralized upon complexation with functional groups of humic or fulvic acid, e.g. carboxylic and phenolic groups, which are known as heterogeneously cross-linked polyelectrolytes. The photon energy transfer experiment with laser light excitation has shown that the actinide ion binding with the functional groups is certainly a chelation process accompanied by metal ion charge neutralization. This fact is in accordance with the experimental evidence of the postulated thermodynamic equilibrium reaction. The experimental results are found to be independent of origin of humic or fulvic acid and applicable for a broad range of pH. (authors). 23 refs., 7 figs., 1 tab

  2. Spectro Analytical, Computational and In Vitro Biological Studies of Novel Substituted Quinolone Hydrazone and it's Metal Complexes.

    Nagula, Narsimha; Kunche, Sudeepa; Jaheer, Mohmed; Mudavath, Ravi; Sivan, Sreekanth; Ch, Sarala Devi

    2018-01-01

    Some novel transition metal [Cu (II), Ni (II) and Co (II)] complexes of nalidixic acid hydrazone have been prepared and characterized by employing spectro-analytical techniques viz: elemental analysis, 1 H-NMR, Mass, UV-Vis, IR, TGA-DTA, SEM-EDX, ESR and Spectrophotometry studies. The HyperChem 7.5 software was used for geometry optimization of title compound in its molecular and ionic forms. Quantum mechanical parameters, contour maps of highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbitals (LUMO) and corresponding binding energy values were computed using semi empirical single point PM3 method. The stoichiometric equilibrium studies of metal complexes carried out spectrophotometrically using Job's continuous variation and mole ratio methods inferred formation of 1:2 (ML 2 ) metal complexes in respective systems. The title compound and its metal complexes screened for antibacterial and antifungal properties, exemplified improved activity in metal complexes. The studies of nuclease activity for the cleavage of CT- DNA and MTT assay for in vitro cytotoxic properties involving metal complexes exhibited high activity. In addition, the DNA binding properties of Cu (II), Ni (II) and Co (II) complexes investigated by electronic absorption and fluorescence measurements revealed their good binding ability and commended agreement of K b values obtained from both the techniques. Molecular docking studies were also performed to find the binding affinity of synthesized compounds with DNA (PDB ID: 1N37) and "Thymidine phosphorylase from E.coli" (PDB ID: 4EAF) protein targets.

  3. Investigation of fatigue strength of tool steels in sheet-bulk metal forming

    Pilz, F.; Gröbel, D.; Merklein, M.

    2018-05-01

    To encounter trends regarding an efficient production of complex functional components in forming technology, the process class of sheet-bulk metal forming (SBMF) can be applied. SBMF is characterized by the application of bulk forming operations on sheet metal, often in combination with sheet forming operations [1]. The combination of these conventional process classes leads to locally varying load conditions. The resulting load conditions cause high tool loads, which lead to a reduced tool life, and an uncontrolled material flow. Several studies have shown that locally modified tool surfaces, so-called tailored surfaces, have the potential to control the material flow and thus to increase the die filling of functional elements [2]. A combination of these modified tool surfaces and high tool loads in SBMF is furthermore critical for the tool life and leads to fatigue. Tool fatigue is hardly predictable and due to a lack of data [3], a challenge in tool design. Thus, it is necessary to provide such data for tool steels used in SBMF. The aim of this study is the investigation of the influence of tailored surfaces on the fatigue strength of the powder metallurgical tool steel ASP2023 (1.3344, AISI M3:2), which is typically used in cold forging applications, with a hardness 60 HRC ± 1 HRC. To conduct this investigation, the rotating bending test is chosen. As tailored surfaces, a DLC-coating and a surface manufactured by a high-feed-milling process are chosen. As reference a polished surface which is typical for cold forging tools is used. Before the rotating bending test, the surface integrity is characterized by measuring topography and residual stresses. After testing, the determined values of the surface integrity are correlated with the reached fracture load cycle to derive functional relations. Based on the gained results the investigated tailored surfaces are evaluated regarding their feasibility to modify tool surfaces within SBMF.

  4. Novel process chain for hot metal gas forming of ferritic stainless steel 1.4509

    Mosel, André; Lambarri, Jon; Degenkolb, Lars; Reuther, Franz; Hinojo, José Luis; Rößiger, Jörg; Eurich, Egbert; Albert, André; Landgrebe, Dirk; Wenzel, Holger

    2018-05-01

    Exhaust gas components of automobiles are often produced in ferritic stainless steel 1.4509 due to the low thermal expansion coefficient and the low material price. Until now, components of the stainless steel with complex geometries have been produced in series by means of multi-stage hydroforming at room temperature with intermediate annealing operations. The application of a single-stage hot-forming process, also referred to as hot metal gas forming (HMGF), offers great potential to significantly reduce the production costs of such components. The article describes a novel process chain for the HMGF process. Therefore the tube is heated in two steps. After pre-heating of the semi-finished product outside the press, the tube is heated up to forming start temperature by means of a tool-integrated conductive heating before forming. For the tube of a demonstrator geometry, a simulation model for the conduction heating was set up. In addition to the tool development for this process, experimental results are also described for the production of the demonstrator geometry.

  5. Supramolecular Complexes Formed in Systems Bile Salt-Bilirubin-Silica

    Vlasova, N. N.; Severinovskaya, O. V.; Golovkova, L. P.

    The formation of supramolecular complexes between bilirubin and primary micelles of bile salts has been studied. The association constants of bile salts and binding of bilirubin with these associates have been determined. The adsorption of bilirubin and bile salts from individual and mixed aqueous solutions onto hydrophobic silica surfaces has been investigated. The interaction of bilirubin with primary bile salt micelles and the strong retention in mixed micelles, which are supramolecular complexes, result in the adsorption of bilirubin in free state only.

  6. Oxidation kinetics of reaction products formed in uranium metal corrosion

    Totemeier, T. C.

    1998-01-01

    The oxidation behavior of uranium metal ZPPR fuel corrosion products in environments of Ar-4%O 2 and Ar-20%O 2 were studied using thermo-gravimetric analysis (TGA). These tests were performed to extend earlier work in this area specifically, to assess plate-to-plate variations in corrosion product properties and the effect of oxygen concentration on oxidation behavior. The corrosion products from two relatively severely corroded plates were similar, while the products from a relatively intact plate were not reactive. Oxygen concentration strongly affected the burning rate of reactive products, but had little effect on low-temperature oxidation rates

  7. Oxidation kinetics of reaction products formed in uranium metal corrosion.

    Totemeier, T. C.

    1998-04-22

    The oxidation behavior of uranium metal ZPPR fuel corrosion products in environments of Ar-4%O{sub 2} and Ar-20%O{sub 2} were studied using thermo-gravimetric analysis (TGA). These tests were performed to extend earlier work in this area specifically, to assess plate-to-plate variations in corrosion product properties and the effect of oxygen concentration on oxidation behavior. The corrosion products from two relatively severely corroded plates were similar, while the products from a relatively intact plate were not reactive. Oxygen concentration strongly affected the burning rate of reactive products, but had little effect on low-temperature oxidation rates.

  8. Complexing agent and heavy metal removals from metal plating effluent by electrocoagulation with stainless steel electrodes.

    Kabdaşli, Işik; Arslan, Tülin; Olmez-Hanci, Tuğba; Arslan-Alaton, Idil; Tünay, Olcay

    2009-06-15

    In the present study, the treatability of a metal plating wastewater containing complexed metals originating from the nickel and zinc plating process by electrocoagulation using stainless steel electrodes was experimentally investigated. The study focused on the effect of important operation parameters on electrocoagulation process performance in terms of organic complex former, nickel and zinc removals as well as sludge production and specific energy consumption. The results indicated that increasing the applied current density from 2.25 to 9.0 mA/cm(2) appreciably enhanced TOC removal efficiency from 20% to 66%, but a further increase in the applied current density to 56.25 mA/cm(2) did not accelerate TOC removal rates. Electrolyte concentration did not affect the process performance significantly and the highest TOC reduction (66%) accompanied with complete heavy metal removals were achieved at the original chloride content ( approximately 1500 mg Cl/L) of the wastewater sample. Nickel removal performance was adversely affected by the decrease of initial pH from its original value of 6. Optimum working conditions for electrocoagulation of metal plating effluent were established as follows: an applied current density of 9 mA/cm(2), the effluent's original electrolyte concentration and pH of the composite sample. TOC removal rates obtained for all electrocoagulation runs fitted pseudo-first-order kinetics very well (R(2)>92-99).

  9. Reversible photochromic system based on rhodamine B salicylaldehyde hydrazone metal complex.

    Li, Kai; Xiang, Yu; Wang, Xiaoyan; Li, Ji; Hu, Rongrong; Tong, Aijun; Tang, Ben Zhong

    2014-01-29

    Photochromic molecules are widely applied in chemistry, physics, biology, and materials science. Although a few photochromic systems have been developed before, their applications are still limited by complicated synthesis, low fatigue resistance, or incomplete light conversion. Rhodamine is a class of dyes with excellent optical properties including long-wavelength absorption, large absorption coefficient, and high photostability in its ring-open form. It is an ideal chromophore for the development of new photochromic systems. However, known photochromic rhodamine derivatives, such as amides, exhibit only millisecond lifetimes in their colored ring-open forms, making their application very limited and difficult. In this work, rhodamine B salicylaldehyde hydrazone metal complex was found to undergo intramolecular ring-open reactions upon UV irradiation, which led to a distinct color and fluorescence change both in solution and in solid matrix. The complex showed good fatigue resistance for the reversible photochromism and long lifetime for the ring-open state. Interestingly, the thermal bleaching rate was tunable by using different metal ions, temperatures, solvents, and chemical substitutions. It was proposed that UV light promoted isomerization of the rhodamine B derivative from enol-form to keto-form, which induced ring-opening of the rhodamine spirolactam in the complex to generate color. The photochromic system was successfully applied for photoprinting and UV strength measurement in the solid state. As compared to other reported photochromic molecules, the system in this study has its advantages of facile synthesis and tunable thermal bleaching rate, and also provides new insights into the development of photochromic materials based on metal complex and spirolactam-containing dyes.

  10. Humic substances in natural waters and their complexation with trace metals and radionuclides: a review. [129 references

    Boggs, S. Jr.; Livermore, D.; Seitz, M.G.

    1985-07-01

    Dissolved humic substances (humic and fulvic acids) occur in surface waters and groundwaters in concentrations ranging from less than 1 mg(C)/L to more than 100 mg(C)/L. Humic substances are strong complexing agents for many trace metals in the environment and are also capable of forming stable soluble complexes or chelates with radionuclides. Concentrations of humic materials as low as 1 mg(C)/L can produce a detectable increase in the mobility of some actinide elements by forming soluble complexes that inhibit sorption of the radionuclides onto rock materials. The stability of trace metal- or radionuclide-organic complexes is commonly measured by an empirically determined conditional stability constant (K'), which is based on the ratio of complexed metal (radionuclide) in solution to the product concentration of uncomplexed metal and humic complexant. Larger values of stability constants indicate greater complex stability. The stability of radionuclide-organic complexes is affected both by concentration variables and envionmental factors. In general, complexing is favored by increased of radionuclide, increased pH, and decreased ionic strength. Actinide elements are generally most soluble in their higher oxidation states. Radionuclides can also form stable, insoluble complexes with humic materials that tend to reduce radionuclide mobility. These insoluble complexes may be radionuclide-humate colloids that subsequently precipitate from solution, or complexes of radionuclides and humic substances that sorb to clay minerals or other soil particulates strongly enough to immobilize the radionuclides. Colloid formation appears to be favored by increased radionuclide concentration and lowered pH; however, the conditions that favor formation of insoluble complexes that sorb to particulates are still poorly understood. 129 refs., 25 figs., 19 tabs.

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

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

    1985-01-01

    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 4 - , 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 4 - 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

  12. Equation of limiting plasticity of the metal upon complex stress state

    Tin'gaev, A.K.

    2002-01-01

    A method for evaluation of the limiting plasticity of the metal in the zones of complex 3D stress state is presented. An analytic equation is derived for limiting plasticity. Parameters of the equation are expresses through the standard characteristics of the mechanical properties determined upon static tension of the smooth sample. Introduced into the obtained analytical equation is a universal fracture constant which indirectly characterizes the state of the material from the point of view of its capacity for elastic overstrain relaxation in the form of plastic flow or fracture. The new equation makes it possible to estimate the limiting plasticity of the metal in a state of complex stress on the basis of traditional characteristics of mechanical properties, which are not difficult to determine [ru

  13. Characteristics of metal waste forms containing technetium and uranium

    Fortner, J.A.; Kropf, A.J.; Ebert, W.L. [Argonne National Laboratory, Argonne, IL 60439 (United States)

    2013-07-01

    2 prototype alloys: RAW-1(Tc) and RAW-2(UTc) suitable for a wide range of waste stream compositions are being evaluated to support development of a waste form degradation model that can be used to calculate radionuclide source terms for a range of waste form compositions and disposal environments. Tests and analyses to support formulation of waste forms and development of the degradation model include detailed characterizations of the constituent phases using SEM/EDS and TEM, electrochemical tests to quantify the oxidation behavior and kinetics of the individual and coupled phases under a wide range of environmental conditions, and corrosion tests to measure the gross release kinetics of radionuclides under aggressive test conditions.

  14. Corrosion resistant amorphous metals and methods of forming corrosion resistant amorphous metals

    Farmer, Joseph C [Tracy, CA; Wong, Frank M. G. [Livermore, CA; Haslam, Jeffery J [Livermore, CA; Yang, Nancy [Lafayette, CA; Lavernia, Enrique J [Davis, CA; Blue, Craig A [Knoxville, TN; Graeve, Olivia A [Reno, NV; Bayles, Robert [Annandale, VA; Perepezko, John H [Madison, WI; Kaufman, Larry [Brookline, MA; Schoenung, Julie [Davis, CA; Ajdelsztajn, Leo [Walnut Creek, CA

    2009-11-17

    A system for coating a surface comprises providing a source of amorphous metal, providing ceramic particles, and applying the amorphous metal and the ceramic particles to the surface by a spray. The coating comprises a composite material made of amorphous metal that contains one or more of the following elements in the specified range of composition: yttrium (.gtoreq.1 atomic %), chromium (14 to 18 atomic %), molybdenum (.gtoreq.7 atomic %), tungsten (.gtoreq.1 atomic %), boron (.ltoreq.5 atomic %), or carbon (.gtoreq.4 atomic %).

  15. Metastability and thermophysical properties of metallic bulk glass forming alloys

    Wunderlich, R.K.; Fecht, H.J.

    1998-01-01

    The absence of crystallization over a wide time/temperature window can be used to produce bulk metallic glass by relatively slow cooling of the melt. For a number of alloys, including several multicomponent Zr-based alloys, the relevant thermodynamic and thermomechanical properties of the metastable glassy and undercooled liquid states have been measured below and above the glass transition temperature. These measurements include specific heat, viscosity, volume, and elastic properties as a function of temperature. As a result, it becomes obvious that the maximum undercooling for these alloys is given by an isentropic condition before an enthalpic or isochoric instability is reached. Alternatively, these glasses can also be produced by mechanical alloying, thus replacing the thermal disorder by static disorder and resulting in the same thermodynamic glass state. During heating through the undercooled liquid, a nanoscale phase separation occurs for most glasses as a precursor of crystallization

  16. Leaching characteristics of the metal waste form from the electrometallurgical treatment process: Product consistency testing

    Johnson, S. G.; Keiser, D. D.; Frank, S. M.; DiSanto, T.; Noy, M.

    1999-01-01

    Argonne National Laboratory is developing an electrometallurgical treatment for spent fuel from the experimental breeder reactor II. A product of this treatment process is a metal waste form that incorporates the stainless steel cladding hulls, zirconium from the fuel and the fission products that are noble to the process, i.e., Tc, Ru, Nb, Pd, Rh, Ag. The nominal composition of this waste form is stainless steel/15 wt% zirconium/1--4 wt% noble metal fission products/1--2 wt % U. Leaching results are presented from several tests and sample types: (1) 2 week monolithic immersion tests on actual metal waste forms produced from irradiated cladding hulls, (2) long term (>2 years) pulsed flow tests on samples containing technetium and uranium and (3) crushed sample immersion tests on cold simulated metal waste form samples. The test results will be compared and their relevance for waste form product consistency testing discussed

  17. Deposited Micro Porous Layer as Lubricant Carrier in Metal Forming

    Arentoft, Mogens; Bay, Niels; Tang, Peter Torben

    2008-01-01

    as lubricant reservoirs. Conventional friction tests for cold forming; ring compression and double cup extrusion tests are carried out with Molykote DX paste and mineral oil as lubricant. Both lubricants act as intended for the ring compressions test whereas only the low viscosity oil perform successfully...... in the cup extrusion test. For all specimens without the porous coating, high friction conditions are identified....

  18. Contour forming of various metals--deformation and recrystallization characteristics

    Muller, J.F.

    1978-01-01

    The effects of different forming and annealing sequences on resultant grain size were investigated for several materials. Deep drawing as well as forging techniques were employed during the course of this study. One evaluation was additionally performed to determine the contribution of size effects

  19. Hybrid plasmonic waveguides formed by metal coating of dielectric ridges

    Zenin, Volodymyr; Choudhury, Sajid; Saha, Soham

    2017-01-01

    Bound hybrid plasmon-polariton modes supported by waveguides, which are formed by gold coating of ridges etched into a silica substrate, are analyzed using numerical simulations and investigated experimentally using near-field microscopy at telecom wavelengths (1425-1625 nm). Drastic modification...

  20. Efficient implicit FEM simulation of sheet metal forming

    van den Boogaard, Antonius H.; Meinders, Vincent T.; Huetink, Han

    2003-01-01

    For the simulation of industrial sheet forming processes, the time discretisation is one of the important factors that determine the accuracy and efficiency of the algorithm. For relatively small models, the implicit time integration method is preferred, because of its inherent equilibrium check.

  1. IRMPD Action Spectroscopy of Alkali Metal Cation-Cytosine Complexes: Effects of Alkali Metal Cation Size on Gas Phase Conformation

    Yang, B.; Wu, R.R.; Polfer, N.C.; Berden, G.; Oomens, J.; Rodgers, M.T.

    2013-01-01

    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both

  2. Tool Monitoring and Electronic Event Logging for Sheet Metal Forming Processes

    Gerd Heiserich

    2010-06-01

    Full Text Available This contribution describes some innovative solutions regarding sensor systems for tool monitoring in the sheet metal industry. Autonomous and tamper-proof sensors, which are integrated in the forming tools, can detect and count the strokes carried out by a sheet metal forming press. Furthermore, an electronic event logger for documentary purposes and quality control was developed. Based on this technical solution, new business models such as leasing of sheet metal forming tools can be established for cooperation among enterprises. These models allow usage-based billing for the contractors, taking the effectively produced number of parts into account.

  3. Phosphorylated derivatives of anabasine: synthesis, constitution and complex forming properties

    Babaev, B.N.

    2004-01-01

    Full text: With the purpose of detection of new effective extra gents of metals from number of sulphur containing derivatives of acids of phosphorus with different functional groups, analysis of effect of the different factors on selectivity of allocation of metals, installation of optimum conditions of an extraction, the detections of effective extra gents of noble metals from industrial sewage waters, are synthesized phosphorylated derivatives of the anabasine - O-alkyl-O-(anaba-sinoisopropyl)- and O-alkyl-O-(anabasinobutyn-2-yl)phenyl phosphonates and O-(anabasinoisopropyl)- and O-(anabasinobutyn-2-yl)diphenyl phosphonates In an IR-spectrum about O-pentyl-O-[anabasinoisopropyl]phenylphosphonate There are absorption band of the following functional groups (ν, cm -1 ): (P-O-C 5 H 11 ) 990-1000, (P = 0) 1250, (P-C 6 H 5 )1450, (C-N in cycle) 1550. In a spectrum PMR O-(anabasinobutyn-2-yl)phenylphosphonate in the field of a weak field apart from signals of two phenylic radicals the signals of a b-displaced pyridine, reference for a molecule anabasine are observed: Hαa-8,46 p.m., H α '-8,41 p.m., H γ -7,60 p.m. And H β -7,15 p.m. A double triplet at 4,70 p.m. And triplet at 3,05 p.m. Belong to signals OCH 2 and N-CH 2 of groups, accordingly, separated by acetylene bond. The signals of piperidine cycle of anabasine have the following chemical shifts: H 2a -3,27 p.m., H 6e -2,78 p.m., H 6a -2,45 p.m., and remaining protons (6H, m, CH 2 ) are in resonance in the field of 1,1-1,9 p.m. The analysis of mass-spectrometer decay of the synthesized connections has shown, that the mass-spectrometer fragmentation M * about - O-alkyl-O- (anabasinoisopropyl) phenylphosphonates flows past in different directions and is characterized, as against about O-alkyl-O-(anabasinobutyn-2-yl)phenyl-phosphonates, large number of phosphor containing ions; the availability of the second phenylic radical in molecules anabasincontaining derivatives of a diphenyl phosphinic acid essentially

  4. Bulk forming of industrial micro components in conventional metals and bulk metallic glasses

    Arentoft, Mogens; Paldan, Nikolas Aulin; Eriksen, Rasmus Solmer

    2007-01-01

    For production of micro components in large numbers, forging is an interesting and challenging process. The conventional metals like silver, steel and aluminum often require multi-step processes, but high productivity and increased strength justify the investment. As an alternative, bulk metallic...

  5. Increasing the Robustness of the Sheet Metal Forming Simulation by the Prediction of the Forming Limit Band

    Banabic, D.; Vos, M.; Paraianu, L.; Jurco, P.

    2007-05-01

    The experimental research on the formability of metal sheets has shown that there is a significant dispersion of the limit strains in an area delimited by two curves: a lower curve (LFLC) and an upper one (UFLC). The region between the two curves defines the so-called Forming Limit Band (FLB). So far, this forming band has only been determined experimentally. In this paper the authors suggested a method to predict the Forming Limit Band. The proposed method is illustrated on the AA6111-T43 aluminium alloy.

  6. Increasing the Robustness of the Sheet Metal Forming Simulation by the Prediction of the Forming Limit Band

    Banabic, D.; Paraianu, L.; Vos, M.; Jurco, P.

    2007-01-01

    The experimental research on the formability of metal sheets has shown that there is a significant dispersion of the limit strains in an area delimited by two curves: a lower curve (LFLC) and an upper one (UFLC). The region between the two curves defines the so-called Forming Limit Band (FLB). So far, this forming band has only been determined experimentally. In this paper the authors suggested a method to predict the Forming Limit Band. The proposed method is illustrated on the AA6111-T43 aluminium alloy

  7. Semi-solid metal forming of beryllium-reinforced aluminum alloys

    Haws, W.; Lane, L.; Marder, J.; Nicholas, N.

    1995-01-01

    A Powder Metallurgy (PM) based, Semi-Solid Metal (SSM) forming process has been developed to produce low cost near-net shapes of beryllium-reinforced aluminum alloys. Beryllium acts as a reinforcing additive to the aluminum, in which there is nearly no mutual solid solubility. The modulus of elasticity of the alloy dramatically increases, while the density and thermal expansion coefficient decrease with increasing beryllium content. The material is suitable for complex thermal management and vibration resistance applications, as well as for airborne components which are density and stiffness sensitive. The forming process involves heating a blank of the material to a temperature at which the aluminum is semi-solid and the beryllium is solid. The semi-solid blank is then injected without turbulence into a permanent mold. High quality, near net shape components can be produced which are functionally superior to those produced by other permanent mold processes. Dimensional accuracy is equivalent to or better than that obtained in high pressure die casting. Cost effectiveness is the primary advantage of this technique compared to other forming processes. The advantages and limitations of the process are described. Physical and mechanical property data are presented, as well as directions for future investigation

  8. Sequential optimization and reliability assessment method for metal forming processes

    Sahai, Atul; Schramm, Uwe; Buranathiti, Thaweepat; Chen Wei; Cao Jian; Xia, Cedric Z.

    2004-01-01

    Uncertainty is inevitable in any design process. The uncertainty could be due to the variations in geometry of the part, material properties or due to the lack of knowledge about the phenomena being modeled itself. Deterministic design optimization does not take uncertainty into account and worst case scenario assumptions lead to vastly over conservative design. Probabilistic design, such as reliability-based design and robust design, offers tools for making robust and reliable decisions under the presence of uncertainty in the design process. Probabilistic design optimization often involves double-loop procedure for optimization and iterative probabilistic assessment. This results in high computational demand. The high computational demand can be reduced by replacing computationally intensive simulation models with less costly surrogate models and by employing Sequential Optimization and reliability assessment (SORA) method. The SORA method uses a single-loop strategy with a series of cycles of deterministic optimization and reliability assessment. The deterministic optimization and reliability assessment is decoupled in each cycle. This leads to quick improvement of design from one cycle to other and increase in computational efficiency. This paper demonstrates the effectiveness of Sequential Optimization and Reliability Assessment (SORA) method when applied to designing a sheet metal flanging process. Surrogate models are used as less costly approximations to the computationally expensive Finite Element simulations

  9. Determining the magnitude and direction of photoinduced ligand field switching in photochromic metal-organic complexes: molybdenum-tetracarbonyl spirooxazine complexes.

    Paquette, Michelle M; Patrick, Brian O; Frank, Natia L

    2011-07-06

    The ability to optically switch or tune the intrinsic properties of transition metals (e.g., redox potentials, emission/absorption energies, and spin states) with photochromic metal-ligand complexes is an important strategy for developing "smart" materials. We have described a methodology for using metal-carbonyl complexes as spectroscopic probes of ligand field changes associated with light-induced isomerization of photochromic ligands. Changes in ligand field between the ring-closed spirooxazine (SO) and ring-opened photomerocyanine (PMC) forms of photochromic azahomoadamantyl and indolyl phenanthroline-spirooxazine ligands are demonstrated through FT-IR, (13)C NMR, and computational studies of their molybdenum-tetracarbonyl complexes. The frontier molecular orbitals (MOs) of the SO and PMC forms differ considerably in both electron density distributions and energies. Of the multiple π* MOs in the SO and PMC forms of the ligands, the LUMO+1, a pseudo-b(1)-symmetry phenanthroline-based MO, mixes primarily with the Mo(CO)(4) fragment and provides the major pathway for Mo(d)→phen(π*) backbonding. The LUMO+1 is found to be 0.2-0.3 eV lower in energy in the SO form relative to the PMC form, suggesting that the SO form is a better π-acceptor. Light-induced isomerization of the photochromic ligands was therefore found to lead to changes in the energies of their frontier MOs, which in turn leads to changes in π-acceptor ability and ligand field strength. Ligand field changes associated with photoisomerizable ligands allow tuning of excited-state and ground-state energies that dictate energy/electron transfer, optical/electrical properties, and spin states of a metal center upon photoisomerization, positioning photochromic ligand-metal complexes as promising targets for smart materials.

  10. Frustration across the periodic table: heterolytic cleavage of dihydrogen by metal complexes.

    Bullock, R Morris; Chambers, Geoffrey M

    2017-08-28

    This perspective examines frustrated Lewis pairs (FLPs) in the context of heterolytic cleavage of H 2 by transition metal complexes, with an emphasis on molecular complexes bearing an intramolecular Lewis base. FLPs have traditionally been associated with main group compounds, yet many reactions of transition metal complexes support a broader classification of FLPs that includes certain types of transition metal complexes with reactivity resembling main group-based FLPs. This article surveys transition metal complexes that heterolytically cleave H 2 , which vary in the degree that the Lewis pairs within these systems interact. Many of the examples include complexes bearing a pendant amine functioning as the base with the metal functioning as the hydride acceptor. Consideration of transition metal compounds in the context of FLPs can inspire new innovations and improvements in transition metal catalysis.This article is part of the themed issue 'Frustrated Lewis pair chemistry'. © 2017 The Author(s).

  11. Failure mechanisms in single-point incremental forming of metals

    Silva, Maria B.; Nielsen, Peter Søe; Bay, Niels

    2011-01-01

    The last years saw the development of two different views on how failure develops in single-point incremental forming (SPIF). Today, researchers are split between those claiming that fracture is always preceded by necking and those considering that fracture occurs with suppression of necking. Each...... on formability limits and development of fracture. The unified view conciliates the aforementioned different explanations on the role of necking in fracture and is consistent with the experimental observations that have been reported in the past years. The work is performed on aluminium AA1050-H111 sheets...

  12. Copper Benzenetricarboxylate Metal-Organic Framework Nucleation Mechanisms on Metal Oxide Powders and Thin Films formed by Atomic Layer Deposition.

    Lemaire, Paul C; Zhao, Junjie; Williams, Philip S; Walls, Howard J; Shepherd, Sarah D; Losego, Mark D; Peterson, Gregory W; Parsons, Gregory N

    2016-04-13

    Chemically functional microporous metal-organic framework (MOF) crystals are attractive for filtration and gas storage applications, and recent results show that they can be immobilized on high surface area substrates, such as fiber mats. However, fundamental knowledge is still lacking regarding initial key reaction steps in thin film MOF nucleation and growth. We find that thin inorganic nucleation layers formed by atomic layer deposition (ALD) can promote solvothermal growth of copper benzenetricarboxylate MOF (Cu-BTC) on various substrate surfaces. The nature of the ALD material affects the MOF nucleation time, crystal size and morphology, and the resulting MOF surface area per unit mass. To understand MOF nucleation mechanisms, we investigate detailed Cu-BTC MOF nucleation behavior on metal oxide powders and Al2O3, ZnO, and TiO2 layers formed by ALD on polypropylene substrates. Studying both combined and sequential MOF reactant exposure conditions, we find that during solvothermal synthesis ALD metal oxides can react with the MOF metal precursor to form double hydroxy salts that can further convert to Cu-BTC MOF. The acidic organic linker can also etch or react with the surface to form MOF from an oxide metal source, which can also function as a nucleation agent for Cu-BTC in the mixed solvothermal solution. We discuss the implications of these results for better controlled thin film MOF nucleation and growth.

  13. Structural and thermal characterization of ternary complexes of piroxicam and alanine with transition metals: Uranyl binary and ternary complexes of piroxicam. Spectroscopic characterization and properties of metal complexes

    Mohamed, Gehad G.

    2005-12-01

    Ternary Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and UO 2(II) complexes with piroxicam (Pir) drug (H 2L 1) and dl-alanine (Ala) (HL 2) and also the binary UO 2(II) complex with Pir were studied. The structures of the complexes were elucidated using elemental, IR, molar conductance, magnetic moment, diffused reflectance and thermal analyses. The UO 2(II) binary complex was isolated in 1:2 ratio with the formula [UO 2(H 2L) 2](NO 3) 2. The ternary complexes were isolated in 1:1:1 (M:H 2L 1:L 2) ratios. The solid complexes were isolated in the general formulae [M(H 2L)(L 2)(Cl) n(H 2O) m]· yH 2O (M = Fe(III) ( n = 2, m = 0, y = 1), Co(II) ( n = 1, m = 1, y = 2) and Ni(II) ( n = 1, m = 1, y = 0)); [M(H 2L)(L 2)](X) z· yH 2O (M = Cu(II) (X = AcO, z = 1, y = 0), Zn(II) (X = AcO, z = 1, y = 3) and UO 2(II) (X = NO 3, z = 1, y = 2)). Pir behaves as a neutral bidentate ligand coordinated to the metal ions via the pyridine-N and carbonyl-O groups, while Ala behaves as a uninegatively bidentate ligand coordinated to the metal ions via the deprotonated carboxylate-O and amino-N. The magnetic and reflectance spectral data show that the complexes have octahedral geometry except Cu(II) and Zn(II) complexes have tetrahedral structures. The thermal decomposition of the complexes was discussed in relation to structure, and the thermodynamic parameters of the decomposition stages were evaluated.

  14. Solving optimisation problems in metal forming using Finite Element simulation and metamodelling techniques

    Bonte, M.H.A.; van den Boogaard, Antonius H.; Huetink, Han

    2005-01-01

    During the last decades, Finite Element (FEM) simulations of metal forming processes have become important tools for designing feasible production processes. In more recent years, several authors recognised the potential of coupling FEM simulations to mathematical optimisation algorithms to design

  15. Neutron diffraction studies of transition metal hydride complexes

    Koetzle, T.F.; Bau, R.

    1976-01-01

    Investigations of H 3 Ta(C 5 H 5 ) 2 (III), HW 2 (CO) 9 (NO) (IV), and HW 2 (CO) 8 (NO) (P(OCH 3 ) 3 ) (V) have been completed. Preliminary results are available for HFeCo 3 (CO) 9 [P(OCH 3 ) 3 ] 3 (VII). This work, together with studies of HMo 2 (C 5 H 5 ) 2 (CO) 4 (P(CH 3 ) 2 ) (VI) and [(C 2 H 5 ) 4 N] + [HCr 2 (CO) 10 ] - carried out at Argonne has led to some general observations on the geometry and the nature of bonding in these compounds. For example, in the structures of IV and V, both of which have bent W--H--W linkages (less than W--H--W in the range 125-130 0 ), there is conclusive evidence for the existence of a closed three-center W--H--W bond with significant metal-metal interaction. Such is the case, because extensions of the axial W--C and W--N bonds trans to the hydride intersect at a point near the center of the W--H--W triangle. The geometry of VI, which also contains a bent M--H--M bond, is consistent with that of IV and V. Bridging M--H bonds in these second- and third-row hydrides range in length from 1.85 to 1.89 A, compared to 1.75 A in the first-row polynuclear complex VII. For metals of corresponding rows, bridging M--H bonds are about 0.1 A longer than terminal bonds, which are classified as single covalent bonds

  16. Derivatized Pentadentate Macrocyclic Ligands and Their Transition Metal Complexes

    Muhammad S. Khan

    2002-06-01

    Full Text Available The reaction of the pendant hydroxyethyl group in the planar pentadentate macrocyclic ligand,1,11-bis(2’-hydroxyethyl-4,8;12,16;17,21-trinitrilo-1,2,10,11-tetraazacyclohenicosa- 2,4,6,9,12,14,18,20-octaene (L2, derived from the condensation of 2,6-pyridinedialdehyde with 6,6’-bis(2’ hydroxyethylhydrazino -2,2’-bipyridine (L1, has been investigated. Esterification reactions are facile, and the reaction of the hydroxyethyl-substituted macrocycle with thionyl chloride yields a chloroethyl derivative. Metal complexes of the new derivatized macrocyclic ligands L3-6having general formula ML3-6X2.nH2O (M = Mn, Fe, Co, Ni, Cu, Zn are readily prepared.

  17. Electron spin resonance of radicals and metal complexes

    1993-01-01

    The materials are a collection of extended synopsis of papers presented at the conference sessions. The broad area of magnetic techniques applications has been described as well as their spectra interpretation methods. The ESR, NMR, ENDOR and spin echo were applied for studying the radiation and UV induced radicals in chemical and biological systems. Also in the study of complexes of metallic ions (having the paramagnetic properties) and their interaction with the matrix, the magnetic techniques has been commonly used. They are also very convenient tool for the study of reaction kinetics and mechanism as well as interaction of paramagnetic species with themselves and crystal lattice or with the surface as for thee catalytic processes

  18. Friction and solid-solid adhesion on complex metallic alloys

    Dubois, Jean-Marie; Belin-Ferré, Esther

    2014-01-01

    The discovery in 1987 of stable quasicrystals in the Al–Cu–Fe system was soon exploited to patent specific coatings that showed reduced friction in ambient air against hard antagonists. Henceforth, it was possible to develop a number of applications, potential or commercially exploited to date, that will be alluded to in this topical review. A deeper understanding of the characteristics of complex metallic alloys (CMAs) may explain why material made of metals like Al, Cu and Fe offers reduced friction; low solid–solid adhesion came later. It is linked to the surface energy being significantly lower on those materials, in which translational symmetry has become a weak property, that is determined by the depth of the pseudo-gap at the Fermi energy. As a result, friction is anisotropic in CMAs that builds up according to the translation symmetry along one direction, but is aperiodic along the other two directions. A review is given in this article of the most salient data found along these lines during the past two decades or so. PMID:27877675

  19. Structural, theoretical and corrosion inhibition studies on some transition metal complexes derived from heterocyclic system

    Gupta, Shraddha Rani; Mourya, Punita; Singh, M. M.; Singh, Vinod P.

    2017-06-01

    A Schiff base, (E)-N‧-((1H-indol-3-yl)methylene)-2-aminobenzohydrazide (Iabh) and its Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes have been synthesized. These compounds have been characterized by different physico-chemical and spectroscopic tools (UV-Vis, IR, NMR and ESI-Mass). The molecular structure of Iabh is determined by single crystal X-ray diffraction technique. The ligand Iabh displays E-configuration about the >Cdbnd N- bond. The structure of ligand is stabilized by intra-molecular H-bonding. In all the metal complexes the ligand coordinates through azomethine-N and carbonyl-O resulting a distorted octahedral geometry for Mn(II), Co(II) and Cu(II) complexes in which chloride ions occupy axial positions. Ni(II) and Zn(II) complexes, however, form 4-coordinate distorted square planer and tetrahedral geometry around metal ion, respectively. The structures of the complexes have been satisfactorily modeled by calculations based on density functional theory (DFT) and time dependent-DFT (TD-DFT). The corrosion inhibition study of the compounds have been performed against mild steel in 0.5 M H2SO4 solution at 298 K by using weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). They show appreciable corrosion inhibition property.

  20. Structure-activity relationships of mononuclear metal-thiosemicarbazone complexes endowed with potent antiplasmodial and antiamoebic activities.

    Bahl, Deepa; Athar, Fareeda; Soares, Milena Botelho Pereira; de Sá, Matheus Santos; Moreira, Diogo Rodrigo Magalhães; Srivastava, Rajendra Mohan; Leite, Ana Cristina Lima; Azam, Amir

    2010-09-15

    A useful concept for the rational design of antiparasitic drug candidates is the complexation of bioactive ligands with transition metals. In view of this, an investigation was conducted into a new set of metal complexes as potential antiplasmodium and antiamoebic agents, in order to examine the importance of metallic atoms, as well as the kind of sphere of co-ordination, in these biological properties. Four functionalized furyl-thiosemicarbazones (NT1-4) treated with divalent metals (Cu, Co, Pt, and Pd) to form the mononuclear metallic complexes of formula [M(L)2Cl2] or [M(L)Cl2] were examined. The pharmacological characterization, including assays against Plasmodium falciparum and Entamoeba histolytica, cytotoxicity to mammalian cells, and interaction with pBR 322 plasmid DNA was performed. Structure-activity relationship data revealed that the metallic complexation plays an essential role in antiprotozoal activity, rather than the simple presence of the ligand or metal alone. Important steps towards identification of novel antiplasmodium (NT1Cu, IC50 of 4.6 microM) and antiamoebic (NT2Pd, IC50 of 0.6 microM) drug prototypes were achieved. Of particular relevance to this work, these prototypes were able to reduce the proliferation of these parasites at concentrations that are not cytotoxic to mammalian cells. Copyright (c) 2010. Published by Elsevier Ltd.

  1. The role of microorganisms in the mobility of radionuclides in soil II. Evaluation of siderophone-cation complex forming capacity

    Konyi, J.; Koska, P.; Berzsenyi, G.; Gazso, L.G.; Appanna, V.D.

    1997-01-01

    Siderophores are cation binding agents produced by microorganisms. They are specific for Fe(III) but may bind other cations, too. Gram positive bacteria, Gram negative bacteria, filamentous bacteria and fungi isolated from soil samples were examined for siderophore production using chrome-asurol agar plates. We found that 44.5% of the isolates are able to produce siderophores. Spectral analysis of the produced exudates shoved cobalt and zinc binding capacity. Adding of a strong complexing agent (EDDHA) does not influence the stability of the formed metal-complex. (authors)

  2. Metallic elements in fossil fuel combustion products: amounts and form of emissions and evaluation of carcinogenicity and mutagenicity.

    Vouk, V B; Piver, W T

    1983-01-01

    Metallic elements contained in coal, oil and gasoline are mobilized by combustion processes and may be emitted into the atmosphere, mainly as components of submicron particles. The information about the amounts, composition and form of metal compounds is reviewed for some fuels and combustion processes. Since metal compounds are always contained in urban air pollutants, they have to be considered whenever an evaluation of biological impact of air pollutants is made. The value of currently used bioassays for the evaluation of the role of trace metal compounds, either as major biologically active components or as modifiers of biological effects of organic compounds is assessed. The whole animal bioassays for carcinogenicity do not seem to be an appropriate approach. They are costly, time-consuming and not easily amenable to the testing of complex mixtures. Some problems related to the application and interpretation of short-term bioassays are considered, and the usefulness of such bioassays for the evaluation of trace metal components contained in complex air pollution mixtures is examined.

  3. Complex band structures of transition metal dichalcogenide monolayers with spin–orbit coupling effects

    Szczęśniak, Dominik; Ennaoui, Ahmed; Ahzi, Saïd

    2016-01-01

    Recently, the transition metal dichalcogenides have attracted renewed attention due to the potential use of their low-dimensional forms in both nano- and opto-electronics. In such applications, the electronic and transport properties of monolayer transition metal dichalcogenides play a pivotal role. The present paper provides a new insight into these essential properties by studying the complex band structures of popular transition metal dichalcogenide monolayers (MX 2 , where M   =  Mo, W; X   =  S, Se, Te) while including spin–orbit coupling effects. The conducted symmetry-based tight-binding calculations show that the analytical continuation from the real band structures to the complex momentum space leads to nonlinear generalized eigenvalue problems. Herein an efficient method for solving such a class of nonlinear problems is presented and yields a complete set of physically relevant eigenvalues. Solutions obtained by this method are characterized and classified into propagating and evanescent states, where the latter states manifest not only monotonic but also oscillatory decay character. It is observed that some of the oscillatory evanescent states create characteristic complex loops at the direct band gap of MX 2 monolayers, where electrons can directly tunnel between the band gap edges. To describe these tunneling currents, decay behavior of electronic states in the forbidden energy region is elucidated and their importance within the ballistic transport regime is briefly discussed. (paper)

  4. Complex band structures of transition metal dichalcogenide monolayers with spin-orbit coupling effects

    Szczęśniak, Dominik; Ennaoui, Ahmed; Ahzi, Saïd

    2016-09-01

    Recently, the transition metal dichalcogenides have attracted renewed attention due to the potential use of their low-dimensional forms in both nano- and opto-electronics. In such applications, the electronic and transport properties of monolayer transition metal dichalcogenides play a pivotal role. The present paper provides a new insight into these essential properties by studying the complex band structures of popular transition metal dichalcogenide monolayers (MX 2, where M  =  Mo, W; X  =  S, Se, Te) while including spin-orbit coupling effects. The conducted symmetry-based tight-binding calculations show that the analytical continuation from the real band structures to the complex momentum space leads to nonlinear generalized eigenvalue problems. Herein an efficient method for solving such a class of nonlinear problems is presented and yields a complete set of physically relevant eigenvalues. Solutions obtained by this method are characterized and classified into propagating and evanescent states, where the latter states manifest not only monotonic but also oscillatory decay character. It is observed that some of the oscillatory evanescent states create characteristic complex loops at the direct band gap of MX 2 monolayers, where electrons can directly tunnel between the band gap edges. To describe these tunneling currents, decay behavior of electronic states in the forbidden energy region is elucidated and their importance within the ballistic transport regime is briefly discussed.

  5. Highly Fluorescent Group 13 Metal Complexes with Cyclic, Aromatic Hydroxamic Acid Ligands

    Seitz, Michael; Moore, Evan G.; Raymond, Kenneth N.

    2008-02-11

    The neutral complexes of two ligands based on the 1-oxo-2-hydroxy-isoquinoline (1,2-HOIQO) motif with group 13 metals (Al, Ga, In) show bright blue-violet luminescence in organic solvents. The corresponding transition can be attributed to ligand-centered singlet emission, characterized by a small Stokes shifts of only a few nm combined with lifetimes in the range between 1-3 ns. The fluorescence efficiency is high, with quantum yields of up to 37% in benzene solution. The crystal structure of one of the indium(III) complexes (trigonal space group R-3, a = b = 13.0384(15) {angstrom}, c = 32.870(8) {angstrom}, ? = {beta} = 90{sup o}, {gamma} = 120{sup o}, V = 4839.3(14) {angstrom}{sup 3}, Z = 6) shows a six-coordinate geometry around the indium center which is close to trigonal-prismatic, with a twist angle between the two trigonal faces of 20.7{sup o}. Time-dependent density functional theory (TD-DFT) calculations (Al and Ga: B3LYP/6-31G(d)); In: B3LYP/LANL2DZ of the fac and mer isomers with one of the two ligands indicate that there is no clear preference for either one of the isomeric forms of the metal complexes. In addition, the metal centers do not have a significant influence on the electronic structure, and as a consequence, on the predominant intraligand optical transitions.

  6. Reactive solute transport in streams: A surface complexation approach for trace metal sorption

    Runkel, Robert L.; Kimball, Briant A.; McKnight, Diane M.; Bencala, Kenneth E.

    1999-01-01

    A model for trace metals that considers in-stream transport, metal oxide precipitation-dissolution, and pH-dependent sorption is presented. Linkage between a surface complexation submodel and the stream transport equations provides a framework for modeling sorption onto static and/or dynamic surfaces. A static surface (e.g., an iron- oxide-coated streambed) is defined as a surface with a temporally constant solid concentration. Limited contact between solutes in the water column and the static surface is considered using a pseudokinetic approach. A dynamic surface (e.g., freshly precipitated metal oxides) has a temporally variable solid concentration and is in equilibrium with the water column. Transport and deposition of solute mass sorbed to the dynamic surface is represented in the stream transport equations that include precipitate settling. The model is applied to a pH-modification experiment in an acid mine drainage stream. Dissolved copper concentrations were depressed for a 3 hour period in response to the experimentally elevated pH. After passage of the pH front, copper was desorbed, and dissolved concentrations returned to ambient levels. Copper sorption is modeled by considering sorption to aged hydrous ferric oxide (HFO) on the streambed (static surface) and freshly precipitated HFO in the water column (dynamic surface). Comparison of parameter estimates with reported values suggests that naturally formed iron oxides may be more effective in removing trace metals than synthetic oxides used in laboratory studies. The model's ability to simulate pH, metal oxide precipitation-dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between trace metal chemistry and hydrologic transport at the field scale.

  7. Custom-made, root-analogue direct laser metal forming implant: a case report.

    Mangano, Francesco Guido; Cirotti, Bruno; Sammons, Rachel Lilian; Mangano, Carlo

    2012-11-01

    In the last few years, the application of digital technology in dentistry has become widespread with the introduction of cone beam computed tomography (CBCT) scan technology, and considerable progress has been made in the development of computer-aided design/ computer-aided manufacturing (CAD/CAM) techniques, including direct laser metal forming (DLMF). DLMF is a technology which allows solids with complex geometry to be produced by annealing metal powder microparticles in a focused laser beam, according to a computer-generated three-dimensional (3D) model. For dental implants, the fabrication process involves the laser-induced fusion of titanium microparticles, in order to build, layer by layer, the desired object. At present, the combined use of CBCT 3D data and CAD/CAM technology makes it possible to manufacture custom-made, root-analogue implants (RAI) with sufficient precision. This report demonstrates the successful clinical use of a custom-made, root-analogue DLMF implant. CBCT images of a non-restorable right maxillary first premolar were acquired and transformed into a 3D model. From this model, a custom-made, root-analogue DLMF implant was fabricated. Immediately after tooth extraction, the RAI with a pre-operatively designed abutment was placed in the extraction socket and restored with a single crown. At the 1-year follow-up examination, the RAI showed a good functional and aesthetic integration. The introduction of DLMF technology signals the start of a new revolutionary era for implant dentistry as its immense potential for producing highly complex macro- and microstructures is receiving vast interest in different medical fields.

  8. The Effect of Grinding and Polishing Procedure of Tool Steels in Sheet Metal Forming

    Lindvall, F.; Bergström, J.; Krakhmalev, P.

    2010-01-01

    The surface finish of tools in sheet metal forming has a large influence on the performance of the forming tool. Galling, concern of wear in sheet metal forming, is a severe form of adhesive wear where sheet material is transferred on to the tool surface. By polishing the tools to a fine surface ...... 40 and Vanadis 6 and up to ten different grinding and polishing treatments were tested against AISI 316 stainless steel. The tests showed that an optimum surface preparation might be found at the transition between abrasive and adhesive wear....

  9. Modeling the degradation of a metallic waste form intended for geologic disposal

    Bauer, T.H.; Morris, E.E.

    2007-01-01

    Nuclear reactors operating with metallic fuels have led to development of robust metallic waste forms intended to immobilize hazardous constituents in oxidizing environments. Release data from a wide range of tests where small waste form samples have been immersed in a variety of oxidizing solutions have been analyzed and fit to a mechanistically-derived 'logarithmic growth' form for waste form degradation. A bounding model is described which plausibly extrapolates these fits to long-term degradation in a geologic repository. The resulting empirically-fit degradation model includes dependence on solution pH, temperature, and chloride concentration as well as plausible estimates of statistical uncertainty. (authors)

  10. Solventless acid-free synthesis of mesostructured titania: Nanovessels for metal complexes and metal nanoclusters

    Dag, Oe.; Celik, Oe.; Ozin, G.A. [Department of Chemistry, Bilkent University, 06533 Ankara (Turkey); Soten, I.; Polarz, S.; Coombs, N. [Materials Chemistry Research Group, Chemistry Department, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6 (Canada)

    2003-01-01

    A new and highly reproducible method to obtain mesostructured titania materials is introduced in this contribution. The mesostructured titania is obtained by employing self-assembled structures of non-ionic alkyl-poly(ethylene oxide) surfactants as templates. The materials are produced without additional solvents such as alcohols, or even water. Only the titanium(IV) ethoxide and the surfactant (C{sub 12}EO{sub 10}) are needed. Water, in the form of that attached to the surfactant and from the atmosphere, induces growth of titania nanoclusters in the synthesis sol. It is indicated that these nanoclusters interact with the surfactant EO-head groups to form a new titanotropic amphiphile. The new amphiphiles self-assemble into titanium nanocluster-surfactant hybrid lyotropic phases, which are transformed to the final mesostructured materials by further condensation of the titania network. The titania materials can be obtained also with noble-metal particles immobilized in the mesostructured framework. It is seen that when different metal salts are used as the metal precursors, different interactions with the titania walls are found. The materials are characterized by X-ray diffraction (XRD), polarization optical microscopy (POM), transmission electron microscopy (TEM), UV-vis spectroscopy, and micro-Raman analysis. (Abstract Copyright [2003], Wiley Periodicals, Inc.)

  11. A detailed in vitro study of naproxen metal complexes in quest of ...

    Md. Sharif Hasan

    2016-07-01

    Jul 1, 2016 ... possibilities of using Naproxen metal complexes for different therapeutic ..... FTIR spectra, scanning electron microscopy and HPLC study of Naproxen metal ..... aminobenzoic acid and 2-aminophenol and their coordination.

  12. Distinct atomic structures of the Ni-Nb metallic glasses formed by ion beam mixing

    Tai, K. P.; Wang, L. T.; Liu, B. X.

    2007-01-01

    Four Ni-Nb metallic glasses are obtained by ion beam mixing and their compositions are measured to be Ni 77 Nb 23 , Ni 55 Nb 45 , Ni 31 Nb 69 , and Ni 15 Nb 85 , respectively, suggesting that a composition range of 23-85 at. % of Nb is favored for metallic glass formation in the Ni-Nb system. Interestingly, diffraction analyses show that the structure of the Nb-based Ni 31 Nb 69 metallic glass is distinctly different from the structure of the Nb-based Ni 15 Nb 85 metallic glass, as the respective amorphous halos are located at 2θ≅38 and 39 deg. To explore an atomic scale description of the Ni-Nb metallic glasses, an n-body Ni-Nb potential is first constructed with an aid of the ab initio calculations and then applied to perform the molecular dynamics simulation. Simulation results determine not only the intrinsic glass forming range of the Ni-Nb system to be within 20-85 at. % of Nb, but also the exact atomic positions in the Ni-Nb metallic glasses. Through a statistical analysis of the determined atomic positions, a new dominant local packing unit is found in the Ni 15 Nb 85 metallic glass, i.e., an icositetrahedron with a coordination number to be around 14, while in Ni 31 Nb 69 metallic glasses, the dominant local packing unit is an icosahedron with a coordination number to be around 12, which has been reported for the other metallic glasses. In fact, with increasing the irradiation dose, the Ni 31 Nb 69 metallic glasses are formed through an intermediate state of face-centered-cubic-solid solution, whereas the Ni 15 Nb 85 metallic glass is through an intermediate state of body-centered-cubic-solid solution, suggesting that the structures of the constituent metals play an important role in governing the structural characteristics of the resultant metallic glasses

  13. Advanced solid elements for sheet metal forming simulation

    Mataix, Vicente; Rossi, Riccardo; Oñate, Eugenio; Flores, Fernando G.

    2016-08-01

    The solid-shells are an attractive kind of element for the simulation of forming processes, due to the fact that any kind of generic 3D constitutive law can be employed without any additional hypothesis. The present work consists in the improvement of a triangular prism solid-shell originally developed by Flores[2, 3]. The solid-shell can be used in the analysis of thin/thick shell, undergoing large deformations. The element is formulated in total Lagrangian formulation, and employs the neighbour (adjacent) elements to perform a local patch to enrich the displacement field. In the original formulation a modified right Cauchy-Green deformation tensor (C) is obtained; in the present work a modified deformation gradient (F) is obtained, which allows to generalise the methodology and allows to employ the Pull-Back and Push-Forwards operations. The element is based in three modifications: (a) a classical assumed strain approach for transverse shear strains (b) an assumed strain approach for the in-plane components using information from neighbour elements and (c) an averaging of the volumetric strain over the element. The objective is to use this type of elements for the simulation of shells avoiding transverse shear locking, improving the membrane behaviour of the in-plane triangle and to handle quasi-incompressible materials or materials with isochoric plastic flow.

  14. Stimulated X-Ray Emission Spectroscopy in Transition Metal Complexes

    Kroll, Thomas; Weninger, Clemens; Alonso-Mori, Roberto; Sokaras, Dimosthenis; Zhu, Diling; Mercadier, Laurent; Majety, Vinay P.; Marinelli, Agostino; Lutman, Alberto; Guetg, Marc W.; Decker, Franz-Josef; Boutet, Sébastien; Aquila, Andy; Koglin, Jason; Koralek, Jake; DePonte, Daniel P.; Kern, Jan; Fuller, Franklin D.; Pastor, Ernest; Fransson, Thomas; Zhang, Yu; Yano, Junko; Yachandra, Vittal K.; Rohringer, Nina; Bergmann, Uwe

    2018-03-01

    We report the observation and analysis of the gain curve of amplified K α x-ray emission from solutions of Mn(II) and Mn(VII) complexes using an x-ray free electron laser to create the 1 s core-hole population inversion. We find spectra at amplification levels extending over 4 orders of magnitude until saturation. We observe bandwidths below the Mn 1 s core-hole lifetime broadening in the onset of the stimulated emission. In the exponential amplification regime the resolution corrected spectral width of ˜1.7 eV FWHM is constant over 3 orders of magnitude, pointing to the buildup of transform limited pulses of ˜1 fs duration. Driving the amplification into saturation leads to broadening and a shift of the line. Importantly, the chemical sensitivity of the stimulated x-ray emission to the Mn oxidation state is preserved at power densities of ˜1020 W /cm2 for the incoming x-ray pulses. Differences in signal sensitivity and spectral information compared to conventional (spontaneous) x-ray emission spectroscopy are discussed. Our findings build a baseline for nonlinear x-ray spectroscopy for a wide range of transition metal complexes in inorganic chemistry, catalysis, and materials science.

  15. A New Approach for Handling of Micro Parts in Bulk Metal Forming

    Mahshid, Rasoul; Hansen, Hans Nørgaard; Arentoft, M.

    2012-01-01

    of production [1]. This can fulfill the demands for mass production and miniaturization in industries and academic communities. According to the recent studies, topics related to materials, process and simulation have been investigated intensively and well documented. Machines, forming tools and handling...... systems are critical elements to complete micro forming technology for transferring knowledge to industries and toward miniature manufacturing systems (micro factory) [2]. Since most metal forming processes are multi stage, making a new handling system with high reliability on accuracy and speed...... have been optimized or handling systems based on new concepts for gripping and releasing micro parts have been proposed. Making a handling system for micro parts made by sheet metals or foils is easier than those in bulk metal forming because parts are attached to the sheet during the forming process...

  16. Preservation of NOM-metal complexes in a modern hyperalkaline stalagmite: Implications for speleothem trace element geochemistry

    Hartland, Adam; Fairchild, Ian J.; Müller, Wolfgang; Dominguez-Villar, David

    2014-03-01

    We report the first quantitative study of the capture of colloidal natural organic matter (NOM) and NOM-complexed trace metals (V, Co, Cu, Ni) in speleothems. This study combines published NOM-metal dripwater speciation measurements with high-resolution laser ablation ICPMS (LA-ICPMS) and sub-annual stable isotope ratio (δ18O and δ13C), fluorescence and total organic carbon (TOC) analyses of a fast-growing hyperalkaline stalagmite (pH ˜11) from Poole’s Cavern, Derbyshire UK, which formed between 1997 and 2008 AD. We suggest that the findings reported here elucidate trace element variations arising from colloidal transport and calcite precipitation rate changes observed in multiple, natural speleothems deposited at ca. pH 7-8. We find that NOM-metal(aq) complexes on the boundary between colloidal and dissolved (˜1 nm diameter) show an annual cyclicity which is inversely correlated with the alkaline earth metals and is explained by calcite precipitation rate changes (as recorded by kinetically-fractionated stable isotopes). This relates to the strength of the NOM-metal complexation reaction, resulting in very strongly bound metals (Co in this system) essentially recording NOM co-precipitation (ternary complexation). More specifically, empirical partition coefficient (Kd) values between surface-reactive metals (V, Co, Cu, Ni) [expressed as ratio of trace element to Ca ratios in calcite and in solution] arise from variations in the ‘free’ fraction of total metal in aqueous solution (fm). Hence, differences in the preservation of each metal in calcite can be explained quantitatively by their complexation behaviour with aqueous NOM. Differences between inorganic Kd values and field measurements for metal partitioning into calcite occur where [free metal] ≪ [total metal] due to complexation reactions between metals and organic ligands (and potentially inorganic colloids). It follows that where fm ≈ 0, apparent inorganic Kd app values are also ≈0, but the

  17. From non-disposable to disposable, treatment of pyrophoric or gas forming waste forms for disposal - Thermal treatment of pyrophoric or gas-forming metals

    Oesterberg, Carl; Lindberg, Maria

    2014-01-01

    In order to dispose of waste in either a deep geological disposal or in a shallower repository there are several demands that the waste and its package must fulfil, one is that it is not to react with oxygen or the waste package or backfill in the repository, i.e. concrete or grout. The waste forms that do not fulfil this particular criterion must be treated in some way to render the waste non-reactive. One of these waste are metallic uranium. Metallic uranium is not only an issue originating from the nuclear industry, as old types of fuel, it is also present in, for example, transport flasks and as samples used in schools, which all has to be disposed of sooner or later. Another waste that arise is magnesium doped with thorium, originating from the aviation, aerospace and missile industry. These alloys are now being replaced with others without thorium so they are in need of handling and possibly treatment before disposal. Magnesium metal is also pyrophoric, in particular in molten or powder form. In order to evaluate thermally treating these metals in a very controlled environment, such as a pyrolysis vessel, experimental work has been performed. The aim of the thermal treatment is to oxidise the metals and obtain an oxide with low leachability. Inactive trials were performed, first using small amount of magnesium tape followed by using Cerium instead of uranium, to check the ability of controlling the process. After the process had been deemed safe the next step was to test the process first with metallic uranium and thereafter with magnesium thorium alloy. The first results show that the oxidation process can be totally controlled and safe. The results show that the metals are oxidised and no longer reactive and can in principle be disposed of. The test will continue and further results will be reported. (authors)

  18. Direct synthesis of metal complexes starting from zero-valent metals

    Gojon-Zorrilla, Gabriel; Kharisov, Boris I. [Universidad Autonoma de Nuevo Leon, Monterrey, Nuevo Leon (Mexico); Garnovskii, Alexander D. [Institute of Physical and Organic Chemistry (Russian Federation)

    1996-06-01

    The recent (1980-1994) literature on metal-vapor synthesis of coordination and organometallic compounds is reviewed. An account is given of the high-and low-temperature reactions between free metal atoms and a large variety of substrates, mainly alkenes, alkynes, dienes, arenes, funtionalized arenes, alkyl halides {beta}-diketones and simple inorganic molecules. The main experimental methods are described, as well as the results obtained thereby. It is shown that in many instances these methods present significant advantages over conventional synthetic procedures, offering unique access to some metal complexes. [Spanish] Se reviso la literatura reciente (1980-1994) sobre la sintesis de compuestos de coordinacion y compuestos organometalicos a partir de vapores metalicos. Se examinan las reacciones de los atomos metalicos libres con una gran variedad de substratos, principalmente alquenos, alquinos, dienos, hidrocarburos aromaticos y sus derivados, haluros de alquilo y arilo, {beta}-dicetonas y moleculas inorganicas simples. Se presentan los principales metodos experimentales, asi como los resultados obtenidos; se concluye que la crisintesis presenta en muchos casos ventajas significativas sobre los procedimientos sinteticos tradicionales, constituyendo frecuentemente la unica opcion disponible.

  19. TiO2 Photocatalyzed Oxidation of Free and Complex Metallic Cyanides.

    Valladares, J. E.; Esteghamatdarsthad, B.; Renteria, J.

    2006-07-01

    The TiO2 photo catalyzed oxidation of free cyanide and transition metal cyanide complexes often found in industrial mining wastes were studied. The photoreactor system used was a UV illuminated and stirred tank with suspended particles of TiO2. After to determine the optimization parameters such as light intensity, concentration of complex and free cyanides, in ideal conditions, the effect of the presence of different type of anions was also studied. The model substances chosen were potassium cyanide and cyanides complexes of Iron, Cobalt and Copper in a strong alkaline solution (pH = 11.0 - 12.0). The experimental results indicate that in the case of the hexaferricyanide complex Fe(CN)6 3, the reaction occur in two steps. The first step is the breakdown of the metal-cyanide bond (photo-dissociation) forming free cyanide (CN-) and Fe3+ ions. The second step is the photo-oxidation of the free cyanides formed before. The ions Fe3+ and OH- present in the alkaline solution, precipitate as iron hydroxide Fe(OH)3. During the photo-dissociation step of the iron complex, free CN- ions produced reaches a maximum concentration before it is eliminated by photo-oxidation. The free cyanide produced from the hexaferricyanide complex disappears rapidly at a velocity of 64.6 + - 5.0 ?M/min. This rate of photo-oxidation is comparable with the experiments using just alkaline solutions of potassium cyanide ('free cyanides'). In contrast, in alkaline solutions of cyanide complexes of Cu and Co the rate of photo-oxidation was substantially reduced (6.17+ - 0.80 ?M/min and 0.04 + - 0.010 ?M/min, respectively) and do not show any initial increase of free cyanides in the suspension. The slower rate of photo-oxidation suggests the formation of very stable hydroxyl-cyanide polymeric metallic complexes in the reaction mix. The photo-oxidation pathway of the nitrogen oxide products was also investigated and found that the final product consists mainly of nitrate ions. (Author)

  20. Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

    Du, Guodong [Iowa State Univ., Ames, IA (United States)

    2003-01-01

    -, bis-alkoxo, and chelating diolato complexes, depending on the identity of diols and the stoichiometry employed. It was also found that tin porphyrin complexes promoted the oxidative cleavage of vicinal diols and the oxidation of α-ketols to α-diketones with dioxygen. In extending the chemistry of metalloporphyrins and analogous complexes, a series of chiral tetraaza macrocyclic ligands and metal complexes were designed and synthesized. Examination of iron(II) complexes showed that they were efficient catalysts for the cyclopropanation of styrene by diazo reagents. Good yields and high diastereoselectivity were obtained with modest enantioselectivity. A rationalization of the stereoselectivity was presented on the basis of structural factors in a carbene intermediate.

  1. Effect of material scatter on the plastic behavior and stretchability in sheet metal forming

    Wiebenga, J.H.; Atzema, E.H.; Atzema, E.H.; An, Y.G.; Vegter, H.; van den Boogaard, Antonius H.

    2014-01-01

    Robust design of forming processes is gaining attention throughout the industry. To analyze the robustness of a sheet metal forming process using Finite Element (FE) simulations, an accurate input in terms of parameter scatter is required. This paper presents a pragmatic, accurate and economic

  2. The effect of tooling deformation on process control in multistage metal forming

    Havinga, Gosse Tjipke; van den Boogaard, Antonius H.; Chinesta, F; Cueto, E; Abisset-Chavanne, E.

    2016-01-01

    Forming of high-strength steels leads to high loads within the production process. In multistage metal forming, the loads in different process stages are transferred to the other stages through elastic deformation of the stamping press. This leads to interactions between process steps, affecting the

  3. Synthesis, spectroscopic and biological studies of transition metal complexes of novel schiff bases derived from amoxicillin and sugars

    Naz, N.

    2009-01-01

    Fe (II), Co (II) and Ni (II) metal complexes of new Schiff bases derived from amoxicillin with sugars (D-Glucose, D-Galactose and D-Mannose) have been synthesized and characterized by elemental analysis, FTIR, electronic absorption, and atomic absorption spectroscopy, magnetic moment measurements and thermal analysis. It has been found that Schiff bases behave as bi-dentate ligands forming complexes with 1:2 (metal:ligand) stoichiometry. The complexes were neutral as confirmed by their low conductance values. The biological applications of complexes have been studied on two gram negative (Escherichia coli and Pseudomonas aeruginosa) and two gram positive (Bacillus subtilis and Staphylococcus aureus) microorganisms by Agar diffusion disc method. It has been found that all the complexes have higher biological activities than the pure amoxicillin. (author)

  4. Synthesis, spectroscopic and biological studies of transition metal complexes of novel schiff bases derived from cephradine and sugars

    Naz, N.; Iqbal, M.Z.

    2011-01-01

    Fe(II), Co(II) and Ni(II) metal complexes of novel schiff bases derived from Cephradine and sugars (D-Glucose, L. Arabinose and D-Galactose) were synthesized and characterized by elemental analysis, magnetic susceptibility, thermal analysis, electronic absorption and FT-IR spectral studies. It has been found that schiff bases behave as bi-dentate-ligands forming complexes with 1:2 (metal:ligand) stoichiometry. the neutral nature of the complexes was confirmed by their low conductance values. The biological activities of complexes have been evaluated against two gram negative (Escherichia coli and Pseudomonas aeruginosa) and two gram positive (Bacillus subtilis and staphylococcus aureus) bacteria by Agar diffusion disc method. It has been found that the complexes have higher activity as compared to the pure Cephradine against the same bacteria. (author)

  5. Decomposition of uranyl peroxo-carbonato complex ion in the presence of metal oxides in carbonate media

    Dong-Yong Chung; Min-Sung Park; Keun-Young Lee; Eil-Hee Lee; Kwang-Wook Kim; Jei-Kwon Moon

    2015-01-01

    Uranium oxide was dissolved in the form of the uranyl peroxo-carbonato complex ion, UO 2 (O 2 )(CO 3 ) 2 4- in carbonate solutions with hydrogen peroxide. When UO 2 (O 2 )(CO 3 ) 2 4- ions lose their peroxide component, they become a stable species of uranyl tricarbonato complex ion, UO 2 (O 2 )(CO 3 ) 2 4- . The uranyl peroxo-carbonato complex self-decomposed more rapidly into the uranyl tricarbonato complex ion in the presence of a metal oxide in the carbonate solution. In this study, decomposition of the uranyl peroxo-carbonato complex in a carbonate solution was investigated in the presence of several metal oxides using absorption spectroscopy. (author)

  6. Influence of part orientation on the geometric accuracy in robot-based incremental sheet metal forming

    Störkle, Denis Daniel; Seim, Patrick; Thyssen, Lars; Kuhlenkötter, Bernd

    2016-10-01

    This article describes new developments in an incremental, robot-based sheet metal forming process (`Roboforming') for the production of sheet metal components for small lot sizes and prototypes. The dieless kinematic-based generation of the shape is implemented by means of two industrial robots, which are interconnected to a cooperating robot system. Compared to other incremental sheet metal forming (ISF) machines, this system offers high geometrical form flexibility without the need of any part-dependent tools. The industrial application of ISF is still limited by certain constraints, e.g. the low geometrical accuracy. Responding to these constraints, the authors present the influence of the part orientation and the forming sequence on the geometric accuracy. Their influence is illustrated with the help of various experimental results shown and interpreted within this article.

  7. Crystal structure of glucose isomerase in complex with xylitol inhibitor in one metal binding mode.

    Bae, Ji-Eun; Kim, In Jung; Nam, Ki Hyun

    2017-11-04

    Glucose isomerase (GI) is an intramolecular oxidoreductase that interconverts aldoses and ketoses. These characteristics are widely used in the food, detergent, and pharmaceutical industries. In order to obtain an efficient GI, identification of novel GI genes and substrate binding/inhibition have been studied. Xylitol is a well-known inhibitor of GI. In Streptomyces rubiginosus, two crystal structures have been reported for GI in complex with xylitol inhibitor. However, a structural comparison showed that xylitol can have variable conformation at the substrate binding site, e.g., a nonspecific binding mode. In this study, we report the crystal structure of S. rubiginosus GI in a complex with xylitol and glycerol. Our crystal structure showed one metal binding mode in GI, which we presumed to represent the inactive form of the GI. The metal ion was found only at the M1 site, which was involved in substrate binding, and was not present at the M2 site, which was involved in catalytic function. The O 2 and O 4 atoms of xylitol molecules contributed to the stable octahedral coordination of the metal in M1. Although there was no metal at the M2 site, no large conformational change was observed for the conserved residues coordinating M2. Our structural analysis showed that the metal at the M2 site was not important when a xylitol inhibitor was bound to the M1 site in GI. Thus, these findings provided important information for elucidation or engineering of GI functions. Copyright © 2017 Elsevier Inc. All rights reserved.

  8. Synthesis and properties of 5,10,15,20-tetra[4-(3,5-dioctoxybenzamidephenyl] porphyrin and its metal complexes

    Lian Wenhui

    2012-01-01

    Full Text Available A novel 5,10,15,20-tetra[4-(3,5-dioctoxybenzamidephenyl]porphyrin and its transition metal complexes are reported in this paper. Their molecular structures were characterized by elemental analysis, IR spectra, 1HNMR spectra and UV-Vis spectra. Their spectroscopic properties were studied by Raman spectra, fluorescence spectra and X-ray photoelectron spectra (XPS. The fluorescence quantum yields have been measured at room temperature. The fluorescence intensity of porphyrin ligand was stronger than that of the complexes. In Raman spectra, there was much difference between porphyrin ligand and its metal complexes due to changes of the symmetry of porphyrin plane. In the XPS spectra, the replacement of the free-base protons by a metal ion to form the metalloporphyrin increases the symmetry of the molecule also introduces an electron with-drawing group into the center of the porphyrin ligand which increases the N1s binding energy.

  9. Photoluminescent properties of complex metal oxide nanopowders for gas sensing

    Bovhyra, R. V.; Mudry, S. I.; Popovych, D. I.; Savka, S. S.; Serednytski, A. S.; Venhryn, Yu. I.

    2018-03-01

    This work carried out research on the features of photoluminescence of the mixed and complex metal oxide nanopowders (ZnO/TiO2, ZnO/SnO2, Zn2SiO4) in vacuum and gaseous ambient. The nanopowders were obtained using pulsed laser reactive technology. The synthesized nanoparticles were characterized by X-ray diffractometry, energy-dispersive X-ray analysis, and scanning and transmission electron microscopy analysis for their sizes, shapes and collocation. The influence of gas environment on the photoluminescence intensity was investigated. A change of ambient gas composition leads to a rather significant change in the intensity of the photoluminescence spectrum and its deformation. The most significant changes in the photoluminescent spectrum were observed for mixed ZnO/TiO2 nanopowders. This obviously is the result of a redistribution of existing centers of luminescence and the appearance of new adsorption centers of luminescence on the surface of nanopowders. The investigated nanopowders can be effectively used as sensing materials for the construction of the multi-component photoluminescent sensing matrix.

  10. Characterization of a Fe-based alloy system for an AFCI metallic waste form - 16134

    Williamson, Mark J.; Sindelar, Robert L.

    2009-01-01

    The AFCI waste management program aims to provide a minimum volume stable waste form for high level radioactive waste from the various process streams. The AFCI Integrated Waste Management Strategy document has identified a Fe-Zr metallic waste form (MWF) as the baseline alloy for disposal of Tc metal, undissolved solids, and TRUEX fission product wastes. Several candidate alloys have been fabricated using vacuum induction melting to investigate the limits of waste loading as a function of Fe and Zr content. Additional melts have been produced to investigate source material composition. These alloys have been characterized using SEM/EDS and XRD. Phase assemblage and specie partitioning of Re metal (surrogate for Tc) and noble metal FP elements into the phases is reported. (authors)

  11. Complexation-Induced Phase Separation: Preparation of Metal-Rich Polymeric Membranes

    Villalobos Vazquez de la Parra, Luis Francisco

    2017-08-01

    The majority of state-of-the-art polymeric membranes for industrial or medical applications are fabricated by phase inversion. Complexation induced phase separation (CIPS)—a surprising variation of this well-known process—allows direct fabrication of hybrid membranes in existing facilities. In the CIPS process, a first step forms the thin metal-rich selective layer of the membrane, and a succeeding step the porous support. Precipitation of the selective layer takes place in the same solvent used to dissolve the polymer and is induced by a small concentration of metal ions. These ions form metal-coordination-based crosslinks leading to the formation of a solid skin floating on top of the liquid polymer film. A subsequent precipitation in a nonsolvent bath leads to the formation of the porous support structure. Forming the dense layer and porous support by different mechanisms while maintaining the simplicity of a phase inversion process, results in unprecedented control over the final structure of the membrane. The thickness and morphology of the dense layer as well as the porosity of the support can be controlled over a wide range by manipulating simple process parameters. CIPS facilitates control over (i) the thickness of the dense layer throughout several orders of magnitude—from less than 15 nm to more than 6 μm, (ii) the type and amount of metal ions loaded in the dense layer, (iii) the morphology of the membrane surface, and (iv) the porosity and structure of the support. The nature of the CIPS process facilitates a precise loading of a high concentration of metal ions that are located in only the top layer of the membrane. Moreover, these metal ions can be converted—during the membrane fabrication process—to nanoparticles or crystals. This simple method opens up fascinating possibilities for the fabrication of metal-rich polymeric membranes with a new set of properties. This dissertation describes the process in depth and explores promising

  12. Synthesis, structure and complex forming ability of phosphorylated derivatives of heterocyclic compounds

    Babaev, B.N.

    2004-01-01

    Full text: The derivatives of acids of phosphorus, due to variety of properties, are a subject of numerous researches. Now it is known, that the derivatives of acids of phosphorus apart from insect, neurotoxic, antienzym and other kinds of physiological activity have also complex forming properties. As extra gents of noble metals particularly are analyzed by the derivatives of dithio phosphor of acids although organ phosphorus compounds with one nuclear of sulfur make extraction properties. Therefore, with the purpose of detection of effective extra gents of ions of argentum the phosphorylated derivatives of heterogeneous ring compounds were synthesized: Ph(RO)P(O)Cl + HOCH(CH 3 )CH 2 -R ' -> Ph(RO)P(O)OCH(CH 3 )CH 2 -R ' + HCl. R C 2 H 5 - C 6 H 13 , R ' = a piperidine, morpholine, anabasine Structure of the obtained connections is confirmed by the results IR -, Pm- and mass- spectrometry. In an IR-spectrum O-hexyl-O - [piperidynoisopropyl] phenylphosphonate has lines of absorption bands of the following functional groups (ν, cm -1 ): (P-O-C 5 H 11 ) 990-1000, (P = 0) 1260, (P-C 6 H 5 )1450, (C-N in cycle) 1550. In an IR-spectrum O-pentyl-[anabasinoisopropyl] phenylphosphonate has lines of absorption bands of the following functional groups (ν, cm -1 ): (P-O-C 5 H 11 ) 990-1000, (P = 0) 1250, (P-C 6 H 5 )1450, (C-N in cycle) 1550. In a spectrum PMR about O-pentyl-[morpholyniisopropyl] phenylphosphonate in the field of a weak field (7, 18-7, 29 p.m.) the multiplet about tones of phenyl group is watched. Me tin proton resonate at 4,66 m.d.as multiplet The signals O-CH 2 of protons of morpholinic cycle appear at 3,58 m.d.. 4H) by the way of triplet. The protons N-CH 2 (6H) three methylene groups will derivate a composite multiple at 2, 10-2, 70 m.d.. The signal of metil group's protons (3H) is watched at 1,15m.d.as doublet. Final metal group resonates at 0, 87 p.m. Six of C-CH 2 of groups give a complex signal in the field of 1, 2-1, 8 m.d. The obtained connections

  13. Kinetic studies of the solvent extraction of metal complexes

    Mirza, M.Y.; Nwabue, F.I.; Okafo, E.N.

    1981-01-01

    The rate of forward extraction of Zr(IV) from 2M sulphuric acid into 1-phenyl-3-methyl-4-benzoyl-pyrazole-5-one (HPsub (z)) dissolved in chloroform and backward extraction of the tetrakis-chelate, Zr(Pz) 4 have been measured under various conditions. The rate of forward reaction is proportional to [Zr 4+ ], [HPsub(z)] 2 and [H + ] -2 , while that of back extraction to [Zr(Pz) 4 ]sub(org), [HPsub(z)] -2 sub(org) and [H + ] 2 . The rate determining step in the forward extraction is established to be the formation of the second complex between the dissociated form of HPz, Pz - and the Zr(H 2 O) 2 SO 4 Pz + species in the aqueous phase while it is the reverse in the backward extraction. The velocity constants for both rate controlling steps have been determined and the extraction constant agrees with the value obtained from the equilibrium data. (author)

  14. Novel Bioactive Titanate Layers Formed on Ti Metal and Its Alloys by Chemical Treatments

    Tadashi Kokubo

    2009-12-01

    Full Text Available Sodium titanate formed on Ti metal by NaOH and heat treatments induces apatite formation on its surface in a body environment and bonds to living bone. These treatments have been applied to porous Ti metal in artificial hip joints, and have been used clinically in Japan since 2007. Calcium titanate formed on Ti-15Zr-4Nb-4Ta alloy by NaOH, CaCl2, heat, and water treatments induces apatite formation on its surface in a body environment. Titanium oxide formed on porous Ti metal by NaOH, HCl, and heat treatments exhibits osteoinductivity as well as osteoconductivity. This is now under clinical tests for application to a spinal fusion device.

  15. Improvements in or relating to the production of metal-containing material in particulate form

    Woodhead, J.L.; Scott, K.T.B.; Ball, P.W.

    1977-01-01

    The process described refers mainly to production of the material in the form of very small spheres. It comprises forming a metal compound-containing gel precipitate by mixing a solution or sol of the metal compound with a soluble organic polymer and contacting the mixture with a precipitating reagent to precipitate the metal as an insoluble compound bound with the polymer. The precipitate is then subjected in the liquid phase to a breaking down and dispersing process to produce an intermediate product suitable for spray drying, and the intermediate product is spray dried to form the particulate product. The breaking down and dispersing process may be performed by means of a colloid mill or vibratory stirrer. Examples of application of the process are described. (U.K.)

  16. Studies on chelation properties of ampicillin with trace metal ions and comparison with penicillin complexes

    Rehmani, F.S.; Hameed, W.

    2003-01-01

    The penicillin is highly effective antibiotic with extremely wide margin of safety. Ampicillin e is the penicillin group of antibiotic in which side chain is phenyl group i.e. D-amino benzyl penicillin. The side chain determines many of anti bacterial and pharmacological characteristics. They inhibit the protein synthesis in bacterial cell wall. The chelating properties of the antibiotic may be used in the metal transport across the membrane. The present investigations are helpful in drug metabolism and their effects on minerals contents of the body. The complex formation between Ampicillin and penicillin with trace metal ions such as Fe(III), Cr(III), Al(III), Mn(II), Ni(II), Co(II), Ca(II), Mg(II), Cu(III) and Zn(II) were studied by potentiometric titrations and spectrophotometric methods. Stoichiometry of these complexes were studied by mole ratio method. It was found that the Fe(III) and Cu(II) ions form most stable complexes near physiological pH and the mole ratio was 1:1. (author)

  17. Hydrogen storage in metal hydrides and complex hydrides; Wasserstoffspeicherung in Metall- und komplexen Hydriden - Schlussbericht

    Bielmann, M.; Zuettel, A.

    2007-07-01

    This final report for the Swiss Federal Office of Energy (SFOE), reports on work done in 2007 at the Swiss Federal Laboratories for Materials Science and Technology EMPA on the storage of hydrogen in metal hydrides and complex hydrides. In particular, the use of tetrahydroborates is noted. The potential of this class of materials is stressed. The structures at room-temperature were examined using neutron and X-ray diffraction methods. Thermodynamic methods helped determine the thermodynamic stability of the materials. Also, a complete energy diagram for the materials was developed. The use of silicon oxide to reduce activation energy and its catalytic effects are discussed. The challenges placed by desorption mechanisms are noted. The authors note that reversibility is basically proven.

  18. Studies on Oligomer Metal Complexes Derived from Bisamic Acid of Pyromellitic Dianhydride and 4-Bromoaniline.

    Patel, Yogesh S

    2014-01-01

    Novel oligomer metal complexes (2a-f) of the ligand 2,5-bis((4-bromophenyl)carbamoyl) terephthalic acid (1) were prepared using transition metal salts and characterized by various spectroscopic techniques. The geometry of oligomer metal complexes was carried out by electronic spectral analysis and magnetic measurement studies. Polymeric properties have also been carried out. Ligand was synthesized using pyromellitic dianhydride and 4-bromoaniline. It was duly characterized. All novel synthesized compounds 1 and 2a-f were evaluated for their antibacterial and antifungal activity. The results showed significantly higher antibacterial and antifungal activity of oligomer metal complexes compared to the ligand.

  19. Detection of defects in formed sheet metal using medial axis transformation

    Murmu, Naresh C.; Velgan, Roman

    2003-05-01

    In the metal forming processes, the sheet metals are often prone to various defects such as thinning, dents, wrinkles etc. In the present manufacturing environments with ever increasing demand of higher quality, detecting the defects of formed sheet metal using an effective and objective inspection system is the foremost norm to remain competitive in market. The defect detection using optical techniques aspire to satisfy its needs to be non-contact and fast. However, the main difficulties to achieve this goal remain essentially on the development of efficient evaluation technique and accurate interpretation of extracted data. The defect like thinning is detected by evaluating the deviations of the thickness in the formed sheet metal against its nominal value. The present evaluation procedure for determination of thickness applied on the measurements data is not without deficiency. To improve this procedure, a new evaluation approach based on medial axis transformation is proposed here. The formed sheet metals are digitized using fringe projection systems in different orientations, and afterwards registered into one coordinate frame. The medial axis transformation (MAT) is applied on the point clouds, generating the point clouds of MAT. This data is further processed and medial surface is determined. The thinning defect is detected by evaluating local wall thickness and other defects like wrinkles are determined using the shape recognition on the medial surface. The applied algorithm is simple, fast and robust.

  20. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    Peresypkina, Eugenia V. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Samsonenko, Denis G. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Vostrikova, Kira E., E-mail: vosk@niic.nsc.ru [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); LMI, Université Claude Bernard Lyon 1, 69622 Villeurbanne Cedex (France)

    2015-04-15

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [(Mn(acacen)){sub 2}Ru(NO)(CN){sub 5}]{sub n} and two complexes composed of different cyanorhenates, [Ni(cyclam)]{sub 2}[ReO(OH)(CN){sub 4}](ClO{sub 4}){sub 2}(H{sub 2}O){sub 1.25} and [Cu(cyclam)]{sub 2}[Re(CN){sub 7}](H{sub 2}O){sub 12}, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN){sub n}]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu{sub 4}N){sub 2}[Ru(NO)(CN){sub 5}], soluble in organic media. - Graphical abstract: The very first results in the design of 2D coordination polymers based on penta- and heptacyanometallates of 4d and5d transitions metals are presented. - Highlights: • Design of coordination polymers based on penta- and heptacyanometallates. • New Ru and Re cyanide based heterobimetallic coordination complexes. • Hydrolysis and ox/red processes involving [Re(CN){sub 7}]{sup 3+} during crystallization. • High magnetic anisotropy of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2}(H{sub 2}O){sub n}, M=Cu, Ni, complexes.

  1. On the possibility of removing of transition metal ions from sewage using polymeric complexes

    Tazhibaeva, S.M.; Abilov, Zh.A.; Musabekov, K.V.

    1997-01-01

    The possibility of using of complexation in the system polyethylene-imine transition metal ions (Cu 2+ , Ni 2+ , Co 2+ )-surface active substance for removing of metal ions from solution and sewage has been investigated. It is shown, that pH of medium, hydro-fugitive of system and ratio between component of the triply complex effect on purification of solution. (author)

  2. Complexation with dissolved organic matter and solubility control of heavy metals in sandy soil

    Weng, L.; Temminghoff, E.J.M.; Lofts, S.; Tipping, E.; Riemsdijk, van W.H.

    2002-01-01

    The complexation of heavy metals with dissolved organic matter (DOM) in the environment influences the solubility and mobility of these metals. In this paper, we measured the complexation of Cu, Cd, Zn, Ni, and Pb with DOM in the soil solution at pH 3.7-6.1 using a Donnan membrane technique. The

  3. Reactivity of olefin and allyl ligands in π-complexes of metals

    Kukushkin, Yu.N.

    1987-01-01

    The data on reactivity of olefin and allyl ligands in transition metal (Ru, W) π-complexes, published up to 1984 are presented. Metal ion coordination of olefins causes their appreciable reactivity change. Transformations of π-olefin ligands into σ-alkyl ones, interaction of π-complexes with oxygen nucleophilic reagents, amines, halogenides and pseudohalogenides are considered

  4. Feasibility Study on Flexibly Reconfigurable Roll Forming Process for Sheet Metal and Its Implementation

    Jun-Seok Yoon

    2014-06-01

    Full Text Available A multicurved sheet metal surface for a skin structure has usually been manufactured using a conventional die forming process involving the use of both a die and a press machine in accordance with the product shape. However, such processes are economically inefficient because additional production costs are incurred for the development and management of forming tools. To overcome this drawback, many alternative processes have been developed; however, these still suffer from problems due to defects such as dimples and wrinkles occurring in the sheet. In this study, a new sheet metal forming process called the flexibly reconfigurable roll forming (FRRF process is proposed as an alternative to existing processes. Unlike existing processes, FRRF can reduce additional production costs resulting from material loss and significantly reduce forming errors. Furthermore, it involves the use of a smaller apparatus. The methodology and applicable procedure of the FRRF process are described. Numerical forming simulations of representative multicurved sheet surfaces are conducted using FEM. In addition, a simple apparatus is developed for verifying the feasibility of this process, and a doubly curved metal is formed to verify the applicability of the reconfigurable roller, a critical component in this forming process.

  5. Time dependent enhanced resistance against antibiotics & metal salts by planktonic & biofilm form of Acinetobacter haemolyticus MMC 8 clinical isolate

    Sharvari Vijaykumar Gaidhani

    2014-01-01

    Full Text Available Background & objectives: Available literature shows paucity of reports describing antibiotic and metal resistance profile of biofilm forming clinical isolates of Acinetobacter haemolyticus. The present study was undertaken to evaluate the antibiotic and metal resistance profile of Indian clinical isolate of A. haemolyticus MMC 8 isolated from human pus sample in planktonic and biofilm form. Methods: Antibiotic susceptibility and minimum inhibitory concentration were determined employing broth and agar dilution techniques. Biofilm formation was evaluated quantitatively by microtiter plate method and variation in complex architecture was determined by scanning electron microscopy. Minimum biofilm inhibiting concentration was checked by Calgary biofilm device. Results: Planktonic A. haemolyticus MMC 8 was sensitive to 14 antibiotics, AgNO 3 and HgC1 2 resistant to streptomycin and intermediately resistant to netilmycin and kanamycin. MMC 8 exhibited temporal variation in amount and structure of biofilm. There was 32 - 4000 and 4 - 256 fold increase in antibiotic and metal salt concentration, respectively to inhibit biofilm over a period of 72 h as against susceptible planktonic counterparts. Total viable count in the range of 10 5 -10 6 cfu / ml was observed on plating minimum biofilm inhibiting concentration on Muller-Hinton Agar plate without antimicrobial agents. Biofilm forming cells were several folds more resistant to antibiotics and metal salts in comparison to planktonic cells. Presence of unaffected residual cell population indicated presence of persister cells. Interpretation & conclusions: The results indicate that biofilm formation causes enhanced resistance against antibiotics and metal salts in otherwise susceptible planktonic A. haemolyticus MMC 8.

  6. Metal waste forms from the electrometallurgical treatment of spent nuclear fuel

    Abraham, D.P.; McDeavitt, S.M.; Park, J.

    1996-01-01

    Stainless steel-zirconium alloys are being developed for the disposal of radioactive metal isotopes isolated using an electrometallurgical treatment technique to treat spent nuclear fuel. The nominal waste forms are stainless steel-15 wt% zirconium alloy and zirconium-8 wt% stainless steel alloy. These alloys are generated in yttria crucibles by melting the starting materials at 1,600 C under an argon atmosphere. This paper discusses the microstructures, corrosion and mechanical test results, and thermophysical properties of the metal waste form alloys

  7. Metallic complexes with glyphosate: a review; Complexos metalicos com o herbicida glifosato: revisao

    Coutinho, Claudia F.B.; Mazo, Luiz Henrique [Sao Paulo Univ., Sao Carlos, SP (Brazil). Inst. de Quimica]. E-mail: claudiabreda@iqsc.usp.br

    2005-11-15

    We present studies involving metallic ions and the herbicide glyphosate. The metallic complexes of Cu(II), Zn(II), Mn(II), Ni(II), Cd(II), Pb(II), Cr(III), Fe(III), Co(III), ammonium, sodium, Ag(I), alkaline earth metals and of some lanthanides ions are described. The complexes are discussed in terms of their synthesis, identification, stability and structural properties, based on data from the current literature. (author)

  8. Studies on Oligomer Metal Complexes Derived from Bisamic Acid of Pyromellitic Dianhydride and 4-Bromoaniline

    Patel, Yogesh S.

    2014-01-01

    Novel oligomer metal complexes (2a–f) of the ligand 2,5-bis((4-bromophenyl)carbamoyl) terephthalic acid (1) were prepared using transition metal salts and characterized by various spectroscopic techniques. The geometry of oligomer metal complexes was carried out by electronic spectral analysis and magnetic measurement studies. Polymeric properties have also been carried out. Ligand was synthesized using pyromellitic dianhydride and 4-bromoaniline. It was duly characterized. All novel synthesi...

  9. FT-IR Spectroscopic study on the 4-(3-Cyclohexen-1-yl)pyridine metal (II) tetracyanonickelate complex

    Parlak, C.

    2005-01-01

    New Hofmann type complex in the form of M(4-Chpy) 2 Ni(CN) 4 (where 4-Chpy=4-(3- Cyclohexen-1-yl)pyridine and M = Ni) was prepared in powder form and its infrared spectra is reported in the range of 4000-400 cm - 1. The spectral findings suggest that this compound is similar in structure to the Hofmann type complexes and its structure consists of polymeric layers | M-Ni(CN) 4 |∞ with the 4-(3-Cyclohexen-1-yl)pyridine molecule bound to the metal atom (M)

  10. Some regularities in formation and solvent extraction of complexes in metal-salicylic acid or its derivative- organic base systems

    Alimarin, I.P.; Fadeeva, V.I.; Tikhomirova, T.I.

    1982-01-01

    The influence of concentrations of the reagents, pH and solvent on the conditions for the formation and extraction of Sc, Ti, Zr, Hf, Th complexes has been examined in salicylic acid (H 2 Sal)-heterocyclic amine systems. The extraction chemism and factors, which affect the reactions between the metal ions and the ligands, are discussed. It has been shown that Zr, Hf, Ti form species of ion associate type, Sc and Th form different-ligand complexes under conditions for interphase equilibrium in a Me-H 2 Sal-heterocyclic amine system

  11. Colour interceptions, thermal stability and surface morphology of polyester metal complexes

    Zohdy, M.H.

    2005-01-01

    Chelating copolymers via grafting of acrylic acid (AAc) and acrylamide (AAm/AAc) comonomer mixture onto polyester micro fiber fabrics (PETMF) using gamma-radiation technique were prepared. The prepared graft chains (PETMF-g-AAc) and (PETMF-g-PAAc/PAAm) acted as chelating sites for some selected transition metal ions. The prepared graft copolymers and their metal complexes were characterized using thermogravimetric analysis (TGA), colour parameters and surface morphology measurements. The colour interception and strength measurements showed that the metal complexation is homogeneously distributed. The results showed that the thermal stability of PETMF was improved after graft copolymerization and metal complexes. Moreover, the degree of grafting enhanced the thermal stability values of the grafted and complexed copolymers up to 25% of magnitude, on the other hand the activation energy of the grafted-copolymer with acrylic acid increased up to 80%. The SEM observation gives further supports to the homogenous distribution of grafting and metal complexation

  12. NUMISHEET 2016: 10th International Conference and Workshop on Numerical Simulation of 3D Sheet Metal Forming Processes

    2016-01-01

    The NUMISHEET conference series have been established as a world-class forum through which new intellectual ideas and technologies in the area of sheet metal forming simulation are exchanged. Previous NUMISHEET conferences have given enormous contributions to industry and academia in what regards the development of new methods and ideas for the numerical simulation of sheet metal forming processes. Previous NUMISHEET conferences were held in: Zurich (Switzerland, 1991), Isehara (Japan, 1993), Dearborn (USA, 1996), Besancon (France, 1999), Jeju Island (South Korea, 2002), Detroit (USA, 2005), Interlaken (Switzerland, 2008), Seoul (South Korea, 2011) and Melbourne (Australia, 2014). The NUMISHEET 2016 conference will be held in Bristol, UK. It features technical, keynote and plenary sessions and mini-symposiums in diverse sheet metal forming areas including the recently introduced incremental sheet forming and electromagnetic forming, as well as new prominent numerical methods such as IsoGeometric Analysis and meshless methods for sheet analysis. NUMISHEET 2016 will have eight academic plenary lectures delivered by worldwide recognised experts in the areas of sheet metal forming, material modelling and numerical methods in general. Also, NUMISHEET 2016 will have three industrial plenary lectures which will be addressed by three different companies with strong businesses in sheet metal forming processes: AutoForm, Crown Technology and Jaguar Land Rover. One of the most distinguishing features of NUMISHEET conference series is the industrial benchmark sessions, during which numerical simulations of industrial sheet formed parts are compared with experimental results from the industry. The benchmark sessions provide an extraordinary opportunity for networking, for the exchange of technologies related to sheet metal forming and for the numerical validation of sheet metal forming codes/software. Three benchmark studies have been organised in NUMISHEET 2016: BM1) &apos

  13. Intracellular trafficking of a pH-responsive drug metal complex.

    Kheirolomoom, Azadeh; Ingham, Elizabeth S; Commisso, Joel; Abushaban, Neveen; Ferrara, Katherine W

    2016-12-10

    .4-fold in both cancer and endothelial cells. Endothelial cytotoxicity was similarly augmented with mild hyperthermia applied prior to treatment with released CuDox. In summary, we find that the drug-metal complex formed in temperature-sensitive particles can be internalized by cancer and endothelial cells resulting in therapeutic efficacy that is similar to free doxorubicin, and this efficacy can be enhanced by elevated temperature. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Mechanical and physical simulation of complex 3-D bulk forming processes with Forge3

    Chenot, J-L.; Chastel, Y.

    2000-01-01

    To-day there is a growing need to predict numerically not only the mechanical parameters, but also the final microstructure of the work-piece. On the other hand, the use of simulation codes to analyze complex laboratory experiments can be viewed as a powerful way to improve the analysis of physical data. We outline basic methods for developing a finite element model of unsteady metal forming processes. At first the thermal and mechanical equations are recalled with several integral formulations. The most important issues are discussed, including time integration, evolving contact with rigid or deformable tools, meshing, remeshing, and parallel computing. Physical coupling is presented with the two possible approaches: introduction of internal parameters describing the evolution of microstructure and coupling with constitutive equations; multi-scale computation illustrated by the texture prediction. Finally it is shown that the inverse approach can be successfully applied to improve parameters identification from data acquisition of laboratory tests, or possibly from industrial experiments. This methodology can be utilized for: constitutive modeling, friction behavior, or even for internal parameters laws describing physical evolution. (author)

  15. Metal ion complex formation in small lakes of the Western Siberian Arctic zone

    Kremleva, Tatiana; Dinu, Marina

    2017-04-01

    The paper is based on joint investigation of the Tyumen State University (Russia, Tyumen) and the Geochemistry and Analytical Chemistry Vernadsky Institute of Russian Academy of Sciences (Moscow, Russia) during 2012-2014 period. It presents the results of research of chemical composition of about 70 small lakes located in the area of tundra and northern taiga of West Siberia (Russia, Yamal-Nenets and Khanty-Mansi Autonomous Districts of the Tyumen region). The investigation includes determination of different parameters of natural water samples: • content of trace elements (Al, Fe, Mn, Cr, Cu, Ni, Zn, Cd, Co, Pb, etc., total more than 60 elements) by emission method with an inductively coupled plasma (ICP-MS) using mass spektrometrometre Element 2 equipment; • content of inorganic and total carbon (TIC and TC) by elemental analysis and the difference between the total and inorganic carbon gives the organic carbon content (TOC); • pH value by potentiometric method; • content of basic ions (Na+, Ca2+, K+, Mg2+, NH4+, Cl-, SO42-, NO3-, PO43-) by ion chromatography. Determination of the chemical composition of samples was conducted in the accredited laboratory according to standard procedures with regular quality control of results. Heavy metals in natural waters can exist in various forms: free (hydrated) ions bound in complexes with organic or inorganic ligands, as well as in the form of suspensions. The form of metal existence has a significant influence on their availability to transport in aquatic organisms. Metal ions associated in stable complexes with organic substances are considered less toxic. From the previous investigations state that the most stable complexes are ligands with organic ions Fe3+, Al3+. The main conclusion of the present research states that if the total content of aluminum, iron and manganese ions (meq/dm3) is equal to or greater than the concentration of dissolved organic carbon (TOC, mg/dm3) in lakes water other heavy metals will

  16. AB INITIO molecular orbital studies of some high temperature metal halide complexes

    Curtiss, L.A.

    1978-01-01

    The use of ab initio molecular orbital calculations to aid in the characterization, i.e., structures and energies, of metal halide complexes present in high temperature salt vapors has been investigated. Standard LCAO-SCF methods were used and calculations were carried out using the minimal STO-3G basis set. The complexes included in this study were Al 2 F 6 , Al 2 Cl 6 , AlF 3 NH 3 , AlCl 3 NH 3 , and AlF 3 N 2 . The Al 2 X 6 complexes are found to have D/sub 2h/ symmetry in agreement with most experimental results. A planar form was found to be considerably higher in energy. The AlX 3 NH 3 complexes are found to have C/sub 3v/ symmetry with a small barrier to rotation about the Al-N axis. The AlF 3 N 2 complex is found to be weakly bound together with a binding energy of -8.2 kcal/mole at the STO-3G level

  17. Feature Size Effect on Formability of Multilayer Metal Composite Sheets under Microscale Laser Flexible Forming

    Huixia Liu

    2017-07-01

    Full Text Available Multilayer metal composite sheets possess superior properties to monolithic metal sheets, and formability is different from monolithic metal sheets. In this research, the feature size effect on formability of multilayer metal composite sheets under microscale laser flexible forming was studied by experiment. Two-layer copper/nickel composite sheets were selected as experimental materials. Five types of micro molds with different diameters were utilized. The formability of materials was evaluated by forming depth, thickness thinning, surface quality, and micro-hardness distribution. The research results showed that the formability of two-layer copper/nickel composite sheets was strongly influenced by feature size. With feature size increasing, the effect of layer stacking sequence on forming depth, thickness thinning ratio, and surface roughness became increasingly larger. However, the normalized forming depth, thickness thinning ratio, surface roughness, and micro-hardness of the formed components under the same layer stacking sequence first increased and then decreased with increasing feature size. The deformation behavior of copper/nickel composite sheets was determined by the external layer. The deformation extent was larger when the copper layer was set as the external layer.

  18. A guide for validation of FE-Simulations in bulk metal forming

    Tekkaya, A. Erman

    2005-01-01

    Numerical analysis of metal forming processes is an everyday practice in industry. Forming loads, material flow, forming defects such as underfills, laps and even cracks, stresses in dies and punches, as well as product properties like new hardness distribution, dimensional accuracies and residual stresses are predicted by numerical analysis and used for technology generation. Most of the numerical analysis is done by the finite element method made available for engineers and technicians by numerous by powerful commercial software packages. These software packages act as black-boxes and usually hide the complicated numerical procedures and even their crucial parameters from the applier. Therefore, the question arises during the industrial applications: how accurate is the simulation and how can the results can be assessed? The aim of this paper is to provide a guideline to assess the results of metal forming simulations. Although some ideas are valid for any metal forming process, bulk forming is the process concern. The paper will address firstly the possible sources of error in a finite element analysis of bulk forming processes. Then, some useful elementary knowledge will be summarized. Various levels of validation such as result and ability validation and assessment will be discussed. Finally, interpretation of results will be treated. In this content also some suggestions will be given. (author)

  19. On the capacity to the complexing of alkaline earth metal and magnesium chromates

    Orekhov, O.L.

    1978-01-01

    Considered is the capacity to the complexing of magnesium chromates and alkaline earth metal chromates with ammonium chromates in aqueous solutions. It has been established that the complexing of alkaline earth metal and magnesium chromates is effected by a nature of initial salts as well as their solubilities and the presence of crystallization water. Capacity of magnesium ions and alkaline rare earth metals to the complexing decreases in a series of Mg-Ca-Sr-Ba. Ca complexes exceed magnesium derivatives in respect of stability

  20. Impact of electrostatics on the chemodynamics of highly charged metal-polymer nanoparticle complexes.

    Duval, Jérôme F L; Farinha, José Paulo S; Pinheiro, José P

    2013-11-12

    In this work, the impact of electrostatics on the stability constant, the rate of association/dissociation, and the lability of complexes formed between Cd(II), Pb(II), and carboxyl-modified polymer nanoparticles (also known as latex particles) of radius ∼ 50 nm is systematically investigated via electroanalytical measurements over a wide range of pHs and NaNO3 electrolyte concentrations. The corresponding interfacial structure and key electrostatic properties of the particles are independently derived from their electrokinetic response, successfully interpreted using soft particle electrohydrodynamic formalism, and complemented by Förster resonance energy transfer (FRET) analysis. The results underpin the presence of an ∼0.7-1 nm thick permeable and highly charged shell layer at the surface of the polymer nanoparticles. Their electrophoretic mobility further exhibits a minimum versus NaNO3 concentration due to strong polarization of the electric double layer. Integrating these structural and electrostatic particle features with recent theory on chemodynamics of particulate metal complexes yields a remarkable recovery of the measured increase in complex stability with increasing pH and/or decreasing solution salinity. In the case of the strongly binding Pb(II), the discrepancy at pH > 5.5 is unambiguously assigned to the formation of multidendate complexes with carboxylate groups located in the particle shell. With increasing pH and/or decreasing electrolyte concentration, the theory further predicts a kinetically controlled formation of metal complexes and a dramatic loss of their lability (especially for lead) on the time-scale of diffusion toward a macroscopic reactive electrode surface. These theoretical findings are again shown to be in agreement with experimental evidence.

  1. The Origin of the Relation between Metallicity and Size in Star-forming Galaxies

    Sánchez Almeida, J.; Dalla Vecchia, C.

    2018-06-01

    For the same stellar mass, physically smaller star-forming galaxies are also metal richer. What causes the relation remains unclear. The central star-forming galaxies in the EAGLE cosmological numerical simulation reproduce the observed trend. We use them to explore the origin of the relation assuming that the physical mechanism responsible for the anticorrelation between size and gas-phase metallicity is the same in the simulated and the observed galaxies. We consider the three most likely causes: (1) metal-poor gas inflows feeding the star formation (SF) process, (2) metal-rich gas outflows particularly efficient in shallow gravitational potentials, and (3) enhanced efficiency of the SF process in compact galaxies. Outflows (cause 2) and enhanced SF efficiency (cause 3) can be discarded. Metal-poor gas inflows (cause 1) produce the correlation in the simulated galaxies. Galaxies grow in size with time, so those that receive gas later are both metal poorer and larger, giving rise to the observed anticorrelation. As expected within this explanation, larger galaxies have younger stellar populations. We explore the variation with redshift of the relation, which is maintained up to, at least, redshift 8.

  2. Speciation Studies of Some Toxic Metal Complexes of Glycylglycine ...

    NICO

    mixtures apart from its established utility in understanding ... Chemical speciation of metals is important for an understand- ... Titrations with differ- ent ratios (1:2.5, 1:3.5 and 1:5) of metal-ligand were performed with 0.4 mol L–1 sodium hydroxide solution. The mixtures obtained from PG and water are non-ideal due.

  3. Metal waste forms from treatment of EBR-II spent fuel

    Abraham, D. P.

    1998-01-01

    Demonstration of Argonne National Laboratory's electrometallurgical treatment of spent nuclear fuel is currently being conducted on irradiated, metallic driver fuel and blanket fuel elements from the Experimental Breeder Reactor-II (EBR-II) in Idaho. The residual metallic material from the electrometallurgical treatment process is consolidated into an ingot, the metal waste form (MWF), by employing an induction furnace in a hot cell. Scanning electron microscopy (SEM) and chemical analyses have been performed on irradiated cladding hulls from the driver fuel, and on samples from the alloy ingots. This paper presents the microstructures of the radioactive ingots and compares them with observations on simulated waste forms prepared using non-irradiated material. These simulated waste forms have the baseline composition of stainless steel - 15 wt % zirconium (SS-15Zr). Additions of noble metal elements, which serve as surrogates for fission products, and actinides are made to that baseline composition. The partitioning of noble metal and actinide elements into alloy phases and the role of zirconium for incorporating these elements is discussed in this paper

  4. Humic Acid Complexation of Th, Hf and Zr in Ligand Competition Experiments: Metal Loading and Ph Effects

    Stern, Jennifer C.; Foustoukos, Dionysis I.; Sonke, Jeroen E.; Salters, Vincent J. M.

    2014-01-01

    The mobility of metals in soils and subsurface aquifers is strongly affected by sorption and complexation with dissolved organic matter, oxyhydroxides, clay minerals, and inorganic ligands. Humic substances (HS) are organic macromolecules with functional groups that have a strong affinity for binding metals, such as actinides. Thorium, often studied as an analog for tetravalent actinides, has also been shown to strongly associate with dissolved and colloidal HS in natural waters. The effects of HS on the mobilization dynamics of actinides are of particular interest in risk assessment of nuclear waste repositories. Here, we present conditional equilibrium binding constants (Kc, MHA) of thorium, hafnium, and zirconium-humic acid complexes from ligand competition experiments using capillary electrophoresis coupled with ICP-MS (CE- ICP-MS). Equilibrium dialysis ligand exchange (EDLE) experiments using size exclusion via a 1000 Damembrane were also performed to validate the CE-ICP-MS analysis. Experiments were performed at pH 3.5-7 with solutions containing one tetravalent metal (Th, Hf, or Zr), Elliot soil humic acid (EHA) or Pahokee peat humic acid (PHA), and EDTA. CE-ICP-MS and EDLE experiments yielded nearly identical binding constants for the metal- humic acid complexes, indicating that both methods are appropriate for examining metal speciation at conditions lower than neutral pH. We find that tetravalent metals form strong complexes with humic acids, with Kc, MHA several orders of magnitude above REE-humic complexes. Experiments were conducted at a range of dissolved HA concentrations to examine the effect of [HA]/[Th] molar ratio on Kc, MHA. At low metal loading conditions (i.e. elevated [HA]/[Th] ratios) the ThHA binding constant reached values that were not affected by the relative abundance of humic acid and thorium. The importance of [HA]/[Th] molar ratios on constraining the equilibrium of MHA complexation is apparent when our estimated Kc, MHA values

  5. Crown Ether Complexes of Alkali-Metal Chlorides from SO2.

    Reuter, Kirsten; Rudel, Stefan S; Buchner, Magnus R; Kraus, Florian; von Hänisch, Carsten

    2017-07-18

    The structures of alkali-metal chloride SO 2 solvates (Li-Cs) in conjunction with 12-crown-4 or 1,2-disila-12-crown-4 show strong discrepancies, despite the structural similarity of the ligands. Both types of crown ethers form 1:1 complexes with LiCl to give [Li(1,2-disila-12-crown-4)(SO 2 Cl)] (1) and [Li(12-crown-4)Cl]⋅4 SO 2 (2). However, 1,2-disila-12-crown-4 proved unable to coordinate cations too large for the cavity diameter, for example, by the formation of sandwich-type complexes. As a result, 12-crown-4 reacts exclusively with the heavier alkali-metal chlorides NaCl, KCl and RbCl. Compounds [Na(12-crown-4) 2 ]Cl⋅4 SO 2 (3) and [M(12-crown-4) 2 (SO 2 )]Cl⋅4 SO 2 (4: M=K; 5: M=Rb) all showed S-coordination to the chloride ions through four SO 2 molecules. Compounds 4 and 5 additionally exhibit the first crystallographically confirmed non-bridging O,O'-coordination mode of SO 2 . Unexpectedly, the disila-crown ether supports the dissolution of RbCl and CsCl in the solvent and gives the homoleptic SO 2 -solvated alkali-metal chlorides [MCl⋅3 SO 2 ] (6: M=Rb; 7: M=Cs), which incorporate bridging μ-O,O'-coordinating moieties and the unprecedented side-on O,O'-coordination mode. All compounds were characterised by single-crystal X-ray diffraction. The crown ether complexes were additionally studied by using NMR spectroscopy, and the presence of SO 2 at ambient temperature was revealed by IR spectroscopy of the neat compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Dry metal forming of high alloy steel using laser generated aluminum bronze tools

    Freiße Hannes

    2015-01-01

    Full Text Available Regarding the optimization of forming technology in economic and environmental aspects, avoiding lubricants is an approach to realize the vision of a new green technology. The resulting direct contact between the tool and the sheet in non-lubricated deep drawing causes higher stress and depends mainly on the material combination. The tribological system in dry sliding has to be assessed by means on the one hand of the resulting friction coefficient and on the other hand of the wear of the tool and sheet material. The potential to generate tailored tribological systems for dry metal forming could be shown within the investigations by using different material combinations and by applying different laser cladding process parameters. Furthermore, the feasibility of additive manufacturing of a deep drawing tool was demonstrated. The tool was successfully applied to form circular cups in a dry metal forming process.

  7. Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes

    Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M. Arif

    2016-05-01

    We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica.

  8. Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes.

    Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M Arif

    2016-05-15

    We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Springback prediction in sheet metal forming process based on the hybrid SA

    Guo Yuqin; Jiang Hong; Wang Xiaochun; Li Fuzhu

    2005-01-01

    In terms of the intensive similarity between the sheet metal forming-springback process and that of the annealing of metals, it is suggested that the simulation of the sheet metal forming process is performed with the Nonlinear FEM and the springback prediction is implemented by solving the large-scale combinational optimum problem established on the base of the energy descending and balancing in deformed part. The BFGS-SA hybrid SA approach is proposed to solve this problem and improve the computing efficiency of the traditional SA and its capability of obtaining the global optimum solution. At the same time, the correlative annealing strategies for the SA algorithm are determined in here. By comparing the calculation results of sample part with those of experiment measurement at the specified sections, the rationality of the schedule of springback prediction used and the validity of the BFGS-SA algorithm proposed are verified

  10. Development of parallel benchmark code by sheet metal forming simulator 'ITAS'

    Watanabe, Hiroshi; Suzuki, Shintaro; Minami, Kazuo

    1999-03-01

    This report describes the development of parallel benchmark code by sheet metal forming simulator 'ITAS'. ITAS is a nonlinear elasto-plastic analysis program by the finite element method for the purpose of the simulation of sheet metal forming. ITAS adopts the dynamic analysis method that computes displacement of sheet metal at every time unit and utilizes the implicit method with the direct linear equation solver. Therefore the simulator is very robust. However, it requires a lot of computational time and memory capacity. In the development of the parallel benchmark code, we designed the code by MPI programming to reduce the computational time. In numerical experiments on the five kinds of parallel super computers at CCSE JAERI, i.e., SP2, SR2201, SX-4, T94 and VPP300, good performances are observed. The result will be shown to the public through WWW so that the benchmark results may become a guideline of research and development of the parallel program. (author)

  11. Linking structure to fragility in bulk metallic glass-forming liquids

    Wei, Shuai; Stolpe, Moritz; Gross, Oliver; Gallino, Isabella; Hembree, William; Busch, Ralf; Evenson, Zach; Bednarcik, Jozef; Kruzic, Jamie J.

    2015-01-01

    Using in-situ synchrotron X-ray scattering, we show that the structural evolution of various bulk metallic glass-forming liquids can be quantitatively connected to their viscosity behavior in the supercooled liquid near T g . The structural signature of fragility is identified as the temperature dependence of local dilatation on distinct key atomic length scales. A more fragile behavior results from a more pronounced thermally induced dilatation of the structure on a length scale of about 3 to 4 atomic diameters, coupled with shallower temperature dependence of structural changes in the nearest neighbor environment. These findings shed light on the structural origin of viscous slowdown during undercooling of bulk metallic glass-forming liquids and demonstrate the promise of predicting the properties of bulk metallic glasses from the atomic scale structure

  12. Linking structure to fragility in bulk metallic glass-forming liquids

    Wei, Shuai, E-mail: shuai.wei@asu.edu, E-mail: m.stolpe@mx.uni-saarland.de [Department of Materials Science and Engineering, Saarland University, Campus C63, 66123 Saarbrücken (Germany); Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287 (United States); Stolpe, Moritz, E-mail: shuai.wei@asu.edu, E-mail: m.stolpe@mx.uni-saarland.de; Gross, Oliver; Gallino, Isabella; Hembree, William; Busch, Ralf [Department of Materials Science and Engineering, Saarland University, Campus C63, 66123 Saarbrücken (Germany); Evenson, Zach [Department of Materials Science and Engineering, Saarland University, Campus C63, 66123 Saarbrücken (Germany); Institut für Materialphysik im Weltraum, Deutsches Zentrum für Luft- und Raumfahrt (DLR), 51170 Köln (Germany); Bednarcik, Jozef [Deutsches Elektronen-Synchrotron DESY, Notkestrasse 85, D-22603 Hamburg (Germany); Kruzic, Jamie J. [Material Science, School of Mechanical, Industrial, and Manufacturing Engineering, Oregon State University, Corvallis, Oregon 97331 (United States)

    2015-05-04

    Using in-situ synchrotron X-ray scattering, we show that the structural evolution of various bulk metallic glass-forming liquids can be quantitatively connected to their viscosity behavior in the supercooled liquid near T{sub g}. The structural signature of fragility is identified as the temperature dependence of local dilatation on distinct key atomic length scales. A more fragile behavior results from a more pronounced thermally induced dilatation of the structure on a length scale of about 3 to 4 atomic diameters, coupled with shallower temperature dependence of structural changes in the nearest neighbor environment. These findings shed light on the structural origin of viscous slowdown during undercooling of bulk metallic glass-forming liquids and demonstrate the promise of predicting the properties of bulk metallic glasses from the atomic scale structure.

  13. Direct testing of scale effects in metal forming friction and lubrication

    Nielsen, Peter Søe; Calaon, Matteo; Paldan, Nikolas Aulin

    2010-01-01

    Downscaling of metal forming operations from macro to micro scale implies significant changes caused by size effects, among these the friction increase, which has been reported by researchers using indirect test methods such as ring-compression test and double-cup-extrusion test. In the present w...

  14. Testing and modelling of industrial tribo-systems for sheet metal forming

    Friis, Kasper Leth; Nielsen, Peter Søe; Bay, Niels

    2008-01-01

    Galling is a well-known problem in sheet metal forming of tribological difficult materials such as stainless steel. In this work new, environmentally friendly lubricants and wear resistant tool materials are tested in a laboratory environment using a strip reduction test as well as in a real...

  15. Numerical modelling of microscopic lubricant flow in sheet metal forming. Application to plane strip drawing

    Carretta, Y.; Boman, R.; Bech, Jakob Ilsted

    2017-01-01

    This paper presents a numerical investigation of microscopic lubricant flows from the cavities to the plateaus of the surface roughness of metal sheets during forming processes. This phenomenon, called micro-plasto-hydrodynamic (MPH) lubrication, was observed experimentally in various situations...

  16. Static friction in rubber-metal contacts with application to rubber pad forming processes

    Deladi, E.L.

    2006-01-01

    A static friction model suitable for rubber-metal contact is presented in this dissertation. In introduction, the motivation and the aims of the research are introduced together with the background regarding the related industrial application, which is the rubber pad forming process.

  17. Estimating product-to-product variations in metal forming using force measurements

    Havinga, Gosse Tjipke; Van Den Boogaard, Ton

    2017-01-01

    The limits of production accuracy of metal forming processes can be stretched by the development of control systems for compensation of product-to-product variations. Such systems require the use of measurements from each semi-finished product. These measurements must be used to estimate the final

  18. Development of millimeter-wave accelerating structures using precision metal forming technology

    None

    2003-06-03

    High gradients in radio-frequency (RF) driven accelerators require short wavelengths that have the concomitant requirements of small feature size and high tolerances, 1-2 {micro}m for millimeter wavelengths. Precision metal-forming stampling has the promise of meeting those tolerances with high production rates. This STI will evaluate that promise.

  19. Friction modelling in sheet metal forming simulations: application and validation on an U-Bend product

    Sigvant, Mats; Hol, Johan; Chezan, Toni; van den Boogaard, Ton; Hora, P.

    2015-01-01

    The accuracy of sheet metal forming simulations strongly depends on, amongst others, friction modelling. The industrial standard is to use the Coulomb friction model with a constant coefficient of friction. However, it is known that the true friction conditions are dependent on the tribology system,

  20. Improvements in FE-analysis of real-life sheet metal forming

    Huetink, Han; van den Boogaard, Antonius H.; Geijselaers, Hubertus J.M.; Meinders, Vincent T.

    2000-01-01

    An overview will be presented of recent developments concerning the application and development of computer codes for numerical simulation of sheet metal forming processes. In this paper attention is paid to some strategies which are followed to improve the accuracy and to reduce the computation

  1. Glassy slags as novel waste forms for remediating mixed wastes with high metal contents

    Feng, X.; Wronkiewicz, D.J.; Bates, J.K.; Brown, N.R.; Buck, E.C.; Gong, M.; Ebert, W.L.

    1994-01-01

    Argonne National Laboratory (ANL) is developing a glassy slag final waste form for the remediation of low-level radioactive and mixed wastes with high metal contents. This waste form is composed of various crystalline and metal oxide phases embedded in a silicate glass phase. This work indicates that glassy slag shows promise as final waste form because (1) it has similar or better chemical durability than high-level nuclear waste (HLW) glasses, (2) it can incorporate large amounts of metal wastes, (3) it can incorporate waste streams having low contents of flux components (boron and alkalis), (4) it has less stringent processing requirements (e.g., viscosity and electric conductivity) than glass waste forms, (5) its production can require little or no purchased additives, which can result in greater reduction in waste volume and overall treatment costs. By using glassy slag waste forms, minimum additive waste stabilization approach can be applied to a much wider range of waste streams than those amenable only to glass waste forms

  2. Convection in complex shaped vessel; Convection dans des enceintes de forme complexe

    NONE

    2000-07-01

    The 8 november 2000, the SFT (Societe Francaise de Thermique) organized a technical day on the convection in complex shaped vessels. Nine papers have been presented in the domains of the heat transfers, the natural convection, the fluid distribution, the thermosyphon effect, the steam flow in a sterilization cycle and the transformers cooling. Eight papers are analyzed in ETDE and one paper dealing with the natural convection in spent fuels depository is analyzed in INIS. (A.L.B.)

  3. METALLICITY IN THE GRB 100316D/SN 2010bh HOST COMPLEX

    Levesque, Emily M.; Berger, Edo; Soderberg, Alicia M.; Chornock, Ryan

    2011-01-01

    The recent long-duration GRB 100316D, associated with supernova SN 2010bh and detected by Swift, is one of the nearest gamma-ray burst (GRB)-supernovae (SNe) ever observed (z = 0.059). This provides us with a unique opportunity to study the explosion environment on ∼kpc scale in relation to the host galaxy complex. Here we present spatially resolved spectrophotometry of the host galaxy, focusing on both the explosion site and the brightest star-forming regions. Using these data, we extract the spatial profiles of the relevant emission features (Hα, Hβ, [O III]λ5007, and [N II]λ6584) and use these profiles to examine variations in metallicity and star formation rate (SFR) as a function of position in the host galaxy. We conclude that GRB 100316D/SN2010bh occurred in a low-metallicity host galaxy, and that the GRB-SN explosion site corresponds to the region with the lowest metallicity and highest SFR sampled by our observations.

  4. Multiheteromacrocycles that Complex Metal Ions. Sixth Progress Report, 1 May 1979-30 April 1980

    Cram, D. J.

    1980-01-15

    Objective is to design synthesize, and evaluate cyclic and polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions, their complexes, and their clusters. Host organic compounds consist of strategically placed solvating, coordinating, and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions or by metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; number of binding sites; character of binding sites; and valences. During this period, hemispherands based on an aryloxy or cyclic urea unit, spherands based on aryloxyl units only, and their complexes with alkali metals and alkaline earths were investigated. An attempt to separate {sup 6}Li and {sup 7}Li by gel permeation chromatography of lithiospherium chloride failed. (DLC)

  5. Structure and catalytic properties of metal β-diketonate complexes with oxygen-containing compounds

    Nizel'skij, Yu.N.; Ishchenko, S.S.; Lipatova, T.Eh.

    1985-01-01

    The results of researches published in recent 15-20 years of complexes of metal β-diketonates (including Cr 3+ , VO 2+ , MoOΛ2 2+ , Co 3+ , Mn 3+ , Ni 2+ , Fe 3+ ) with oxygen-containing compounds (alcohols, glycols, phenols, hydroperoxides, aldehydes, esters, etc.) playing an important role in catalytic processes of oxidation, addition, polymerization and copolymerization are reviewed. Data on the nature of chemical bond of oxygen-containing reacting agents with metal β-diketonates, on structure of metal β-diketonate complexes with oxygen-containing reacting agents and thermodynamics of complexing as well as on activation of reacting agents in complexes and catalytic properties of metal β-diketonates are discussed. Stored materials make it possible to exercise directed control of metal β-diketonate activity

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

    a

    derivative of 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, atrazine (ATZ) --- a well known herbicide has ... development while the other is the metal ion associated degradation or deactivation of the herbicides .... Colour M.p./decomp.

  7. Study of complex amalgams containing alkali metals by method of broken thermometric titration

    Filippova, L.M.; Zebreva, A.I.; Espenbetov, A.A.

    1977-01-01

    Complex potassium-cadmium and sodium-cadmium amalgams containing different amounts of the alkali metal nad cadmium have been studied by thermometric titration with mercury. The experiments have been carried out in argon atmosphere at 25 deg C. As evidenced by the titration of sodium-cadmium amalgams, in the range of concentrations studied (Csub(Na)=0.71-2.95, Csub(Cd)=4.38-6.45 g-at/lHg) no solid phase is formed in them. Potassium-cadmium amalgams where the metals content is no higher than their individual solubility in mercury, display, when being mercury-titrated, negative heat effects due to solid phase formation. An estimation is made of the solid phase composition, its solubility in mercury and the heat of dissolution. The solid phase appearing in complex K-Cd amalgams is likely to contain K and Cd in a ratio 1:1 its conventional solubility product is 5.4 g-at/l Hg, and the heat of dissolution in mercury at 25 deg is -21 +-4 kJ/g-at

  8. Bis(pentamethylcyclopentadienyl) ytterbium: Electron-transfer reactions with organotransition metal complexes

    Matsunaga, P.T.

    1991-11-01

    The divalent lanthanide complex, (Me{sub 5}C{sub 5}){sub 2}Yb, reacts with methylcopper to produce the base-free, ytterbium-methyl complex, (Me{sub 5}C{sub 5}){sub 2}YbMe. This product forms a asymmetric, methyl-bridged dimer in the solid state. The bulky alkyl complex, (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}, displays similar chemistry to (Me{sub 5}C{sub 5}){sub 2}YbMe, but at a reduced reaction rate due to the limited accessibility of the metal in (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}. Copper and silver halide salts react with (Me{sub 5}C{sub 5}){sub 2}V to produce the trivalent halide derivatives, (Me{sub 5}C{sub 5}){sub 2}VX (X + F, Cl, Br, I). The chloride complex, (Me{sub 5}C{sub 5}){sub 2}VCl, reacts with lithium reagents to form the phenyl and borohydride species. Nitrous oxide transfers an oxygen atom to (Me{sub 5}C{sub 5}){sub 2}V producing the vanadium-oxo complex, (Me{sub 5}Ce{sub 5}){sub 2}VO. The trivalent titanium species, (Me{sub 5}C{sub 5}){sub 2}TiX (X = Cl, Br, Me, BH{sub 4}), form bimetallic coordination complexes with (Me{sub 5}C{sub 5}){sub 2}Yb. The magnetic behavior of the products indicates that electron transfer has not occurred. The solid state structures of the chloride and bromide complexes show unusual bend angles for the halide bridges between ytterbium and titanium. A model based on frontier orbital theory has been proposed to account for the bending behavior in these species. The bimetallic methyl complex contains a linear methyl bridge between ytterbium and titanium.

  9. Bis(pentamethylcyclopentadienyl) ytterbium: Electron-transfer reactions with organotransition metal complexes

    Matsunaga, Phillip Thomas [Univ. of California, Berkeley, CA (United States)

    1991-11-01

    The divalent lanthanide complex, (Me5C5)2Yb, reacts with methylcopper to produce the base-free, ytterbium-methyl complex, (Me5C5)2YbMe. This product forms a asymmetric, methyl-bridged dimer in the solid state. The bulky alkyl complex, (Me5C5)2YbCH(SiMe3)2, displays similar chemistry to (Me5C5)2YbMe, but at a reduced reaction rate due to the limited accessibility of the metal in (Me5C5)3YbCH(SiMe5)2. Copper and silver halide salts react with (Me5C5)2V to produce the trivalent halide derivatives, (Me5C5)2VX (X + F, Cl, Br, I). The chloride complex, (Me5C5)2VCl, reacts with lithium reagents to form the phenyl and borohydride species. Nitrous oxide transfers an oxygen atom to (Me5C5)2V producing the vanadium-oxo complex, (Me5Ce5)2VO. The trivalent titanium species, (Me5C5)2TiX (X = Cl, Br, Me, BH4), form bimetallic coordination complexes with (Me5C5)2Yb. The magnetic behavior of the products indicates that electron transfer has not occurred. The solid state structures of the chloride and bromide complexes show unusual bend angles for the halide bridges between ytterbium and titanium. A model based on frontier orbital theory has been proposed to account for the bending behavior in these species. The bimetallic methyl complex contains a linear methyl bridge between ytterbium and titanium.

  10. Metal ion-improved complexation countercurrent chromatography for enantioseparation of dihydroflavone enantiomers.

    Han, Chao; Wang, Wenli; Xue, Guimin; Xu, Dingqiao; Zhu, Tianyu; Wang, Shanshan; Cai, Pei; Luo, Jianguang; Kong, Lingyi

    2018-01-12

    Cu(II) ion was selected as an additive to improve the enantioseparation efficiency of three dihydroflavone enantiomers in high-speed counter-current chromatography (HSCCC), using hydroxypropyl-β-cyclodextrin (HP-β-CyD) as the chiral selector. The influences of important parameters, including the metal ion, the concentrations of HP-β-CyD and the Cu(II) ion, and the sample size were investigated. Under optimal conditions, three dihydroflavone enantiomers, including (±)-hesperetin, (±)-naringenin, and (±)-farrerol, were successfully enantioseparated. The chiral recognition mechanism was investigated. The enantioseparation was attributed to the different thermodynamic stabilities of the binary complexes of HP-β-CyD and (±)-hesperetin, and Cu(II) ion could enhance this difference by forming ternary complexes with the binary complexes. This Cu(II) ion-improved complexation HSCCC system exhibited improved performance for chiral separation, and therefore it has great application potential in the preparative enantioseparation of other compounds with similar skeletons. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Transition metal complexes with oxygen donor ligands: a synthesis, spectral, thermal and antimicrobial study

    VAIBHAV N. PATANGE

    2008-10-01

    Full Text Available Transition metal complexes of chalcones derived from the conden¬sation of 3-acetyl-6-methyl-2H-pyran-2,4(3H-dione (dehydroacetic acid and p-methoxybenzaldehyde (HL1 or p-nitrobenzaldehyde (HL2 were synthesized and characterized by elemental analysis, conductometry, thermal analysis, magnetic measurements, IR, 1H-NMR, UV–Vis spectroscopy and a microbial study. From the analytical and thermal data, the stoichiometry of the complexes was found to be 1:2 (metal:ligand. The molar conductance data revealed that all the metal chelates were non-electrolytes. The thermal stability of the complexes was studied by thermogravimetry and the decomposition schemes of the complexes are given. The ligands and their metal complexes were screened for antibacterial activity against Staphylococcus aureus and Escherichia coli, and fungicidal activity against Aspergillus flavus, Curvularia lunata and Penicillium notatum.

  12. Determination of stability constants of aminoglycoside antibiotics with their metal complexes

    Tiwow, Vanny M. A.

    2014-03-01

    One group of aminoglycoside antibiotics contains aminosugars. The aminosugar neomycin B with its derivate product neamine (2-Deoxy-4-0-(2,6-diamino-2,6-dideoxy-α-D-glucopyranosyl)-D-Streptamine) was identified as a free ligands and metal complexes. In particular, the stability constants of metal complexes by potentiometric titration techniques were investigated. Our previous study had determined the acid dissociation constants of these aminosugars with few metal complexes in fair depth. In this work, the complexation of two pyridine-containing amino alcohols and an amino sugar (neamine) have been measured potentiometrically. For instance, the stability constant of copper(II) complexation were determine and the model system generated an excellent fit. Stability constants with several metals have been determined and will be reported.

  13. Yucca Mountain project canister material corrosion studies as applied to the electrometallurgical treatment metallic waste form

    Keiser, D.D.

    1996-11-01

    Yucca Mountain, Nevada is currently being evaluated as a potential site for a geologic repository. As part of the repository assessment activities, candidate materials are being tested for possible use as construction materials for waste package containers. A large portion of this testing effort is focused on determining the long range corrosion properties, in a Yucca Mountain environment, for those materials being considered. Along similar lines, Argonne National Laboratory is testing a metallic alloy waste form that also is scheduled for disposal in a geologic repository, like Yucca Mountain. Due to the fact that Argonne's waste form will require performance testing for an environment similar to what Yucca Mountain canister materials will require, this report was constructed to focus on the types of tests that have been conducted on candidate Yucca Mountain canister materials along with some of the results from these tests. Additionally, this report will discuss testing of Argonne's metal waste form in light of the Yucca Mountain activities

  14. Elg1 forms an alternative RFC complex important for DNA replication and genome integrity

    Bellaoui, Mohammed; Chang, Michael; Ou, Jiongwen; Xu, Hong; Boone, Charles; Brown, Grant W

    2003-01-01

    Genome-wide synthetic genetic interaction screens with mutants in the mus81 and mms4 replication fork-processing genes identified a novel replication factor C (RFC) homolog, Elg1, which forms an alternative RFC complex with Rfc2-5. This complex is distinct from the DNA replication RFC, the DNA

  15. Addition of electric arc furnace dust in hot metal changing the form of addition

    Marques Sobrinho, Vicente de Paulo Ferreira; Oliveira, Jose Roberto de; Vieira, Estefano Aparecido; Telles, Victor Bridi; Grillo, Felipe Fardin; Tenorio, Jorge Alberto Soares; Espinosa, Denise Crocce Romano

    2014-01-01

    This research aims to study the incorporation of the mass of electric arc furnace dust (EAFD), by addition in hot metal (1.78% Si) at a temperature of 1,400 degrees Celsius. The EAFD is from a steel plant producing long steel. The addition of the EAFD was as received, in the form of briquettes without agitation of the hot metal and in the form of briquettes with agitation of the hot metal. Previously, the EAFD was characterized using the following techniques: chemical analysis, size analysis, X-ray diffraction, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) microanalysis. The achievement of fusion experiments in laboratory scale, took place in a vertical tubular furnace with temperature control. The fusion experiments to assess the incorporation of EAFD mass used graphite crucibles. After cooling, the hot metal and the slag, remaining in the crucible, were weighed to do a mass balance. A flow of inert gas (argon) was maintained inside the furnace during the experiments. Results show that the experiment with addition of EAFD as received presents the best result of incorporating the mass of the final hot metal (1.73%) combined with the lowest percentage of volatilized mass of EAFD (46.52%). The experiment addition of EAFD in the form of briquette with agitation of hot metal presents the lowest percentage of slag mass (4.58%). The zinc content of volatilized EAFD (64.30%) is higher than the zinc content of the imported ore concentrate (52%) and zinc content of the national ore concentrate (12% to 39%). The presence of lead and cadmium in the slag characterizing it as a hazardous solid waste. (author)

  16. Metal-ion complexes of functionalised 1,10-Phenanthrolines as hydrolytic synzymes

    Weijnen, J.G.J.

    1993-01-01

    In this thesis metal-ion complexes of functionalised 1,10-phenanthroline derivatives have been studied as model systems for hydrolytic metallo-enzymes. Amphiphilic metallo- complexes incorporated into micelles or vesicles and water-soluble complexes in pure aqueous buffer solutions, have

  17. Preparation and characterization of Zr-based bulk metallic glasses in form of plate

    Pilarczyk, Wirginia

    2014-01-01

    Highlights: • Zr-based BMGs in form of plate was successful produced by die pressure casting method. • Many techniques have been used to characterize the structure of Zr 55 Cu 30 Ni 5 Al 10 alloy. • The calculated GFA parameters show that the alloy exhibits satisfactory GFA. • The studies reveal that tested as-cast Zr-based alloy is in amorphous state. - Abstract: Zr-based bulk metallic glasses present an interesting combination of physical, chemical and mechanical properties. During the last decade, intensive progress has been made and a number of applications have been suggested for these materials. In order to successfully apply these materials, it is necessary to accurately characterize their structure, thermal stability and other properties accurately. The aim of the presented work is the manufacturing, examination of the structure of selected Zr-based bulk metallic alloys and confirmation of an amorphous structure using X-ray analysis, microscopic observation and thermal analysis. In this work, the Zr-based bulk metallic glasses in form of plate was successful produced by die pressure casting method. Designed scientific station for casting zirconium based amorphous alloys in the form of plates and rods with selected dimensions is in our university a comprehensive method for achieving amorphous materials which enables us to maintain repeatability of as-cast samples with the amorphous structure and the assumed dimensions range. The diffraction pattern and exothermic reaction as well as the fracture surface morphology reveal that studied as-cast Zr-based alloy is in amorphous state. The calculated GFA parameters show that the alloy exhibits satisfactory glass-forming ability in form of studied plate. These obtained values can suggest that studied alloys are suitable materials for further planned practical application at welding process. The success of Zr-based bulk metallic glasses production in form of plate with obtained sizes is important for future

  18. Synthesis, spectral, thermal, potentiometric and antimicrobial studies of transition metal complexes of tridentate ligand

    Sarika M. Jadhav

    2014-01-01

    Full Text Available A series of metal complexes of Cu(II, Ni(II, Co(II, Fe(III and Mn(II have been synthesized with newly synthesized biologically active tridentate ligand. The ligand was synthesized by condensation of dehydroacetic acid (3-acetyl-6-methyl-(2H pyran-2,4(3H-dione or DHA, o-phenylene diamine and fluoro benzaldehyde and characterized by elemental analysis, molar conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, IR, 1H-NMR, UV–Vis spectroscopy and mass spectra. From the analytical data, the stoichiometry of the complexes was found to be 1:2 (metal:ligand with octahedral geometry. The molar conductance values suggest the non-electrolyte nature of metal complexes. The IR spectral data suggest that the ligand behaves as a dibasic tridentate ligand with ONN donor atoms sequence towards central metal ion. Thermal behaviour (TG/DTA and kinetic parameters calculated by the Coats–Redfern and Horowitz–Metzger method suggest more ordered activated state in complex formation. To investigate the relationship between stability constants of metal complexes and antimicrobial activity, the dissociation constants of Schiff bases and stability constants of their binary metal complexes have been determined potentiometrically in THF–water (60:40% solution at 25 ± 1 °C and at 0.1 M NaClO4 ionic strength. The potentiometric study suggests 1:1 and 1:2 complexation. Antibacterial and antifungal activities in vitro were performed against Staphylococcus aureus, Escherichia coli and Aspergillus niger, Trichoderma, respectively. The stability constants of the metal complexes were calculated by the Irving–Rosotti method. A relation between the stability constant and antimicrobial activity of complexes has been discussed. It is observed that the activity enhances upon complexation and the order of antifungal activity is in accordance with stability order of metal ions.

  19. Elaboration of the technology of forming a conical product of sheet metal

    W. Matysiak

    2010-01-01

    Full Text Available The work presents a general knowledge about spinning draw pieces of sheets, one of multi-operational processes of spinning a sheet metal conical product without machining. The objective of the work was to elaborate both the technology of forming conical products of sheet metal and execution of technological tests as well as to determine the technological parameters for the process of spinning a conical insert. As a result of the investigations, the products with improved mechanical properties, stricter execution tolerance and low roughness have been obtained. The series of 200 prototype conical inserts for the shipbuilding industry have been made.

  20. Initial Evaluation of Processing Methods for an Epsilon Metal Waste Form

    Crum, Jarrod V.; Strachan, Denis M.; Zumhoff, Mac R.

    2012-01-01

    During irradiation of nuclear fuel in a reactor, the five metals, Mo, Pd, Rh, Ru, and Tc, migrate to the fuel grain boundaries and form small metal particles of an alloy known as epsilon metal ((var e psilon)-metal). When the fuel is dissolved in a reprocessing plant, these metal particles remain behind with a residue - the undissolved solids (UDS). Some of these same metals that comprise this alloy that have not formed the alloy are dissolved into the aqueous stream. These metals limit the waste loading for a borosilicate glass that is being developed for the reprocessing wastes. Epsilon metal is being developed as a waste form for the noble metals from a number of waste streams in the aqueous reprocessing of used nuclear fuel (UNF) - (1) the (var e psilon)-metal from the UDS, (2) soluble Tc (ion-exchanged), and (3) soluble noble metals (TRUEX raffinate). Separate immobilization of these metals has benefits other than allowing an increase in the glass waste loading. These materials are quite resistant to dissolution (corrosion) as evidenced by the fact that they survive the chemically aggressive conditions in the fuel dissolver. Remnants of (var e psilon)-metal particles have survived in the geologically natural reactors found in Gabon, Africa, indicating that they have sufficient durability to survive for ∼ 2.5 billion years in a reducing geologic environment. Additionally, the (var e psilon)-metal can be made without additives and incorporate sufficient foreign material (oxides) that are also present in the UDS. Although (var e psilon)-metal is found in fuel and Gabon as small particles (∼10 (micro)m in diameter) and has survived intact, an ideal waste form is one in which the surface area is minimized. Therefore, the main effort in developing (var e psilon)-metal as a waste form is to develop a process to consolidate the particles into a monolith. Individually, these metals have high melting points (2617 C for Mo to 1552 C for Pd) and the alloy is expected

  1. Forms of iron in soils on basement complex rocks of Kaduna state in ...

    The forms of iron extracted by different methods were studied in soils developed on four basement complex rocks within Northern Guinea Savanna of Nigeria namely: migmatite gneisses, older granite, quartzites and mica schists. The study shows that forms of iron generally decreased in the order of total elemental iron ...

  2. Synthesis and luminescence properties of hybrid organic-inorganic transparent titania thin film activated by in- situ formed lanthanide complexes

    Wang, Yige; Wang, Li; Li, Huanrong; Liu, Peng; Qin, Dashan; Liu, Binyuan; Zhang, Wenjun; Deng, Ruiping; Zhang, Hongjie

    2008-03-01

    Stable transparent titania thin films were fabricated at room temperature by combining thenoyltrifluoroacetone (TTFA)-modified titanium precursors with amphiphilic triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, P123) copolymers. The obtained transparent titania thin films were systematically investigated by IR spectroscopy, PL emission and excitation spectroscopy and transmission electron microscopy. IR spectroscopy indicates that TTFA coordinates the titanium center during the process of hydrolysis and condensation. Luminescence spectroscopy confirms the in-situ formation of lanthanide complexes in the transparent titania thin film. TEM image shows that the in-situ formed lanthanide complexes were homogeneously distributed throughout the whole thin film. The quantum yield and the number of water coordinated to lanthanide metal center have been theoretically determined based on the luminescence data.

  3. Lanthanide Single-Molecule Magnets Framed by Alkali Metals & Magnetic and Spectroscopic Studies of 3d Transition Metal Complexes

    Konstantatos, Andreas

    -molecule magnets (SMMs). Starting from the archetype SMM Mn12 we present the details of the mechanisms governing the relaxation of the magnetization of these systems. In Chapter 2 we present our work on the coordination chemistry of lanthanides with a new Schiff-base ligand, H3L [(E)-3-((2-hydroxyphenyl...... complexes of M3+ or M2+ metal ions (M: 3d transition metal) with the preference to either approximate octahedral or trigonal prismatic coordination geometry. A detailed magnetic characterization for most of the complexes is presented where a trinuclear Co2+ cluster stands out for its pronounced SMM...

  4. Lexical Complexity of Decision-Making Writing Tasks: Form-focused Guided Strategic Planning

    Mahdavirad, Fatemeh

    2016-01-01

    The present study is an attempt to investigate the effect of form-focused guided strategic planning on lexical complexity of learners’ performance in writing tasks. The twenty intermediate level participants of the study performed an unplanned and then a planned decision-making task. In the planned task condition, the participants were provided with form-focused guided strategic planning which contained detailed instructions about how to plan, by being instructed to focus on form. The guidanc...

  5. Forming the management model in industrial partnerships of the machine-building complex of Ukraine

    Reshetilova, T.; Kuvaieva, T.

    2016-01-01

    Stages of development the processes of forming the industrial networks, technological and logistic chains, partnership and their varieties are analyzed. Factors that determine the rate and scale of the process of forming the partnerships in the machine-building complex of Ukraine are established. A group of the factors that lead to forming the vertical partnership based on Partner Relationship Management (PRM) in mining machinery and mining industry are determined and analyzed. It is possible...

  6. Synthesis and characterization of transition metal complexes derived from some biologically active furoic acid hydrazones

    P. Venkateswar Rao

    2007-04-01

    Full Text Available Two new physiologically active ligands, N’-2-[(E-1-hydroxy-4-methyl-2-oxo-2H-8-chromenyl ethylidene-2-furan carbohydrazide (HMCFCH and N’-2-[(Z-1-(4-hydroxy-6-methyl-2-oxo-2H-pyranyl ethylidene]-furan carbohydrazide (HMPFCH and their VO(II, Mn(II, Fe(II, Co(II, Ni(II and Cu(II complexes have been prepared. The ligands and the metal complexes have been characterized by elemental analyses, electrical conductance, magnetic susceptibility measurements, UV-Vis, IR, and ESR spectroscopic data. Basing on the above data, Fe(II and Co(II complexes of HMCFCH and HMPFCH have been assigned a dimeric octahedral geometry. VO(II complexes of HMCFCH and HMPFCH have been assigned sulfate bridged dimeric square pyramidal geometry. Mn(II complex of HMCFCH has been assigned a dimeric octahedral geometry, where as Mn(II complex of HMPFCH has been ascribed to monomeric octahedral geometry. Cu(II and Ni(II complexes of HMCFCH have been ascribed to a polymeric structure. Ni(II complex of HMPFCH has been assigned a dimeric square planar geometry. Cu(II complex of HMPFCH has been proposed an octahedral geometry. The ligands and their metal chelates were screened against S. aureus and P. aeruginosa. The ligands and the metal complexes have been found to be active against these microorganisms. The ligands show more activity than the metal complexes.

  7. Development of JSTAMP-Works/NV and HYSTAMP for Multipurpose Multistage Sheet Metal Forming Simulation

    Umezu, Yasuyoshi; Watanabe, Yuko; Ma, Ninshu

    2005-01-01

    Since 1996, Japan Research Institute Limited (JRI) has been providing a sheet metal forming simulation system called JSTAMP-Works packaged the FEM solvers of LS-DYNA and JOH/NIKE, which might be the first multistage system at that time and has been enjoying good reputation among users in Japan. To match the recent needs, 'faster, more accurate and easier', of process designers and CAE engineers, a new metal forming simulation system JSTAMP-Works/NV is developed. The JSTAMP-Works/NV packaged the automatic healing function of CAD and had much more new capabilities such as prediction of 3D trimming lines for flanging or hemming, remote control of solver execution for multi-stage forming processes and shape evaluation between FEM and CAD.On the other way, a multi-stage multi-purpose inverse FEM solver HYSTAMP is developed and will be soon put into market, which is approved to be very fast, quite accurate and robust.Lastly, authors will give some application examples of user defined ductile damage subroutine in LS-DYNA for the estimation of material failure and springback in metal forming simulation

  8. Development of JSTAMP-Works/NV and HYSTAMP for Multipurpose Multistage Sheet Metal Forming Simulation

    Umezu, Yasuyoshi; Watanabe, Yuko; Ma, Ninshu

    2005-08-01

    Since 1996, Japan Research Institute Limited (JRI) has been providing a sheet metal forming simulation system called JSTAMP-Works packaged the FEM solvers of LS-DYNA and JOH/NIKE, which might be the first multistage system at that time and has been enjoying good reputation among users in Japan. To match the recent needs, "faster, more accurate and easier", of process designers and CAE engineers, a new metal forming simulation system JSTAMP-Works/NV is developed. The JSTAMP-Works/NV packaged the automatic healing function of CAD and had much more new capabilities such as prediction of 3D trimming lines for flanging or hemming, remote control of solver execution for multi-stage forming processes and shape evaluation between FEM and CAD. On the other way, a multi-stage multi-purpose inverse FEM solver HYSTAMP is developed and will be soon put into market, which is approved to be very fast, quite accurate and robust. Lastly, authors will give some application examples of user defined ductile damage subroutine in LS-DYNA for the estimation of material failure and springback in metal forming simulation.

  9. Finite element simulation and Experimental verification of Incremental Sheet metal Forming

    Kaushik Yanamundra, Krishna; Karthikeyan, R., Dr.; Naranje, Vishal, Dr

    2018-04-01

    Incremental sheet metal forming is now a proven manufacturing technique that can be employed to obtain application specific, customized, symmetric or asymmetric shapes that are required by automobile or biomedical industries for specific purposes like car body parts, dental implants or knee implants. Finite element simulation of metal forming process is being performed successfully using explicit dynamics analysis of commercial FE software. The simulation is mainly useful in optimization of the process as well design of the final product. This paper focuses on simulating the incremental sheet metal forming process in ABAQUS, and validating the results using experimental methods. The shapes generated for testing are of trapezoid, dome and elliptical shapes whose G codes are written and fed into the CNC milling machine with an attached forming tool with a hemispherical bottom. The same pre-generated coordinates are used to simulate a similar machining conditions in ABAQUS and the tool forces, stresses and strains in the workpiece while machining are obtained as the output data. The forces experimentally were recorded using a dynamometer. The experimental and simulated results were then compared and thus conclusions were drawn.

  10. Modeling of the inhomogeneity of grain refinement during combined metal forming process by finite element and cellular automata methods

    Majta, Janusz; Madej, Łukasz; Svyetlichnyy, Dmytro S.; Perzyński, Konrad; Kwiecień, Marcin, E-mail: mkwiecie@agh.edu.pl; Muszka, Krzysztof

    2016-08-01

    The potential of discrete cellular automata technique to predict the grain refinement in wires produced using combined metal forming process is presented and discussed within the paper. The developed combined metal forming process can be treated as one of the Severe Plastic Deformation (SPD) techniques that consists of three different modes of deformation: asymmetric drawing with bending, namely accumulated angular drawing (AAD), wire drawing (WD) and wire flattening (WF). To accurately replicate complex stress state both at macro and micro scales during subsequent deformations two stage modeling approach was used. First, the Finite Element Method (FEM), implemented in commercial ABAQUS software, was applied to simulate entire combined forming process at the macro scale level. Then, based on FEM results, the Cellular Automata (CA) method was applied for simulation of grain refinement at the microstructure level. Data transferred between FEM and CA methods included set of files with strain tensor components obtained from selected integration points in the macro scale model. As a result of CA simulation, detailed information on microstructure evolution during severe plastic deformation conditions was obtained, namely: changes of shape and sizes of modeled representative volume with imposed microstructure, changes of the number of grains, subgrains and dislocation cells, development of grain boundaries angle distribution as well as changes in the pole figures. To evaluate CA model predictive capabilities, results of computer simulation were compared with scanning electron microscopy and electron back scattered diffraction images (SEM/EBSD) studies of samples after AAD+WD+WF process.

  11. Off-line testing of multifunctional surfaces for metal forming applications

    Godi, A.; Grønbæk, J.; De Chiffre, L.

    2015-01-01

    In this paper, Bending-Under-Tension, an off-line test method simulating deep-drawing, is chosen for investigating the effectiveness of multifunctional (MUFU) surfaces in metal forming operations. Four different MUFU surfaces, characterized by a plateau bearing area and grooves for lubricant...... retention, are manufactured, together with two polished references. During the tests, surface texture is the only variable. The results show how MUFU surfaces perform better than the polished references, which produce severe galling, while MUFU surfaces with low bearing area display no clear evidence...... of galling. Metal-to-metal contact occurs anyway, but the strip material is pulverized and deposited onto the tool instead of cold-welding to it. The pockets create a discontinuity on the texture hindering pick-up propagation....

  12. Transition metal M(II complexes with isonicotinoylhydrazone-9-anthraldehyde

    Dianu M.L.

    2010-01-01

    Full Text Available New complexes of isonicotinoylhydrazone-9-anthraldehyde with Cu(II, Co(II and Ni(II have been prepared and characterized by analytical and physico-chemical techniques, such as elemental and thermal analyses, magnetic susceptibility and conductivity measurements, and electronic, EPR and IR spectral studies. The infrared spectral studies revealed the bidentate or monodentate nature of the Schiff base in the complexes; the pyridine nitrogen does not participate in the coordination. A tetrahedral geometry is suggested for the nitrate-complexes and an octahedral geometry for the others. Thermal studies support the chemical formulation of these complexes.

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

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

    2005-12-15

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

  14. Phycoremediation of heavy metals by the three-color forms of Kappaphycus alvarezii

    Suresh Kumar, K [Marine Algae and Marine Environment Discipline, Central Salt and Marine Chemicals Research Institute, Gijubhai Badheka Marg, Bhavangar 364 002, Gujarat (India); Ganesan, K [Marine Algae and Marine Environment Discipline, Central Salt and Marine Chemicals Research Institute, Gijubhai Badheka Marg, Bhavangar 364 002, Gujarat (India); Subba Rao, P V [Marine Algae and Marine Environment Discipline, Central Salt and Marine Chemicals Research Institute, Gijubhai Badheka Marg, Bhavangar 364 002, Gujarat (India)

    2007-05-08

    In the present investigation, three living color forms (brown, green and pale yellow) of Kappaphycus alvarezii were examined for their biosorption ability in the laboratory. The brown color form proved to be an excellent metal biosorbent, i.e. it could adsorb good amount of cadmium 3.064 mg/100 g f.wt. and cobalt 3.365 mg/100 g f.wt. It also removed 2.799 mg/100 g f.wt. of chromium. The green color form absorbed 2.684, 3.43 and 2.692 mg/100 g f.wt. of cadmium, cobalt and chromium, respectively. In contrast, the pale yellow form removed almost equal proportion of cadmium 0.961 mg/100 g f.wt. and chromium 0.942 mg/100 g f.wt. It also removed 1.403 mg/100 g f.wt. cobalt. Thus, the living color forms of this seaweed could form an effective biosorbent material for removal of heavy metals.

  15. Phycoremediation of heavy metals by the three-color forms of Kappaphycus alvarezii

    Suresh Kumar, K.; Ganesan, K.; Subba Rao, P.V.

    2007-01-01

    In the present investigation, three living color forms (brown, green and pale yellow) of Kappaphycus alvarezii were examined for their biosorption ability in the laboratory. The brown color form proved to be an excellent metal biosorbent, i.e. it could adsorb good amount of cadmium 3.064 mg/100 g f.wt. and cobalt 3.365 mg/100 g f.wt. It also removed 2.799 mg/100 g f.wt. of chromium. The green color form absorbed 2.684, 3.43 and 2.692 mg/100 g f.wt. of cadmium, cobalt and chromium, respectively. In contrast, the pale yellow form removed almost equal proportion of cadmium 0.961 mg/100 g f.wt. and chromium 0.942 mg/100 g f.wt. It also removed 1.403 mg/100 g f.wt. cobalt. Thus, the living color forms of this seaweed could form an effective biosorbent material for removal of heavy metals

  16. Reactions of transition metal complexes with cyclic ethers

    Milstein, D.

    1977-02-01

    Three novel reactions of epoxides with homogeneous transition-metal catalysts have been explored: (a) the selective rearrangement of internal epoxides to ketones; (b) the cleavage of C-C bond in epoxides having electron-attracting substituents; (c) the transformation of terminal epoxides into esters. Based on an intensive kinetic study, a general mechanism for the transformations of epoxides is postulated

  17. Biological activities of some Fluoroquinolones-metal complexes

    McRoy

    Background: Metal ions play a vital role in the design of more biologically active drugs. Aim: The paper reviewed the .... 2H2O by direct reaction of copper(II) sulphate pentahydrate with ciprofloxacin in distilled water. ... membered ring and the chloride ion completes the seven coordination around the Ca2+ion.[37-39].

  18. Theoretical NMR spectroscopy of N-heterocyclic carbenes and their metal complexes

    Falivene, Laura; Cavallo, Luigi

    2016-01-01

    Recent theoretical analysis of the NMR properties of free N-heterocyclic carbenes (NHC) and Metal-NHC complexes has complemented experiments, allowing the establishment of structure/property relationships and the rationalization of otherwise

  19. Basic deuteroexchange in transition metal complexes with nitrogen-containing aromatic heterocycles

    Tupitsyn, I.F.

    1986-01-01

    Kinetics of deuteroexchange in the methyl group of nitrate complexes of a metal - nickel (2) - with different methyl-substituted aromatic heterocycles and isostructural complexes of a ligand - 2 - methyl quinoline - with different central metal atoms (Mn(2), Ni(2), Cu(2), Zn(2)) is studied. Series for influence of ligand structure on deuteroexchange rate in complexes doesn't correspond qualitatively to series for deuteroexchange rate increase in noncoordinated ligands. Deuteroexchange rate is weakly subjected to influence of exchange in metal-complexing agent. Deuteroexchange mechanism is suggested and discussed. According to this mechanism the structure developed in the course of the exchange process with electron density transfer from the heterocyclic ligand to a metal ion is a transition state of the reaction

  20. Multiheteromacrocycles that complex metal ions. Third progress report, 1 May 1976--30 April 1977

    Cram, D.J.

    1977-01-01

    The overall objective of this research is to design, synthesize and evaluate cyclic and polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions, their complexes and clusters. Host organic compounds consist of strategically placed solvating, coordinating and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions, or metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; numbers of binding sites; characters of binding sites; and valences. The specific compounds synthesized and their complexing and lipophilizing properties are summarized

  1. Density functional study of isoguanine tetrad and pentad sandwich complexes with alkali metal ions.

    Meyer, Michael; Steinke, Thomas; Sühnel, Jürgen

    2007-02-01

    Isoguanine tetraplexes and pentaplexes contain two or more stacked polyads with intercalating metal ions. We report here the results of a density functional study of sandwiched isoguanine tetrad and pentad complexes consisting of two polyads with Na(+), K(+) and Rb(+) ions at the B3LYP level. In comparison to single polyad metal ion complexes, there is a trend towards increased non-planarity of the polyads in the sandwich complexes. In general, the pentad sandwiches have relatively planar polyad structures, whereas the tetrad complexes contain highly non-planar polyad building blocks. As in other sandwich complexes and in metal ion complexes with single polyads, the metal ion-base interaction energy plays an essential role. In iG sandwich structures, this interaction energy is slightly larger than in the corresponding guanine sandwich complexes. Because the base-base interaction energy is even more increased in passing from guanine to isoguanine, the isoguanine sandwiches are thus far the only examples where the base-base interaction energy is larger than the base-metal ion interaction energy. Stacking interactions have been studied in smaller models consisting of two bases, retaining the geometry from the complete complex structures. From the data obtained at the B3LYP and BH&H levels and with Møller-Plesset perturbation theory, one can conclude that the B3LYP method overestimates the repulsion in stacked base dimers. For the complexes studied in this work, this is only of minor importance because the direct inter-tetrad or inter-pentad interaction is supplemented by a strong metal ion-base interaction. Using a microsolvation model, the metal ion preference K(+) approximately Rb(+) > Na(+) is found for tetrad complexes. On the other hand, for pentads the ordering is Rb(+) > K(+) > Na(+). In the latter case experimental data are available that agree with this prediction.

  2. Insights into aquatic toxicities of the antibiotics oxytetracycline and ciprofloxacin in the presence of metal: Complexation versus mixture

    Zhang Yu; Cai Xiyun; Lang Xianming; Qiao Xianliang; Li Xuehua; Chen Jingwen

    2012-01-01

    Co-contamination of ligand-like antibiotics (e.g., tetracyclines and quinolones) and heavy metals prevails in the environment, and thus the complexation between them is involved in environmental risks of antibiotics. To understand toxicological significance of the complex, effects of metal coordination on antibiotics' toxicity were investigated. The complexation of two antibiotics, oxytetracycline and ciprofloxacin, with three heavy metals, copper, zinc, and cadmium, was verified by spectroscopic techniques. The antibiotics bound metals via multiple coordination sites and rendered a mixture of various complexation speciations. Toxicity analysis indicated that metal coordination did modify the toxicity of the antibiotics and that antibiotic, metal, and their complex acted primarily as concentration addition. Comparison of EC 50 values revealed that the complex commonly was highest toxic and predominately correlated in toxicity to the mixture. Finally, environmental scenario analysis demonstrated that ignoring complexation would improperly classify environmental risks of the antibiotics. - Highlights: ► The complex of antibiotic with metal is a mixture of various complexation modes. ► Antibiotic and metal act as various combined interactions when their complexation is ignored. ► Antibiotic, metal, and their complex act as concentration addition interaction. ► Complex commonly is the highest toxicant. ► Neglecting complexation renders improper classification of risks for antibiotics. - Antibiotic, heavy metal and their complex act primarily as concentration addition interaction and the complex commonly is highest toxic.

  3. Insights into aquatic toxicities of the antibiotics oxytetracycline and ciprofloxacin in the presence of metal: Complexation versus mixture

    Yu, Zhang [Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China); Cai Xiyun, E-mail: xiyuncai@dlut.edu.cn [Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China); Xianming, Lang [Liaoning Academy of Environmental Sciences, Shenyang 110031 (China); Xianliang, Qiao; Xuehua, Li; Jingwen, Chen [Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China)

    2012-07-15

    Co-contamination of ligand-like antibiotics (e.g., tetracyclines and quinolones) and heavy metals prevails in the environment, and thus the complexation between them is involved in environmental risks of antibiotics. To understand toxicological significance of the complex, effects of metal coordination on antibiotics' toxicity were investigated. The complexation of two antibiotics, oxytetracycline and ciprofloxacin, with three heavy metals, copper, zinc, and cadmium, was verified by spectroscopic techniques. The antibiotics bound metals via multiple coordination sites and rendered a mixture of various complexation speciations. Toxicity analysis indicated that metal coordination did modify the toxicity of the antibiotics and that antibiotic, metal, and their complex acted primarily as concentration addition. Comparison of EC{sub 50} values revealed that the complex commonly was highest toxic and predominately correlated in toxicity to the mixture. Finally, environmental scenario analysis demonstrated that ignoring complexation would improperly classify environmental risks of the antibiotics. - Highlights: Black-Right-Pointing-Pointer The complex of antibiotic with metal is a mixture of various complexation modes. Black-Right-Pointing-Pointer Antibiotic and metal act as various combined interactions when their complexation is ignored. Black-Right-Pointing-Pointer Antibiotic, metal, and their complex act as concentration addition interaction. Black-Right-Pointing-Pointer Complex commonly is the highest toxicant. Black-Right-Pointing-Pointer Neglecting complexation renders improper classification of risks for antibiotics. - Antibiotic, heavy metal and their complex act primarily as concentration addition interaction and the complex commonly is highest toxic.

  4. Variation of rock-forming metals in sub-annual increments of modern Greenland snow

    Hinkley, T.K.

    1992-01-01

    Modern snowpack from central south Greenland was sampled in sub-seasonal increments and analysed for a suite of major, minor and trace rock-forming metals (K, Rb, Cs, Ca, Sr, Ba). There is a sharp seasonal concentration maximum for all six metals that comes in summer, later than mid-June. Metal concentrations in all other parts of the year's snowpack are up to 10 or more times smaller. The concentration maximum is preceded by low values in autumn-winter, very low values in early-mid-spring, and moderate-to-high values in late spring early summer; this pattern is seen consistently in three separate time stratigraphic intervals representing the same seasonal periods, spanning the time interval 1981-1984. The absolute concentration values of the snow strata representing the low-concentration portion of the year, autumn-winter-spring, may vary substantially from year to year, by a factor of two, or more. The finding that all rock-forming metals are at a sharp concentration maximum in late summer contrasts with the interpretations of several other studies in high-latitude northern regions. Those studies have reported a broad maximum of continental dust-associated metals in late winter and spring. However samples of the other studies have mostly come from regions farther to the north, and the analyses have emphasized industrial pollutant metals rather than the matched rock-forming suite of the present study. The metals measured were chosen to give information about the origin and identity of the rock and soil dusts, and sea salts, present as impurities in the snow. Metal ratios indicate that the dusts in the snowpacks are of continental origin and from ferromagnesian rocks. Source rock types for dusts in central south Greenland snow contrast with the felsic rock dusts of the Sierra Nevada, CA, annual snowpacks, and with the very felsic rock dusts in large south central Alaskan mountain glaciers. Samples in which masses of sea salt are much larger than those of rock dusts

  5. Theories, Methods and Numerical Technology of Sheet Metal Cold and Hot Forming Analysis, Simulation and Engineering Applications

    Hu, Ping; Liu, Li-zhong; Zhu, Yi-guo

    2013-01-01

    Over the last 15 years, the application of innovative steel concepts in the automotive industry has increased steadily. Numerical simulation technology of hot forming of high-strength steel allows engineers to modify the formability of hot forming steel metals and to optimize die design schemes. Theories, Methods and Numerical Technology of Sheet Metal Cold and Hot Forming focuses on hot and cold forming theories, numerical methods, relative simulation and experiment techniques for high-strength steel forming and die design in the automobile industry. Theories, Methods and Numerical Technology of Sheet Metal Cold and Hot Forming introduces the general theories of cold forming, then expands upon advanced hot forming theories and simulation methods, including: • the forming process, • constitutive equations, • hot boundary constraint treatment, and • hot forming equipment and experiments. Various calculation methods of cold and hot forming, based on the authors’ experience in commercial CAE software f...

  6. Some transition metal complexes derived from mono- and di-ethynyl perfluorobenzenes

    Armitt, D.J.; Bruce, M.I.; Gaudio, M.; Zaitseva, N.N.; Skelton, B.W.; White, A.H.; Le Guennic, B.; Halet, J.-F.; Fox, M.A.; Roberts, R.L.; Hartl, F.; Low, P.J.

    2008-01-01

    Transition metal alkynyl complexes containing perfluoroaryl groups have been prepared directly from trimethylsilyl-protected mono- and di-ethynyl perfluoroarenes by simple desilylation/metallation reaction sequences. Reactions between Me3SiC CC6F5 and RuCl(dppe)Cp'[Cp' = Cp, Cp*] in the presence of

  7. Shrinking the Synchrotron : Tabletop Extreme Ultraviolet Absorption of Transition-Metal Complexes

    Zhang, Kaili; Lin, Ming Fu; Ryland, Elizabeth S.; Verkamp, Max A.; Benke, Kristin; De Groot, Frank M F; Girolami, Gregory S.; Vura-Weis, Josh

    2016-01-01

    We show that the electronic structure of molecular first-row transition-metal complexes can be reliably measured using tabletop high-harmonic XANES at the metal M2,3 edge. Extreme ultraviolet photons in the 50-70 eV energy range probe 3p → 3d transitions, with the same selection rules as soft X-ray

  8. Study of the competitive reaction ability of harmine and harmaline during complex formation with transition metals

    Chepulsky, S.A.; Kadirova, Z.Ch.; Parpiev, N.A.

    2006-01-01

    New coordination compounds of d-metals (Zn(II), Co(II), Mn(II), Mo(VI), Cr(VI)) β-carboline alkaloids were synthesized. The structure of obtained substances was established by IR, PMR spectroscopy. The quantum-chemical assessment of the harmine and harmaline reactivity in complexation reactions with d-metals was carried out. (author)

  9. Proton magnetic resonance spectra of metal ammine complexes, 8

    Taura, Toshiaki; Sakaguchi, Ushio; Yoneda, Hayami

    1976-01-01

    The rates of amine hydrogen isotopic exchange in the [Co(O) 2 (N) 4 ] + complex ions, where (O) 2 represents carbonate, oxalate, or malonate ions, and (N) 4 , tetraamine, bis(ethylenediamine), or bis(trimethylenediamine), were measured in D 2 O at 35 0 C by the PMR technique. It was found that: (1) the rates for trans (to oxygen) amines are faster than those for cis amines; (2) the rates, especially for trans amines, in the carbonato complexes are slower than those in the oxalato and malonato analogs, and (3) the difference between the rates for cis and trans amines is smaller in the bis(diamine) complexes than in the tetraammine complexes. These results are discussed in terms of the influence of the chelate geometry in the complex on the exchange reaction. (auth.)

  10. Properties of lotus seed starch-glycerin monostearin complexes formed by high pressure homogenization.

    Chen, Bingyan; Zeng, Shaoxiao; Zeng, Hongliang; Guo, Zebin; Zhang, Yi; Zheng, Baodong

    2017-07-01

    Starch-lipid complexes were prepared using lotus seed starch (LS) and glycerin monostearate (GMS) via a high pressure homogenization (HPH) process, and the effect of HPH on the physicochemical properties of LS-GMS complexes was investigated. The results of Fourier transform infrared spectroscopy and complex index analysis showed that LS-GMS complexes were formed at 40MPa by HPH and the complex index increased with the increase of homogenization pressure. Scanning electron microscopy displayed LS-GMS complexes present more nest-shape structure with increasing homogenization pressure. X-ray diffraction and differential scanning calorimetry results revealed that V-type crystalline polymorph was formed between LS and GMS, with higher homogenization pressure producing an increasingly stable complex. LS-GMS complex inhibited starch granules swelling, solubility and pasting development, which further reduced peak and breakdown viscosity. During storage, LS-GMS complexes prepared by 70-100MPa had higher Avrami exponent values and lower recrystallization rates compared with native starch, which suggested a lower retrogradation trendency. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Supramolecular architecture of metal-organic frameworks involving dinuclear copper paddle-wheel complexes.

    Gomathi, Sundaramoorthy; Muthiah, Packianathan Thomas

    2013-12-15

    The two centrosymmetric dinuclear copper paddle-wheel complexes tetrakis(μ-4-hydroxybenzoato-κ(2)O:O')bis[aquacopper(II)] dimethylformamide disolvate dihydrate, [Cu2(C7H5O3)4(H2O)2]·2C3H7NO·2H2O, (I), and tetrakis(μ-4-methoxybenzoato-κ(2)O:O')bis[(dimethylformamide-κO)copper(II)], [Cu2(C8H7O3)4(C3H7NO)2], (II), crystallize with half of the dinuclear paddle-wheel cage unit in the asymmetric unit and, in addition, complex (I) has one dimethylformamide (DMF) and one water solvent molecule in the asymmetric unit. In both (I) and (II), two Cu(II) ions are bridged by four syn,syn-η(1):η(1):μ carboxylate groups, showing a paddle-wheel cage-type structure with a square-pyramidal coordination geometry. The equatorial positions of (I) and (II) are occupied by the carboxylate groups of 4-hydroxy- and 4-methoxybenzoate ligands, and the axial positions are occupied by aqua and DMF ligands, respectively. The three-dimensional supramolecular metal-organic framework of (I) consists of three different R2(2)(20) and an R4(4)(36) ring motif formed via O-H···O and OW-HW···O hydrogen bonds. Complex (II) simply packs as molecular species.

  12. Chiral phosphites as ligands in asymmetric metal complex catalysis and synthesis of coordination compounds

    Gavrilov, Konstantin N; Bondarev, Oleg G; Polosukhin, Aleksei I

    2004-01-01

    The data published during the last five years on the application of chiral derivatives of phosphorous acid in coordination chemistry and enantioselective catalysis are summarised and discussed. The effect of the nature of these ligands on the structure of metal complexes and on the efficiency of catalytic organic syntheses is shown. Hydroformylation, hydrogenation, allylic substitution and conjugate addition catalysed by transition metal complexes with optically active phosphites and hydrophosphoranes are considered. The prospects for the development of this field of research are demonstrated.

  13. Prediction Of Formability In Sheet Metal Forming Processes Using A Local Damage Model

    Teixeira, P.; Santos, Abel; Cesar Sa, J.; Andrade Pires, F.; Barata da Rocha, A.

    2007-01-01

    The formability in sheet metal forming processes is mainly conditioned by ductile fracture resulting from geometric instabilities due to necking and strain localization. The macroscopic collapse associated with ductile failure is a result of internal degradation described throughout metallographic observations by the nucleation, growth and coalescence of voids and micro-cracks. Damage influences and is influenced by plastic deformation and therefore these two dissipative phenomena should be coupled at the constitutive level. In this contribution, Lemaitre's ductile damage model is coupled with Hill's orthotropic plasticity criterion. The coupling between damaging and material behavior is accounted for within the framework of Continuum Damage Mechanics (CDM). The resulting constitutive equations are implemented in the Abaqus/Explicit code, for the prediction of fracture onset in sheet metal forming processes. The damage evolution law takes into account the important effect of micro-crack closure, which dramatically decreases the rate of damage growth under compressive paths

  14. Computer controlled experimental device for investigations of tribological influences in sheet metal forming

    Milan Djordjevic

    2012-05-01

    Full Text Available Sheet metal forming, especially deep drawing process, is influenced by many factors. Blank holding force and drawbead displacement are two of them that can be controlled during the forming process. For this purpose, electro-hydraulic computerized sheet-metal strip sliding device has been constructed. Basic characteristic of this device is realization of variable contact pressure and drawbead height as functions of time or stripe displacement. There are both, pressure and drawbead, ten linear and nonlinear functions. Additional features consist of the ability to measure drawing force, contact pressure, drawbead displacement etc. Presented in the paper are the device overview and the first results of steel sheet stripe sliding over rounded  drawbead.

  15. COMPUTER CONTROLLED EXPERIMENTAL DEVICE FOR INVESTIGATIONS OF TRIBOLOGICAL INFLUENCES IN SHEET METAL FORMING

    Tomislav Vujinović

    2012-05-01

    Full Text Available Sheet metal forming, especially deep drawing process is influenced by many factors. Blank holding force and drawbead displacement are two of them that can be controlled during the forming process.For this purpose, an electro-hydraulic computerized sheet-metal strip sliding device has been constructed. The basic characteristic of this device is realization of variable contact pressure and drawbead height as functions of time or stripe displacement. There are both, pressure and drawbead, ten linear and nonlinear functions. Additional features consist of the ability to measure drawing force, contact pressure, drawbead displacement etc.The device overview and first results of steel sheet stripe sliding over rounded drawbead are presented in the paper.

  16. Synthesis, physico-chemical characterization and biological activity of 2-aminobenzimidazole complexes with different metal ions

    Podunavac-Kuzmanović Sanja O.

    2004-01-01

    Full Text Available Complexes of 2-aminobenzimidazole (L with nitrates of cobalt(II nickel(II, copper (II, zinc(II and silver(I were synthesized. The molar ratio metal:ligand in the reaction of the complex formation was 1:2. It should be noticed, that the reaction of all the metal salts yielded bis(ligand complexes of the general formula M(L2(NO32 × nH2O (M=Co, Ni Cu, Zn or Ag; n=0, 1, 2 or 6. The complexes were characterized by elemental analysis of the metal, molar conductivity, magnetic susceptibility measurements and IR spectra. Co(II, Ni(II and Cu(II complexes behave as non-electrolytes, whilst Zn(II and Ag(I are 1:1 electrolytes. Cu(II complex has a square-planar stereochemistry, Ag(I complex is linear, whilst the Co(II, Ni(II and Zn(II complexes have a tetrahedral configuration. In all the complexes ligand is coordinated by participation of the pyridine nitrogen of the benzimidazole ring. The antimicrobial activity of the ligand and its complexes against Pseudomonas aeruginosa, Bacillus sp. Staphylococcus aureus and Saccharomyces cerevisiae was investigated. The effect of metal on the ligand antimicrobial activity is discussed.

  17. Irradiation effect on leaching behavior and form of heavy metals in fly ash of municipal solid waste incinerator

    Nam, Sangchul; Namkoong, Wan

    2012-01-01

    Highlights: ► No research has been done to examine effect of electron beam irradiation on leaching behavior of heavy metals in fly ash. ► Electron beam irradiation on fly ash had significant effect on heavy metal leaching. ► Leaching potential of heavy metals in fly ash differed among metal species tested (Pb, Zn, Cu). ► Metal forms in the ash were analyzed to explain the difference. ► The difference could be explained by metal form change. - Abstract: Fly ash from a municipal solid waste incinerator (MSWI) is commonly classified as hazardous waste. High-energy electron beam irradiation systems have gained popularity recently as a clean and promising technology to remove environmental pollutants. Irradiation effects on leaching behavior and form of heavy metals in MSWI fly ash have not been investigated in any significant detail. An electron beam accelerator was used in this research. Electron beam irradiation on fly ash significantly increased the leaching potential of heavy metals from fly ash. The amount of absorbed dose and the metal species affected leaching behavior. When electron beam irradiation intensity increased gradually up to 210 kGy, concentration of Pb and Zn in the leachate increased linearly as absorbed dose increased, while that of Cu underwent no significant change. Concentration of Pb and Zn in the leachate increased up to 15.5% (10.7 mg/kg), and 35.6% (9.6 mg/kg) respectively. However, only 4.8% (0.3 mg/kg) increase was observed in the case of Cu. The results imply that irradiation has significant effect on the leaching behavior of heavy metals in fly ash, and the effect is quite different among the metal species tested in this study. A commonly used sequential extraction analysis which can classify a metal species into five forms was conducted to examine any change in metal form in the irradiated fly ash. Notable change in metal form in fly ash was observed when fly ash was irradiated. Change in Pb form was much greater than that of

  18. Selectivity in inter polymer complexation involving phenolic copolymer, poly electrolytes, non-ionic polymers and transition metal ions

    Vasheghani Farahani, B.; Hosseinpour Rajabi, F.

    2006-01-01

    Selectivity in inter polymer complex formation involving a typical four-component phenolic copolymer (ρ-chloro phenol-ρ-aminophenol-ρ-toluidine-ρ-cresol- HCHO copolymer), poly electrolytes such as polyethylene imine and polyacrylic acid, a non-ionic homopolymer polyvinyl pyrrolidone, and some transition metal ions (e.g., Cu (II), Ni (11)) have been studied in dimethylformamide-methanol solvents mixture. The coordinating groups of phenolic copolymer form complexes through hydrogen bonding and ion-dipole interactions. The different stages of interactions have been studied by several experimental techniques, e.g., viscometry, potentiometry and conductometry. Some schemes have been suggested to explain the mode of interaction between these components

  19. 3d/4f Metal Complexes of Phenolic Oximes New Binding Sites on Anderson Polyoxometalates Metal Complexes of the New THAME Ligand

    Sethi, Waqas

    to be coordinatedto SMMs as well as onto other transition metal complexes, via different synthetic strategies. These synthetic routes did not result in the crystallisation of any new compounds. A new hexadentate ligand tris(((2-hydroxyethyl)-amino)methyl)ethane (THAME) was synthesised and characterised. THAME...

  20. A numerical simulation of thermodynamic processes for cryogenic metal forming of aluminum sheets and comparison with experimental results

    Reichl, Ch.; Schneider, R.; Hohenauer, W.; Grabner, F.; Grant, R.J.

    2017-01-01

    Highlights: • Thermodynamic processes for cryogenic sheet metal forming tools were examined. • Static and transient temperature field simulations are evaluated on a Nakajima tool. • Differently arranged cooling loops lead to homogeneous temperature distribution. • Scaling of the geometry leads to significantly increased heat transfer times. • The temperature management of complex forming tools can be developed numerically. - Abstract: Forming at cryogenic temperatures provides a significant improvement in formability of aluminum sheets. This offers the potential for light, complex and highly integrated one-piece components to be produced out of aluminum alloys at sub-zero temperatures. This would allow weight reduction, environmental conservation and cost reduction of a car body to give one example in the automotive industry. For temperature supported processes special forming tools and cooling strategies are required to be able to reach and maintain process stability. Time dependent numerical simulations of the thermodynamic processes of cryogenic sheet metal forming covering all aspects of heat transfer through conduction, convection and radiation play a vital role in the design and development of future tools and are presented for several geometries. Cooling (and heating) strategies (including selection of the number of cooling loops and their relative positioning) in a Nakajima testing tool were evaluated using computational fluid dynamics. These simulations were performed with static and transient solvers to demonstrate the extraction of tool surface temperature distributions on different forming tool geometries. Comparisons of predicted temperature characteristics of an aluminum sheet and experimentally determined temperature distributions were made. The temperature distribution of the surface of an aluminum sheet could be predicted with high accuracy. Further, the influence of the tool size on the parameters temperature transfer times and

  1. 3-D Modelling of Electromagnetic, Thermal, Mechanical and Metallurgical Couplings in Metal Forming Processes

    Chenot, Jean-Loup; Bay, Francois

    2007-01-01

    The different stages of metal forming processes often involve - beyond the mechanical deformations processes - other physical coupled problems, such as heat transfer, electromagnetism or metallurgy. The purpose of this paper is to focus on problems involving electromagnetic couplings. After a brief recall on electromagnetic modeling, we shall then focus on induction heating processes and present some results regarding heat transfer, as well as mechanical couplings. A case showing coupling for metallurgic microstructure evolution will conclude this paper

  2. Exposing metal and silicate charges to electrical discharges: Did chondrules form by nebular lightning?

    Güttler, C.; Poppe, T.; Wasson, J. T.; Blum, J.

    2007-01-01

    In order to investigate the hypothesis that dust aggregates were transformed to meteoritic chondrules by nebular lightning, we exposed silicatic and metallic dust samples to electric discharges with energies of 120 to 500 J in air at pressures between 10 and 10^5 Pa. The target charges consisted of powders of micrometer-sized particles and had dimensions of mm. The dust samples generally fragmented leaving the major fraction thermally unprocessed. A minor part formed sintered aggregates of 50...

  3. Zirconium sponge and other forms of virgin metal for nuclear applications - approved standard 1973

    Anon.

    1975-01-01

    This specification covers virgin zirconium metal commonly designated as sponge because of its porous, sponge-like texture, but it may also take other forms such as chunklets. One grade is described which is designated as reactor grade R-1, suitable for use in nuclear applications. The most important characteristic of the reactor grade is its low nuclear cross section as achieved by removal of hafnium and careful quality control in manufacturing procedures to prevent contamination with other high cross section materials

  4. Bulk glass formation and crystallization in zirconium based bulk metallic glass forming alloys

    Savalia, R.T.; Neogy, S.; Dey, G.K.; Banerjee, S.

    2002-01-01

    The microstructures of Zr based metallic glasses produced in bulk form have been described in the as-cast condition and after crystallization. Various microscopic techniques have been used to characterize the microstructures. The microstructure in the as-cast condition was found to contain isolated crystals and crystalline aggregates embedded in the amorphous matrix. Quenched-in nuclei of crystalline phases were found to be present in fully amorphous regions. These glasses after crystallization gave rise to nanocrystalline solids. (author)

  5. Near-infrared dichroism of a mesogenic transition metal complex and its solubility in nematic hosts

    Marshall, K.L.; Jacobs, S.D.

    1987-01-01

    A transition metal complex possessing the nematic phase, bis (p-n-butylstyryl-1, 2-dithiolato) nickel, was synthesized and its optical properties and solubility in the nematic hosts K15 and MBBA were investigated. The metal complex displayed a high solubility in both host materials (up to 10% wt/wt) and a strong near-infrared absorption band centered at 860 nm. A blocking extinction of greater than OD = 3 was obtained with a 100 micron pathlength of a 0.5% wt/wt mixture of the nematic metal complex in K15, suggesting its usefulness for passive blocking of near infrared radiation. A 24 micron thick, homogeneously aligned guest-host cell containing a 1% wt/wt mixture of the metal complex in K15 possessed a contrast ratio of nearly 5:1 and a blocking extinction of OD = 3.5 at 860 nm, demonstrating for the first time the existence of near-infrared dichroism in this class of materials. The solubility and blocking extinction of the mesogenic metal complex in K15 was considerably superior to the non-mesogenic near ir laser dye bis(dimethylaminodithiobenzil) nickel in the same host. An interaction of the nematic metal complex in mixtures with MBBA which resulted in the creation of a new absorption band at 1050 nm was also observed. 21 refs., 9 figs

  6. Using metal complex-labeled peptides for charge transfer-based biosensing with semiconductor quantum dots

    Medintz, Igor L.; Pons, Thomas; Trammell, Scott A.; Blanco-Canosa, Juan B.; Dawson, Philip E.; Mattoussi, Hedi

    2009-02-01

    Luminescent colloidal semiconductor quantum dots (QDs) have unique optical and photonic properties and are highly sensitive to charge transfer in their surrounding environment. In this study we used synthetic peptides as physical bridges between CdSe-ZnS core-shell QDs and some of the most common redox-active metal complexes to understand the charge transfer interactions between the metal complexes and QDs. We found that QD emission underwent quenching that was highly dependent on the choice of metal complex used. We also found that quenching traces the valence or number of metal complexes brought into close proximity of the nanocrystal surface. Monitoring of the QD absorption bleaching in the presence of the metal complex provided insight into the charge transfer mechanism. The data suggest that two distinct charge transfer mechanisms can take place. One directly to the QD core states for neutral capping ligands and a second to surface states for negatively charged capping ligands. A basic understanding of the proximity driven charge-transfer and quenching interactions allowed us to construct proteolytic enzyme sensing assemblies with the QD-peptide-metal complex conjugates.

  7. Dissolution of Fe(III) (hydr) oxides by metal-EDTA complexes

    Ngwack, Bernd; Sigg, Laura

    1997-03-01

    The dissolution of Fe(III)(hydr)oxides (goethite and hydrous ferric oxide) by metal-EDTA complexes occurs by ligand-promoted dissolution. The process is initiated by the adsorption of metal-EDTA complexes to the surface and is followed by the dissociation of the complex at the surface and the release of Fe(III)EDTA into solution. The dissolution rate is decreased to a great extent if EDTA is complexed by metals in comparison to the uncomplexed EDTA. The rate decreases in the order EDTA CaEDTA ≫ PbEDTA > ZnEDTA > CuEDTA > Co(II)EDTA > NiEDTA. Two different rate-limiting steps determine the dissolution process: (1) detachment of Fe(III) from the oxide-structure and (2) dissociation of the metal-EDTA complexes. In the case of goethite, step 1 is slower than step 2 and the dissolution rates by various metals are similar. In the case of hydrous ferric oxide, step 2 is rate-limiting and the effect of the complexed metal is very pronounced.

  8. Surface density: a new parameter in the fundamental metallicity relation of star-forming galaxies

    Hashimoto, Tetsuya; Goto, Tomotsugu; Momose, Rieko

    2018-04-01

    Star-forming galaxies display a close relation among stellar mass, metallicity, and star formation rate (or molecular-gas mass). This is known as the fundamental metallicity relation (FMR) (or molecular-gas FMR), and it has a profound implication on models of galaxy evolution. However, there still remains a significant residual scatter around the FMR. We show here that a fourth parameter, the surface density of stellar mass, reduces the dispersion around the molecular-gas FMR. In a principal component analysis of 29 physical parameters of 41 338 star-forming galaxies, the surface density of stellar mass is found to be the fourth most important parameter. The new 4D fundamental relation forms a tighter hypersurface that reduces the metallicity dispersion to 50 per cent of that of the molecular-gas FMR. We suggest that future analyses and models of galaxy evolution should consider the FMR in a 4D space that includes surface density. The dilution time-scale of gas inflow and the star-formation efficiency could explain the observational dependence on surface density of stellar mass.

  9. Comparison of Two Commercial FE-Codes for Sheet Metal Forming

    Revuelta, A.; Larkiola, J.; Kanervo, K.; Korhonen, A. S.; Myllykoski, P.

    2007-01-01

    There is urgent need to develop new advanced fast and cost-effective mass-production methods for small sheet metal components. Traditionally progressive dies have been designed by using various CAD techniques. Recent results in mass production of small sheet metal parts using progressive dies and a transfer press showed that the tool design time may be cut in up to a half by using 3D finite element simulation of forming. In numerical simulation of sheet metal forming better constitutive models are required to obtain more accurate results, reduce the time for tool design and cut the production costs further. Accurate models are needed to describe the initial yielding, subsequent work hardening and to predict the formability. In this work two commercially available finite element simulation codes, PAM-STAMP and LS-DYNA, were compared in forming of small austenitic stainless steel sheet part for electronic industry. Several constitutive models were used in both codes and the results were compared. Comparisons were made between the same models in each of the codes and also between different models in the same code. Material models ranged from very simple to advanced ones, which took into account anisotropy and both isotropic and kinematic hardening behavior. In order to make a valid comparison we employed similar finite element meshes. The effects of the material models parameters were studied and the results were compared with experiments. The effects of the computational time were also studied

  10. Forming of protective nanostructure coatings on metals and glasses and their properties investigation

    Deshkovskaya, A.; Lynkov, L.; Nagibarov, A.; Glybin, V.; Richter, E.; Pham, M.

    2013-01-01

    Transparent heat-resistant coatings of 10-30 nm thickness described by (ZrO 2 ) x •(Y 2 O 3 ) y composition are formed on the surface of metals and glasses by thermolysis technique. Produced coatings possess high adhesive strength, high corrosive and abrasive resistance. Nanocrystalline formations are revealed on samples surface, with quantity of these formations depending on basic solution concentration, formed layers number and thermal treatment mode. Ion-beam modification of obtained coatings under mixing mode enables said properties enhancing owing to zirconium oxiboride formation at substrate-coating interface as a result of ion-beam synthesis. (authors)

  11. A Model Based Approach to Increase the Part Accuracy in Robot Based Incremental Sheet Metal Forming

    Meier, Horst; Laurischkat, Roman; Zhu Junhong

    2011-01-01

    One main influence on the dimensional accuracy in robot based incremental sheet metal forming results from the compliance of the involved robot structures. Compared to conventional machine tools the low stiffness of the robot's kinematic results in a significant deviation of the planned tool path and therefore in a shape of insufficient quality. To predict and compensate these deviations offline, a model based approach, consisting of a finite element approach, to simulate the sheet forming, and a multi body system, modeling the compliant robot structure, has been developed. This paper describes the implementation and experimental verification of the multi body system model and its included compensation method.

  12. Separation of the noble metals ruthenium and palladium from nitric acid solution of the nuclear fuel reprocessing containing complexing agents

    Ghafourian, H.

    1989-06-01

    Two extraction chromatographic techniques have been developed. N'N diethylthiourea (DETU), which forms complexes with ruthenium that can be retained on an AG50W-X2 ion exchanger, has proved to be a suitable reagent. The structures of these complexes were elucidated by electrophoresis, ion exchange and IR spectroscopy. Under the same conditions Pd forms an insoluble DETU-complex of the formula [Pd(DETU) 4 ] 2+ , which allows the separation of this metal quantitatively. With regard to the application of the developed technique for recovery of the mentioned noble metals from dissolver residues of the nuclear fuel reprocessing, comparative studies were carried out for accompanying fission product nuclides and actinides such as Mo, Tc, Zr, Ce, U and Pu. It was found out that no complex between diethylthiourea and the fission products zirconium, molybdenum and cerium and the actinides uranium, plutonium and americium were formed. Technetium, which was originally present as pertechnetate, is reduced to Tc(IV) and retained on the cation exchanger together with ruthenium. Ruthenium was eluted with 6 M HNO 3 . The efficiency of the developed process has been demonstrated with simulated solutions. The achieved decontamination factors ranged from 10 2 to 10 6 depending on the nuclide. (orig./RB) [de

  13. Transition metal complexes of some biologically active ligands; synthesis characterization and bioactivities

    Rehman, S.; Ali, N.; Nisar, M.

    2009-01-01

    Transition/representative transition metals complexes of biologically active chelating agent 1,2-dipyrolodinoethane were synthesized and characterized through spectral and analytical data. The complexes are of the formula (M(L)X/sub 2/). Where (M = Co (II), Ni (II), Cu (II), Zn (II), Hg (II) and Cd (II) and X = CI, Br, NO/sub 3/). Tetrahedral geometry has been proposed to these-metal complexes with the help of magnetic measurements, elemental analysis, chemical stoichiometry and spectroscopic data Antibacterial activity of the ligand and its metal complexes were screened against Eschereschi coli, Klebsiello pneumonia, Proteus mirabilis, Proteus vulhari, Streptococcus pneumonia, Salmonella Iyphi, Bacilh,s anthrax, Streptococcus fecalis and Staphylococcus aureus. Complexes were found to be active against Eschereschi coli, Klebsiella pneumonia, Proteus mirabilis and Proteus vulharis. (author)

  14. Extraction of pertechnetate anion as a ligand in metal complexes with tributylphosphate

    Macasek, F.; Kadrabova, J.

    1979-01-01

    The extraction of the pertechnetate anion has been investigated in the systems tributylphosphate (TBP)-solvent (carbon tetrachloride, n-heptane, chloroform) - metal salt (uranyl nitrate and chloride, thorium nitrate) -ammonium salt. In the absence of a metal, the solvates HTcO 4 xiTBP (i=4) are extracted, while in the presence of uranium and thorium, the distribution of technetium corresponds, to the formation of the mixed complexes: UO 2 (NO 3 )(TcO 4 )x2TBP, UO 2 Cl(TcO 4 )x2TBP and Th(NO 3 ) 3 (TcO 4 )x2TBP. The effective constants of the reactions H + + TcO 4 - + i(TBP)sub(org) reversible (HTcO 4 xiTBP)sub(org), and (MLsub(n)x2TBP)sub(org) + TcO 4 - reversible (MLsub(n-1)TcO 4 x2TBPsub(org) + L were established in the above systems. The extraction of pertechnetate ion is more effective when it is coordinated to a cation solvated by TBP than the extraction in the form of pertechnetate acid solvated by TBP. (author)

  15. Modeling of optimization strategies in the incremental CNC sheet metal forming process

    Bambach, M.; Hirt, G.; Ames, J.

    2004-01-01

    Incremental CNC sheet forming (ISF) is a relatively new sheet metal forming process for small batch production and prototyping. In ISF, a blank is shaped by the CNC movements of a simple tool in combination with a simplified die. The standard forming strategies in ISF entail two major drawbacks: (i) the inherent forming kinematics set limits on the maximum wall angle that can be formed with ISF. (ii) since elastic parts of the imposed deformation can currently not be accounted for in CNC code generation, the standard strategies can lead to undesired deviations between the target and the sample geometry.Several enhancements have recently been put forward to overcome the above limitations, among them a multistage forming strategy to manufacture steep flanges, and a correction algorithm to improve the geometric accuracy. Both strategies have been successful in improving the forming of simple parts. However, the high experimental effort to empirically optimize the tool paths motivates the use of process modeling techniques.This paper deals with finite element modeling of the ISF process. In particular, the outcome of different multistage strategies is modeled and compared to collated experimental results regarding aspects such as sheet thickness and the onset of wrinkling. Moreover, the feasibility of modeling the geometry of a part is investigated as this is of major importance with respect to optimizing the geometric accuracy. Experimental validation is achieved by optical deformation measurement that gives the local displacements and strains of the sheet during forming as benchmark quantities for the simulation

  16. Complexes of 3.6 kDa Maltodextrin with Some Metals

    Christopher H. Schilling

    2004-06-01

    Full Text Available Preparation of magnesium, lanthanum, and bismuth(III complexes of 3.6 kDa maltodextrin and some properties of the resulting materials are presented. The metal derivatives contain metals bound to the oxygen atoms of the hydroxyl groups of maltodextrin. Additionally, the metal atoms are coordinated to the hydroxyl groups of the D-glucose units of the macroligand. Such coordination stabilized the metal – oxygen bond against hydrolysis, even in boiling water. The presence of magnesium and lanthanum atoms increased the thermal stability of maltodextrin, whereas bismuth atoms decreased it.

  17. Quantitative Interpretation of Multifrequency Multimode EPR Spectra of Metal Containing Proteins, Enzymes, and Biomimetic Complexes.

    Petasis, Doros T; Hendrich, Michael P

    2015-01-01

    Electron paramagnetic resonance (EPR) spectroscopy has long been a primary method for characterization of paramagnetic centers in materials and biological complexes. Transition metals in biological complexes have valence d-orbitals that largely define the chemistry of the metal centers. EPR spectra are distinctive for metal type, oxidation state, protein environment, substrates, and inhibitors. The study of many metal centers in proteins, enzymes, and biomimetic complexes has led to the development of a systematic methodology for quantitative interpretation of EPR spectra from a wide array of metal containing complexes. The methodology is now contained in the computer program SpinCount. SpinCount allows simulation of EPR spectra from any sample containing multiple species composed of one or two metals in any spin state. The simulations are quantitative, thus allowing determination of all species concentrations in a sample directly from spectra. This chapter will focus on applications to transition metals in biological systems using EPR spectra from multiple microwave frequencies and modes. © 2015 Elsevier Inc. All rights reserved.

  18. Selective transport of metal ions through cation exchange membrane in the presence of a complexing agent

    Tingchia Huang; Jaukai Wang (National Cheng Kung Univ., Tainan (Taiwan, Province of China))

    1993-01-01

    Selective transport of metal ions through a cation exchange membrane was studied in stirred batch dialyzer for the systems Ni[sup 2+]-Cu[sup 2+] and Cu[sup 2+]-Fe[sup 3+]. Oxalic acid, malonic acid, citric acid, glycine, and ethylenediaminetetraacetic acid were employed as the complexing agents added in the feed solution in order to increase the permselectivity of metal ions. The experimental results show that the selective transport behavior of metal ions depends on the valence and the concentration of metal ions, the stoichiometric ratio of complexing agent to metal ions, and the pH value of the feed solution, but is independent of the concentration of counterion in the stripping phase. A theoretical approach was formulated on the basis of the Nernst-Planck equation and interface quasi-equilibrium. Theoretical solutions obtained from numerical calculation were in agreement with the experimental data.

  19. Structure of the active form of human origin recognition complex and its ATPase motor module

    Tocilj, Ante; On, Kin Fan; Yuan, Zuanning; Sun, Jingchuan; Elkayam, Elad; Li, Huilin; Stillman, Bruce; Joshua-Tor, Leemor

    2017-01-23

    Binding of the Origin Recognition Complex (ORC) to origins of replication marks the first step in the initiation of replication of the genome in all eukaryotic cells. Here, we report the structure of the active form of human ORC determined by X-ray crystallography and cryo-electron microscopy. The complex is composed of an ORC1/4/5 motor module lobe in an organization reminiscent of the DNA polymerase clamp loader complexes. A second lobe contains the ORC2/3 subunits. The complex is organized as a double-layered shallow corkscrew, with the AAA+ and AAA+-like domains forming one layer, and the winged-helix domains (WHDs) forming a top layer. CDC6 fits easily between ORC1 and ORC2, completing the ring and the DNA-binding channel, forming an additional ATP hydrolysis site. Analysis of the ATPase activity of the complex provides a basis for understanding ORC activity as well as molecular defects observed in Meier-Gorlin Syndrome mutations.

  20. Complex forms of mitochondrial DNA in human B cells transformed by Epstein-Barr virus (EBV)

    Christiansen, Gunna; Christiansen, C; Zeuthen, J

    1983-01-01

    Human lymphocytes and lymphoid cell lines were analyzed for the presence of complex forms of mitochondrial DNA (mtDNA) by electron microscopy. A high frequency (9%-14.5%) of catenated dimers, circular dimers, or oligomers were found in samples from Epstein-Barr-virus-(EBV) transformed lymphoblast......Human lymphocytes and lymphoid cell lines were analyzed for the presence of complex forms of mitochondrial DNA (mtDNA) by electron microscopy. A high frequency (9%-14.5%) of catenated dimers, circular dimers, or oligomers were found in samples from Epstein-Barr-virus-(EBV) transformed...

  1. Alkali-crown ether complexes at metal surfaces

    Thontasen, Nicha; Deng, Zhitao; Rauschenbach, Stephan [Max Planck Institute for Solid State Research, Stuttgart (Germany); Levita, Giacomo [University of Trieste, Trieste (Italy); Malinowski, Nikola [Max Planck Institute for Solid State Research, Stuttgart (Germany); Bulgarian Academy of Sciences, Sofia (Bulgaria); Kern, Klaus [Max Planck Institute for Solid State Research, Stuttgart (Germany); EPFL, Lausanne (Switzerland)

    2010-07-01

    Crown ethers are polycyclic ethers which, in solution, selectively bind cations depending on the size of the ring cavity. The study of a single host-guest complex is highly desirable in order to reveal the characteristics of these specific interactions at the atomic scale. Such detailed investigation is possible at the surface where high resolution imaging tools like scanning tunneling microscopy (STM) can be applied. Here, electrospray ion beam deposition (ES-IBD) is employed for the deposition of Dibenzo-24-crown-8 (DB24C8)-H{sup +}, -Na{sup +} and -Cs{sup +} complexes on a solid surface in ultrahigh vacuum (UHV). Where other deposition techniques have not been successful, this deposition technique combines the advantages of solution based preparation of the complex ions with a highly clean and controlled deposition in UHV. Single molecular structures and the cation-binding of DB24C8 at the surface are studied in situ by STM and MALDI-MS (matrix assisted laser desorption ionization mass spectrometry). The internal structure of the complex, i.e. ring and cavity, is observable only when alkali cations are incorporated. The BD24C8-H{sup +} complex in contrast appears as a compact feature. This result is in good agreement with theoretical models based on density functional theory calculations.

  2. Spectroscopic study of divalent copper complexes forming in the systems CuCl2-MCl (M= Na, K, Rb, Cs)

    Utorov, N.P.; Bakshi, Yu.M.; Bazov, V.P.; Gel'bshtejn, A.I.

    1982-01-01

    The structure of complex ions formed in salt systems CuCl 2 -MCl depending on the nature of cation of alkali metal chloride at different mole ratios (n=MCl/CuCl 2 ) is studied. The data obtained using the methods of oscillation and electron spectroscopy enable to consider that during the melting of CuCl 2 and CsCl at n 4 2- ions, have the symmetry Csub(2v) at n=1. π-bonding, which is realized with participation of of Cl - p-orbitals and Cu 2+ d-orbitals plays a very important role in the formation of dimers and polymer chains. π-conjugated systems are characterized by the spectrum of charge transfer in the visible region. Charge transfer promotes metal reduction in the excited state which is adequate to the change of electron configuration of copper from d 9 for d 10 . It results in the decrease of acceptor and increase of dative ability of copper cation in the composition of salt complex. Big (n >= 2) additions of CsCl lead to the formation of separate stable ions of CuCl 4 2- type with the symmetry Dsub(2d)

  3. Catalytic hydrogenation using complexes of base metals with tridentate ligands

    Hanson, Susan K.; Zhang, Guoqi; Vasudevan, Kalyan V.

    2017-02-14

    Complexes of cobalt and nickel with tridentate ligand PNHP.sup.R are effective for hydrogenation of unsaturated compounds. Cobalt complex [(PNHP.sup.Cy)Co(CH.sub.2SiMe.sub.3)]BAr.sup.F.sub.4 (PNHP.sup.Cy=bis[2-(dicyclohexylphosphino)ethyl]amine, BAr.sup.F.sub.4=B(3,5-(CF.sub.3).sub.2C.sub.6H.sub.3).sub.4)) was prepared and used with hydrogen for hydrogenation of alkenes, aldehydes, ketones, and imines under mild conditions (25-60.degree. C., 1-4 atm H.sub.2). Nickel complex [(PNHP.sup.Cy)Ni(H)]BPh.sub.4 was used for hydrogenation of styrene and 1-octene under mild conditions. (PNP.sup.Cy)Ni(H) was used for hydrogenating alkenes.

  4. Catalytic hydrogenation using complexes of base metals with tridentate ligands

    Vasudevan, Kalyan V.; Zhang, Guoqi; Hanson, Susan K.

    2016-09-06

    Complexes of cobalt and nickel with tridentate ligand PNHP.sup.R are effective for hydrogenation of unsaturated compounds. Cobalt complex [(PNHP.sup.Cy)Co(CH.sub.2SiMe.sub.3)]BAr.sup.F.sub.4 (PNHP.sup.Cy=bis[2-(dicyclohexylphosphino)ethyl]amine, BAr.sup.F.sub.4=B(3,5-(CF.sub.3).sub.2C.sub.6H.sub.3).sub.4)) was prepared and used with hydrogen for hydrogenation of alkenes, aldehydes, ketones, and imines under mild conditions (25-60.degree. C., 1-4 atm H.sub.2). Nickel complex [(PNHP.sup.Cy)Ni(H)]BPh.sub.4 was used for hydrogenation of styrene and 1-octene under mild conditions. (PNP.sup.Cy)Ni(H) was used for hydrogenating alkenes.

  5. Complexation induced phase separation: preparation of composite membranes with a nanometer thin dense skin loaded with metal ions

    Villalobos Vazquez de la Parra, Luis Francisco

    2015-04-21

    We present the development of a facile phase-inversion method for forming asymmetric membranes with a precise high metal ion loading capacity in only the dense layer. The approach combines the use of macromolecule-metal intermolecular complexes to form the dense layer of asymmetric membranes with nonsolvent-induced phase separation to form the porous support. This allows the independent optimization of both the dense layer and porous support while maintaining the simplicity of a phase-inversion process. Moreover, it facilitates control over (i) the thickness of the dense layer throughout several orders of magnitude—from less than 15 nm to more than 6 μm, (ii) the type and amount of metal ions loaded in the dense layer, (iii) the morphology of the membrane surface, and (iv) the porosity and structure of the support. This simple and scalable process provides a new platform for building multifunctional membranes with a high loading of well-dispersed metal ions in the dense layer.

  6. Complexation induced phase separation: preparation of composite membranes with a nanometer thin dense skin loaded with metal ions

    Villalobos Vazquez de la Parra, Luis Francisco; Karunakaran, Madhavan; Peinemann, Klaus-Viktor

    2015-01-01

    We present the development of a facile phase-inversion method for forming asymmetric membranes with a precise high metal ion loading capacity in only the dense layer. The approach combines the use of macromolecule-metal intermolecular complexes to form the dense layer of asymmetric membranes with nonsolvent-induced phase separation to form the porous support. This allows the independent optimization of both the dense layer and porous support while maintaining the simplicity of a phase-inversion process. Moreover, it facilitates control over (i) the thickness of the dense layer throughout several orders of magnitude—from less than 15 nm to more than 6 μm, (ii) the type and amount of metal ions loaded in the dense layer, (iii) the morphology of the membrane surface, and (iv) the porosity and structure of the support. This simple and scalable process provides a new platform for building multifunctional membranes with a high loading of well-dispersed metal ions in the dense layer.

  7. Serum albumin forms a lactoferrin-like soluble iron-binding complex in presence of hydrogen carbonate ions.

    Ueno, Hiroshi M; Urazono, Hiroshi; Kobayashi, Toshiya

    2014-02-15

    The iron-lactoferrin complex is a common food ingredient because of its iron-solubilizing capability in the presence of hydrogen carbonate ions. However, it is unclear whether the formation of a stable iron-binding complex is limited to lactoferrin. In this study, we investigated the effects of bovine serum albumin (BSA) on iron solubility and iron-catalyzed lipid oxidation in the presence of hydrogen carbonate ions. BSA could solubilize >100-fold molar equivalents of iron at neutral pH, exceeding the specific metal-binding property of BSA. This iron-solubilizing capability of BSA was impaired by thermally denaturing BSA at ≥ 70 °C for 10 min at pH 8.5. The resulting iron-BSA complex inhibited iron-catalyzed oxidation of soybean oil in a water-in-oil emulsion measured using the Rancimat test. Our study is the first to show that BSA, like lactoferrin, forms a soluble iron-binding complex in the presence of hydrogen carbonate ions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. Biofilm-Forming Staphylococcus epidermidis Expressing Vancomycin Resistance Early after Adhesion to a Metal Surface

    Toshiyuki Sakimura

    2015-01-01

    Full Text Available We investigated biofilm formation and time of vancomycin (VCM resistance expression after adhesion to a metal surface in Staphylococcus epidermidis. Biofilm-forming Staphylococcus epidermidis with a VCM MIC of 1 μg/mL was used. The bacteria were made to adhere to a stainless steel washer and treated with VCM at different times and concentrations. VCM was administered 0, 2, 4, and 8 hours after adhesion. The amount of biofilm formed was evaluated based on the biofilm coverage rates (BCRs before and after VCM administration, bacterial viability in biofilm was visually observed using the fluorescence staining method, and the viable bacterial count in biofilm was measured. The VCM concentration required to decrease BCR significantly compared with that of VCM-untreated bacteria was 4 μg/mL, even in the 0 hr group. In the 4 and 8 hr groups, VCM could not inhibit biofilm growth even at 1,024 μg/mL. In the 8 hr group, viable bacteria remained in biofilm at a count of 104 CFU even at a high VCM concentration (1,024 μg/mL. It was suggested that biofilm-forming Staphylococcus epidermidis expresses resistance to VCM early after adhesion to a metal surface. Resistance increased over time after adhesion as the biofilm formed, and strong resistance was expressed 4–8 hours after adhesion.

  9. A new constitutive model for prediction of springback in sheet metal forming

    Appiah, E.; Jain, M.

    2004-01-01

    With advances in computer capabilities, cost of sheet metal forming has being reducing mainly due to the reduction of trial and error approaches. At the moment, a complete process can be simulated on computer and appropriate forming conditions optimized before actual industrial forming process is carried out. While formability predictions have improved, the problem of springback exhibited by most metal, including aluminum alloy AA6111-T4, after forming persist and often leads to significant part fit-up problems during assembly. There are a number of factors that affect springback and perhaps the most significant one is constitutive equation. In this paper springback predicted by six advanced kinematic models are evaluated. In addition an improved constitutive kinematic model is presented. It is shown that by adding stress correction term (SCT) to Armstrong-Frederick model a relatively simple and yet accurate stress prediction could be obtained. The SCT was developed with the assumption that the yield surface remains convex, yield center depends on translation, size and shape variations of the yield surface. The model is implemented in a commercial finite element code (ABAQUS/Standard) via its user material interface (UMAT). Numerical simulations of U-bending were performed using automotive aluminum sheet material (AA6111-T4). It was noted that springback has inverse relationship with residual stress

  10. Adaptive scallop height tool path generation for robot-based incremental sheet metal forming

    Seim, Patrick; Möllensiep, Dennis; Störkle, Denis Daniel; Thyssen, Lars; Kuhlenkötter, Bernd

    2016-10-01

    Incremental sheet metal forming is an emerging process for the production of individualized products or prototypes in low batch sizes and with short times to market. In these processes, the desired shape is produced by the incremental inward motion of the workpiece-independent forming tool in depth direction and its movement along the contour in lateral direction. Based on this shape production, the tool path generation is a key factor on e.g. the resulting geometric accuracy, the resulting surface quality, and the working time. This paper presents an innovative tool path generation based on a commercial milling CAM package considering the surface quality and working time. This approach offers the ability to define a specific scallop height as an indicator of the surface quality for specific faces of a component. Moreover, it decreases the required working time for the production of the entire component compared to the use of a commercial software package without this adaptive approach. Different forming experiments have been performed to verify the newly developed tool path generation. Mainly, this approach serves to solve the existing conflict of combining the working time and the surface quality within the process of incremental sheet metal forming.

  11. The corrosion properties of Zr-Cr-NM alloy metallic waste form for longterm disposal

    Han, Seung Youb; Jang, Seon Ah; Eun, Hee Chul; Choi, Jung Hoon; Lee, Ki Rak; Park, Hwan Seo; Ahn, Do Hee [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2017-06-15

    KAERI is conducting research on spent cladding hulls and additive metals to generate a solidifcation host matrix for the noble metal fssion product waste in anode sludge from the electro-refning process to minimize the volume of waste that needs to be disposed of. In this study, alloy compositions Zr-17Cr, Zr-22Cr, and Zr-27Cr were prepared with or without eight noble metals representing fuel waste using induction melting. The microstructures of the resulting alloys were characterized and electrochemical corrosion tests were conducted to evaluate their corrosion characteristics. All the compositions had better corrosion characteristics than other Zr-based alloys that were evaluated for comparison. Analysis of the leach solution after the corrosion test of the Zr-22Cr-8NM specimen indicated that the noble metals were not leached during corrosion under 500 mV imposed voltage, which simulates a highly oxidizing disposal environment. The results of this study confrm that Zr-Cr based compositions will likely serve as chemically stable waste forms.

  12. Chaos synchronization and chaotization of complex chaotic systems in series form by optimal control

    Ge Zhengming; Yang, C.-H.

    2009-01-01

    By the method of quadratic optimum control, a quadratic optimal regulator is used for synchronizing two complex chaotic systems in series form. By this method the least error with less control energy is achieved, and the optimization on both energy and error is realized synthetically. The simulation results of two Quantum-CNN chaos systems in series form prove the effectiveness of this method. Finally, chaotization of the system is given by optimal control.

  13. Light induced electron transfer reactions of metal complexes

    Sutin, N.; Creutz, C.

    1980-01-01

    Properties of the excited states of tris(2,2'-bipyridine) and tris(1,10-phenanthroline) complexes of chromium(III), iron(II), ruthenium(II), osmium(II), rhodium(III), and iridium(III) are described. The electron transfer reactions of the ground and excited states are discussed and interpreted in terms of the driving force for the reaction and the distortions of the excited states relative to the corresponding ground states. General considerations relevant to the conversion of light into chemical energy are presented and progress in the use of polypyridine complexes to effect the light decomposition of water into hydrogen and oxygen is reviewed

  14. Electron transfer reactions of metal complexes in solution

    Sutin, N.

    1977-01-01

    A few representative electron-transfer reactions are selected and their kinetic parameters compared with the predictions of activated complex models. Since Taube has presented an elegant treatment of intramolecular electron-transfer reactions, emphasis is on bimolecular reactions. The latter electron-transfer reactions are more complicated to treat theoretically since the geometries of their activated complexes are not as well known as for the intramolecular case. In addition in biomolecular reactions, the work required to bring the two reactants together needs to be calculated. Since both reactants generally carry charges this presents a non-trivial problem at the ionic strengths usually used to study bimolecular electron transfer

  15. Preparation and characterization of Zr-based bulk metallic glasses in form of plate

    Pilarczyk, Wirginia, E-mail: wirginia.pilarczyk@polsl.pl

    2014-12-05

    Highlights: • Zr-based BMGs in form of plate was successful produced by die pressure casting method. • Many techniques have been used to characterize the structure of Zr{sub 55}Cu{sub 30}Ni{sub 5}Al{sub 10} alloy. • The calculated GFA parameters show that the alloy exhibits satisfactory GFA. • The studies reveal that tested as-cast Zr-based alloy is in amorphous state. - Abstract: Zr-based bulk metallic glasses present an interesting combination of physical, chemical and mechanical properties. During the last decade, intensive progress has been made and a number of applications have been suggested for these materials. In order to successfully apply these materials, it is necessary to accurately characterize their structure, thermal stability and other properties accurately. The aim of the presented work is the manufacturing, examination of the structure of selected Zr-based bulk metallic alloys and confirmation of an amorphous structure using X-ray analysis, microscopic observation and thermal analysis. In this work, the Zr-based bulk metallic glasses in form of plate was successful produced by die pressure casting method. Designed scientific station for casting zirconium based amorphous alloys in the form of plates and rods with selected dimensions is in our university a comprehensive method for achieving amorphous materials which enables us to maintain repeatability of as-cast samples with the amorphous structure and the assumed dimensions range. The diffraction pattern and exothermic reaction as well as the fracture surface morphology reveal that studied as-cast Zr-based alloy is in amorphous state. The calculated GFA parameters show that the alloy exhibits satisfactory glass-forming ability in form of studied plate. These obtained values can suggest that studied alloys are suitable materials for further planned practical application at welding process. The success of Zr-based bulk metallic glasses production in form of plate with obtained sizes is

  16. Confirmation of molecular formulas of metallic complexes through X-ray fluorescence quantitative analysis

    Filgueiras, C.A.L.; Marques, E.V.; Machado, R.M.

    1984-01-01

    X-ray fluorescence spectrophotometry was employed to determined the metal content in a series of five transition element complexes (Mn, Ti, Zn, V). The results confirmed the molecular formulas of these complexes, already proposed on the basis of elemental microanalysis, solution condutimetry and other analytical methods. (C.L.B.) [pt

  17. BIOASSAY STUDIES OF METAL(II) COMPLEXES OF 2,2'-(ETHANE ...

    Preferred Customer

    diyldiimino)diacetic acid (EDDA) were prepared and characterized. Coordination complexes of the EDDA ... corresponding amines with alkyl halide to bear diammines of the same class with different substituents. ... Bioassay studies of metal(II) complexes of 2,2'-(ethane-1,2-diyldiimino)diacetic acid. Bull. Chem. Soc. Ethiop.

  18. Hydrogen storage material and process using graphite additive with metal-doped complex hydrides

    Zidan, Ragaiy [Aiken, SC; Ritter, James A [Lexington, SC; Ebner, Armin D [Lexington, SC; Wang, Jun [Columbia, SC; Holland, Charles E [Cayce, SC

    2008-06-10

    A hydrogen storage material having improved hydrogen absorbtion and desorption kinetics is provided by adding graphite to a complex hydride such as a metal-doped alanate, i.e., NaAlH.sub.4. The incorporation of graphite into the complex hydride significantly enhances the rate of hydrogen absorbtion and desorption and lowers the desorption temperature needed to release stored hydrogen.

  19. Characterising the acoustoplastic effect in an ultrasonically assisted metal forming process

    Aziz, S A; Lucas, M

    2012-01-01

    An investigation through experiments and finite element analysis (FEA) has been carried out to study the effects of applying ultrasonic oscillations to the lower platen in forming tests for two different metals. Previous research has shown that by applying ultrasonic vibrations to the lower platen in compression tests on pure aluminium specimens, the resulting stress-strain relationship can be characterised by a temporary effective softening of the material properties during intervals of ultrasonic excitation. The current research demonstrates this effect in two different metal specimens and additionally shows that finite element simulations can be used to model the behaviour in terms of both volume and surface effects. In this study, the ultrasonic excitation was introduced both prior to and post yield and the process simulations were developed in the FEA software Abaqus. The data recorded from experiments and predicted by the FEA illustrate how ultrasonically assisted metal forming can result in a lowering of the static flow stress, consistent with the effective material softening proposed previously in studies of the acoustoplastic effect.

  20. Synthesis and Spectral Characterization of Antifungal Sensitive Schiff Base Transition Metal Complexes

    Sakthivel, A.; Rajasekaran, K.

    2007-01-01

    New N2O2 donor type Schiff base has been designed and synthesized by condensing acetoacetanilido-4-aminoantipyrine with 2-aminobenzoic acid in ethanol. Solid metal complexes of the Schiff base with Cu(II), Ni(II), Co(II), Mn(II), Zn(II), VO(IV), Hg(II) and Cd(II) metal ions were synthesized and characterized by elemental analyses, magnetic susceptibility, molar conduction, fast atom bombardment (FAB) mass, IR, UV-Vis, and 1H NMR spectral studies. The data show that the complexes have the composition of ML type. The UV-Vis. and magnetic susceptibility data of the complexes suggest a square-planar geometry around the central metal ion except VO(IV) complex which has square-pyramidal geometry. The in vitro antifungal activities of the compounds were tested against fungi such as Aspergillus niger, Aspergillus flavus, Rhizopus stolonifer, Candida albicans, Rhizoctonia bataicola and Trichoderma harizanum. All the metal complexes showed stronger antifungal activities than the free ligand. The minimum inhibitory concentrations (MIC) of the metal complexes were found in the range of 10~31 µg/ml. PMID:24015086

  1. Characterization of the adenoassociated virus Rep protein complex formed on the viral origin of DNA replication

    Li Zengi; Brister, J. Rodney; Im, Dong-Soo; Muzyczka, Nicholas

    2003-01-01

    Interaction between the adenoassociated virus (AAV) replication proteins, Rep68 and 78, and the viral terminal repeats (TRs) is mediated by a DNA sequence termed the Rep-binding element (RBE). This element is necessary for Rep-mediated unwinding of duplex DNA substrates, directs Rep catalyzed cleavage of the AAV origin of DNA replication, and is required for viral transcription and proviral integration. Six discrete Rep complexes with the AAV TR substrates have been observed in vitro, and cross-linking studies suggest these complexes contain one to six molecules of Rep. However, the functional relationship between Rep oligomerization and biochemical activity is unclear. Here we have characterized Rep complexes that form on the AAV TR. Both Rep68 and Rep78 appear to form the same six complexes with the AAV TR, and ATP seems to stimulate formation of specific, higher order complexes. When the sizes of these Rep complexes were estimated on native polyacrylamide gels, the four slower migrating complexes were larger than predicted by an amount equivalent to one or two TRs. To resolve this discrepancy, the molar ratio of protein and DNA was calculated for the three largest complexes. Data from these experiments indicated that the larger complexes included multiple TRs in addition to multiple Rep molecules and that the Rep-to-TR ratio was approximately 2. The two largest complexes were also associated with increased Rep-mediated, origin cleavage activity. Finally, we characterized a second, Rep-mediated cleavage event that occurs adjacent to the normal nicking site, but on the opposite strand. This second site nicking event effectively results in double-stranded DNA cleavage at the normal nicking site

  2. Spin crossover in Fe(phen)2(NCS)2 complexes on metallic surfaces

    Gruber, Manuel; Miyamachi, Toshio; Davesne, Vincent; Bowen, Martin; Boukari, Samy; Wulfhekel, Wulf; Alouani, Mebarek; Beaurepaire, Eric

    2017-03-01

    In this review, we give an overview on the spin crossover of Fe(phen)2(NCS)2 complexes adsorbed on Cu(100), Cu2N/Cu(100), Cu(111), Co/Cu(111), Co(100), Au(100), and Au(111) surfaces. Depending on the strength of the interaction of the molecules with the substrates, the spin crossover behavior can be drastically changed. Molecules in direct contact with non-magnetic metallic surfaces coexist in both the high- and low-spin states but cannot be switched between the two. Our analysis shows that this is due to a strong interaction with the substrate in the form of a chemisorption that dictates the spin state of the molecules through its adsorption geometry. Upon reducing the interaction to the surface either by adding a second molecular layer or inserting an insulating thin film of Cu2N, the spin crossover behavior is restored and molecules can be switched between the two states with the help of scanning tunneling microscopy. Especially on Cu2N, the two states of single molecules are stable at low temperature and thus allow the realization of a molecular memory. Similarly, the molecules decoupled from metallic substrates in the second or higher layers display thermally driven spin crossover as has been revealed by X-ray absorption spectroscopy. Finally, we discuss the situation when the complex is brought into contact with a ferromagnetic substrate. This leads to a strong exchange coupling between the Fe spin in the high-spin state and the magnetization of the substrate as deduced from spin-polarized scanning tunneling spectroscopy and ab initio calculation.

  3. A comprehensive in vitro biological investigation of metal complexes ...

    Md. Mahabob Ullah Mazumder

    ... Journal of Medicine journal homepage: http://www.elsevier.com/locate/ajme .... two new complexes containing Fe (III) and Mo(VI) of two tridentate ONO donor · sets ligands. Der Chem Sin. .... Pharmaceuticals (Basel). 2014;7(4):453–463. 13.

  4. Stability constant of the trisglycinto metal complexes | Na'aliya ...

    The stability constants of iron, manganese, cobalt, and nickel complexes of glycine have been determined in aqueous solution by potentiometric titration with standard sodium hydroxide solution. The values of the stepwise stability constants were obtained by ORIGIN '50' program. The overall stability constants of the ...

  5. Influence of complex impurity centres on radiation damage in wide-gap metal oxides

    Lushchik, A., E-mail: aleksandr.lushchik@ut.ee [Institute of Physics, University of Tartu, Ravila 14c, 50411 Tartu (Estonia); Lushchik, Ch. [Institute of Physics, University of Tartu, Ravila 14c, 50411 Tartu (Estonia); Popov, A.I. [Institute of Solid State Physics, University of Latvia, Kengaraga 8, Riga LV-1063 (Latvia); Schwartz, K. [GSI Helmholtzzentrum für Schwerionenforschung (GSI), Planckstr. 1, 64291 Darmstadt (Germany); Shablonin, E.; Vasil’chenko, E. [Institute of Physics, University of Tartu, Ravila 14c, 50411 Tartu (Estonia)

    2016-05-01

    Different mechanisms of radiation damage of wide-gap metal oxides as well as a dual influence of impurity ions on the efficiency of radiation damage have been considered on the example of binary ionic MgO and complex ionic–covalent Lu{sub 3}Al{sub 5}O{sub 12} single crystals. Particular emphasis has been placed on irradiation with ∼2 GeV heavy ions ({sup 197}Au, {sup 209}Bi, {sup 238}U, fluence of 10{sup 12} ions/cm{sup 2}) providing extremely high density of electronic excitations within ion tracks. Besides knock-out mechanism for Frenkel pair formation, the additional mechanism through the collapse of mobile discrete breathers at certain lattice places (e.g., complex impurity centres) leads to the creation of complex defects that involve a large number of host atoms. The experimental manifestations of the radiation creation of intrinsic and impurity antisite defects (Lu|{sub Al} or Ce|{sub Al} – a heavy ion in a wrong cation site) have been detected in LuAG and LuAG:Ce{sup 3+} single crystals. Light doping of LuAG causes a small enhancement of radiation resistance, while pair impurity centres (for instance, Ce|{sub Lu}–Ce|{sub Al} or Cr{sup 3+}–Cr{sup 3+} in MgO) are formed with a rise of impurity concentration. These complex impurity centres as well as radiation-induced intrinsic antisite defects (Lu|{sub Al} strongly interacting with Lu in a regular site) tentatively serve as the places for breathers collapse, thus decreasing the material resistance against dense irradiation.

  6. A slow atomic diffusion process in high-entropy glass-forming metallic melts

    Chen, Changjiu; Wong, Kaikin; Krishnan, Rithin P.; Embs, Jan P.; Chathoth, Suresh M.

    2018-04-01

    Quasi-elastic neutron scattering has been used to study atomic relaxation processes in high-entropy glass-forming metallic melts with different glass-forming ability (GFA). The momentum transfer dependence of mean relaxation time shows a highly collective atomic transport process in the alloy melts with the highest and lowest GFA. However, a jump diffusion process is the long-range atomic transport process in the intermediate GFA alloy melt. Nevertheless, atomic mobility close to the melting temperature of these alloy melts is quite similar, and the temperature dependence of the diffusion coefficient exhibits a non-Arrhenius behavior. The atomic mobility in these high-entropy melts is much slower than that of the best glass-forming melts at their respective melting temperatures.

  7. Electrode-analytical properties of polyvinylchloride membranes based on triple metal-polymeric complexes

    Katerina V. Matorina

    2015-10-01

    Full Text Available The influence of the nature of the electrode-active substances (EAS, the composition of the external and internal solutions on the formation of the analytical signal of polyvinylchloride (PVC membranes based on associates and triple metal-polymeric complexes (TMPC was established. Dehumidification of synthesized membranes increases with the content of polyvinylpyrrolidone (PVP. The value of the swelling degree is more than two times greater for membranes, which contain as EAS TMPC, relative to membranes based on associates. The value of water absorption of membranes is determined by the nature of EAS. They formed a series of increasing of the swelling degree such as associate < background membrane < TMPC. Swelling of the background membrane is explained by the physical sorption of water molecules on the surface of plasticized membrane. Hydration of PVP macromolecules varies with the introduction of metal ions, macromolecules unit undergoes a conformational transition. PVP macromolecules form tunnels or cavities where complex particles distributed and additional water accumulated through the second coordination layer. Constructed sensors based on TMPC have slope of electrode function equal to 25 mV/pC. Linear dependence of potential on the polymer concentration is observed in the range of 5–7 pC units. Sensors based on associates have slope of the electrode function of 20–25 mV/pC that can be varied depending on the nature of the EAS. Working range is 4–8 pC. Response time of sensor is less than 1 min. The optimal time for conditioning of the synthesized PVC membrane is 24 hours. Potentiometric sensors have been developed for the determination of residual amounts of low molecular PVP which is a food additive E 1201 commonly used for thickening, stabilizing and clarifying of food products. The content of PVP was determined in real objects (apple juice, beer, red wine and cognac with using the polyvinylpyrrolidone sensors (Sr < 0.08. The

  8. Radio metal (169Yb) uptake in normal and tumour cells in vitro. Influence of metabolic cell activity and complex structure

    Franke, W.G.; Kampf, G.

    1996-01-01

    Trivalent radio metal tracers have been used for tumour imaging and metastatic pain palliation. For better understanding their tumour accumulation, basic model studies of uptake of different 169 Yb complexes into cultured normal and tumour cells were performed. Whereas the uptake of 169 Yb citrate is strongly dependent on the metabolic activity and is not tumour-cell pacific, the uptake of 169 Yb complexed with amino carbonic acid (NTA, EDTA, DTPA) does not correlate to the metabolic activities. These complexes are taken up to a greater amount by the tumour cells (by a factor of about 2). Uptake of both complex types leads to a stable association to cellular compounds, 169 Yb is not releasable by the strong complexing agent DTPA. Protein binding of the 169 Yb complexes shows great influence on their cellular uptake. The bound proportion is no more available,for cellular uptake. The results indicate that i 0 uptake of 169 Yb citrate is an active cellular transport process which i not tumor-specific, ii) the 169 Yb amino carbonic acid complexes show a weak favouring by the tumour cells, iii) different from earlier acceptions the Yb complexes studied are not taken up by the cells in protein-bound form. The structure of the Yb complex is decisive for its protein binding and cellular uptake. (author). 13 refs., 6 figs

  9. Quantification of trace metals in water using complexation and filter concentration.

    Dolgin, Bella; Bulatov, Valery; Japarov, Julia; Elish, Eyal; Edri, Elad; Schechter, Israel

    2010-06-15

    Various metals undergo complexation with organic reagents, resulting in colored products. In practice, their molar absorptivities allow for quantification in the ppm range. However, a proper pre-concentration of the colored complex on paper filter lowers the quantification limit to the low ppb range. In this study, several pre-concentration techniques have been examined and compared: filtering the already complexed mixture, complexation on filter, and dipping of dye-covered filter in solution. The best quantification has been based on the ratio of filter reflectance at a certain wavelength to that at zero metal concentration. The studied complex formations (Ni ions with TAN and Cd ions with PAN) involve production of nanoparticle suspensions, which are associated with complicated kinetics. The kinetics of the complexation of Ni ions with TAN has been investigated and optimum timing could be found. Kinetic optimization in regard to some interferences has also been suggested.

  10. Impact Of Elastic Modulus Degradation On Springback In Sheet Metal Forming

    Halilovic, Miroslav; Stok, Boris; Vrh, Marko

    2007-01-01

    Strain recovery after removal of forming loads, commonly defined as springback, is of great concern in sheet metal forming, in particular with regard to proper prediction of the final shape of the part. To control the problem a lot of work has been done, either by minimizing the springback on the material side or by increasing the estimation precision in corresponding process simulations. Unfortunately, by currently available software springback still cannot be adequately predicted, because most analyses of springback are using linear, isotropic and constant Young's modulus and Poisson's ratio. But, as it was measured and reported, none of it is true. The aim of this work is to propose an upgraded mechanical model which takes evolution of damage and related orthotropic stiffness degradation into account. Damage is considered by inclusion of ellipsoidal cavities, and their influence on the stiffness degradation is taken in accordance with the Mori-Tanaka theory, adopting the GTN model for plastic flow. In order to improve the numerical springback prediction, two major things are important: first, the correct evaluation of the stress-strain state at the end of the forming process, and second, correctness of the elastic properties used in the elastic relaxation analysis. Since in modelling of the forming process we adopt a damage constitutive model with orthotropic stiffness degradation considered, a corresponding damage parameters identification upon specific experimental tests data must be performed first, independently of the metal forming modelling. An improved identification of material parameters, which simultaneously considers tensile test results with different type of specimens and using neural network, is proposed. With regard to the case in which damage in material is neglected it is shown in the article how the springback of a formed part differs, when we take orthotropic damage evolution into consideration

  11. SINTERING, A PROCESS OF METAL FORMING AS AN ECONOMIC ALTERNATIVE WITH A LOW ENVIRONMENTAL IMPACT

    Ángel Silvio Machado Rodríguez

    2017-07-01

    Full Text Available Sintering is a process of metal forming using metal powders, and it has a wide range of applications including for example, the manufacturing of parts for automotive components, home appliances, cutting tools, power tools, for the manufacturing of dental devices, among others. The process is characterized by the production of large-scale low cost parts and has a low environmental impact compared to other existing technologies, it requires less energy for processing and enables high utilization of raw materials. Also, it has the characteristic of obtaining, in most cases, the parts with final tolerances necessary for direct use by the customer, which ultimately reduces considerably the cost of production. The process is characterized by minimizing the loss of raw materials; facilitating precise control of the desired chemical composition; eliminating or reducing machining operations; providing a good surface finish; being an easy production process of automation; obtaining high purity; and ensuring exactly resistance characteristics required for each project.

  12. Characterization of the whiskerlike products formed by hydriding magnesium metal powders

    Herley, P. J.; Jones, W.; Vigeholm, Bjørn

    1985-01-01

    The structure of filamentary crystals produced during the hydriding of magnesium powder has been studies in detail. The needles of small dimensions (typically 0.5 μm in diameter) have been identified by electron analytical techniques to be oriented microcrystals of metallic magnesium. Their forma......The structure of filamentary crystals produced during the hydriding of magnesium powder has been studies in detail. The needles of small dimensions (typically 0.5 μm in diameter) have been identified by electron analytical techniques to be oriented microcrystals of metallic magnesium....... Their formation has been ascribed to the melting of localized aluminum impurities within the bulk magnesium to form a liquid eutectic. In the presence of sublimed magnesium vapor and hydrogen (as a carrier gas) a vapor-liquid-solid mechanism operates to produce a rapid unidirectional extension followed...

  13. Automated local line rolling forming and simplified deformation simulation method for complex curvature plate of ships

    Y. Zhao

    2017-06-01

    Full Text Available Local line rolling forming is a common forming approach for the complex curvature plate of ships. However, the processing mode based on artificial experience is still applied at present, because it is difficult to integrally determine relational data for the forming shape, processing path, and process parameters used to drive automation equipment. Numerical simulation is currently the major approach for generating such complex relational data. Therefore, a highly precise and effective numerical computation method becomes crucial in the development of the automated local line rolling forming system for producing complex curvature plates used in ships. In this study, a three-dimensional elastoplastic finite element method was first employed to perform numerical computations for local line rolling forming, and the corresponding deformation and strain distribution features were acquired. In addition, according to the characteristics of strain distributions, a simplified deformation simulation method, based on the deformation obtained by applying strain was presented. Compared to the results of the three-dimensional elastoplastic finite element method, this simplified deformation simulation method was verified to provide high computational accuracy, and this could result in a substantial reduction in calculation time. Thus, the application of the simplified deformation simulation method was further explored in the case of multiple rolling loading paths. Moreover, it was also utilized to calculate the local line rolling forming for the typical complex curvature plate of ships. Research findings indicated that the simplified deformation simulation method was an effective tool for rapidly obtaining relationships between the forming shape, processing path, and process parameters.

  14. Separation of metals in the form of ion associates by the method of thin-layer chromatography

    Shapovalova, E.N.; Timerbaev, A.R.; Bol'shova, T.A.; Mel'nik, S.V.; Kordejro, E.

    1990-01-01

    Behaviour of pyridylazo resorcinates of certain metals (Ga, In, Fe, Co) in the form of ionic pairs with tri-n-octylamine (TOA) under conditions of thin-layer chromatography (TLC) has been studied. For all eluents investigated Ga and In complexes possess the highest mobility. Selectivity of ionic associate separation decreases with an increase in mobile phase polarity. Mixtures with 10-15 % content of isopropanol in eluating solution are the optimal ones. Separation of Ga and In from Fe 3+ and Co takes place with separation criterion 3.1 and 4.1 respectively. An attempt to separate ionic associates of In and Ga failed owing to similar stability of their pyridylazoresorcinates. Solution of the problem of In and Ga determination in the presence of iron can contribute to concrete application of the method

  15. Potentiometric studies on the complexes of tetracycline (TC) and oxytetracycline (OTC) with some metal ions

    Ghandour, M.A.; Azab, H.A.; Hassan, A.; Ali, A.M.

    1992-01-01

    The interaction of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Zn(II), Cd(II), Hg(II), Pb(II), Al(III), and UO 2 (II) ions with tetracycline (TC) were studied by potentiometric pH titrations. The formation constants of the different binary complexes formed in such systems have been determined at 25±0.1 deg C and μ=0.1 moll -1 (NaNO 3 ). Potentiometric pH equilibrium measurements have been made under the same conditions for the interaction of oxytetracycline (OTC) and Cu(II), Cd(II), Pb(II), and UO 2 (II). The formation of (1:1) binary complexes are inferred from the potentiometric pH titration curves. The protonation constants of TC and OTC were also determined under the same conditions and refined (ESAB2M computer program). The transition metal stability constants are consistent with the Irving-Williams series. (authors)

  16. Beating Homogeneous Nucleation and Tuning Atomic Ordering in Glass-Forming Metals by Nanocalorimetry.

    Zhao, Bingge; Yang, Bin; Abyzov, Alexander S; Schmelzer, Jürn W P; Rodríguez-Viejo, Javier; Zhai, Qijie; Schick, Christoph; Gao, Yulai

    2017-12-13

    In this paper, the amorphous Ce 68 Al 10 Cu 20 Co 2 (atom %) alloy was in situ prepared by nanocalorimetry. The high cooling and heating rates accessible with this technique facilitate the suppression of crystallization on cooling and the identification of homogeneous nucleation. Different from the generally accepted notion that metallic glasses form just by avoiding crystallization, the role of nucleation and growth in the crystallization behavior of amorphous alloys is specified, allowing an access to the ideal metallic glass free of nuclei. Local atomic configurations are fundamentally significant to unravel the glass forming ability (GFA) and phase transitions in metallic glasses. For this reason, isothermal annealing near T g from 0.001 s to 25,000 s following quenching becomes the strategy to tune local atomic configurations and facilitate an amorphous alloy, a mixed glassy-nanocrystalline state, and a crystalline sample successively. On the basis of the evolution of crystallization enthalpy and overall latent heat on reheating, we quantify the underlying mechanism for the isothermal nucleation and crystallization of amorphous alloys. With Johnson-Mehl-Avrami method, it is demonstrated that the coexistence of homogeneous and heterogeneous nucleation contributes to the isothermal crystallization of glass. Heterogeneous rather than homogeneous nucleation dominates the isothermal crystallization of the undercooled liquid. For the mixed glassy-nanocrystalline structure, an extraordinary kinetic stability of the residual glass is validated, which is ascribed to the denser packed interface between amorphous phase and ordered nanocrystals. Tailoring the amorphous structure by nanocalorimetry permits new insights into unraveling GFA and the mechanism that correlates local atomic configurations and phase transitions in metallic glasses.

  17. Photophysical and physicochemical studies of rare earths complexes formed with calyx(n)arenes

    Ramirez, F.M.; Varbanov, S.; Corine, C.; Muller, G.; Fatin-Rouge, N.; Scopelliti, R.; Bunzli J, C.G.

    2001-01-01

    In this work, some of the photophysical and physicochemical properties are presented which are observed in the rare earths complexes that are formed with diverse functionalized calyx(n)arenes receptors where n=4-6 designed with predetermined properties and synthesized by own methods. (Author)

  18. The Effect of Focus on Form and Task Complexity on L2 Learners' Oral Task Performance

    Salimi, Asghar

    2015-01-01

    Second Language learners' oral task performance has been one of interesting and research generating areas of investigations in the field of second language acquisition specially, task-based language teaching and learning. The main purpose of the present study is to investigate the effect of focus on form and task complexity on L2 learners' oral…

  19. The Optimal Conditions for Form-Focused Instruction: Method, Target Complexity, and Types of Knowledge

    Kim, Jeong-eun

    2012-01-01

    This dissertation investigates optimal conditions for form-focused instruction (FFI) by considering effects of internal (i.e., timing and types of FFI) and external (i.e., complexity and familiarity) variables of FFI when it is offered within a primarily meaning-focused context of adult second language (L2) learning. Ninety-two Korean-speaking…

  20. Selective Decontamination Effect of Metal Ions in Soil Using Supercritical CO2 and TBP Complex

    Park, Jihye; Park, Kwangheon; Jung, Wonyoung

    2014-01-01

    Decontamination of soil pollution is difficult because the type of contamination largely depends on the characteristics of the pollutant and the area. Also, existing soil decontamination methods generate large quantities of secondary waste and additional process costs. For this reason, new decontamination methods are always under active investigation. A method involving the use of supercritical carbon dioxide with excellent permeability in place of chemical solvents is currently being studied. Unlike other heavy metals in fission products, uranium is used as fuel, and must be handled carefully. Therefore, in this paper, we studied a supercritical carbon dioxide method for decontaminating heavy metal ions in soil using tri-n-butyl phosphate(TBP), which is well known as a ligand for the extraction of metal ions of actinium. We investigated the decontamination effect of heavy metal ions in the soil using TBP-HNO 3 Complex and supercritical carbon dioxide. The study results showed that when heavy metals in soil are extracted using supercritical carbon dioxide, the extraction efficiency is different according to the type of pollutant metal ions in the soil. When TBP-HNO 3 Complex is used with an extractant, uranium extraction is very effective, but lithium, strontium, and cesium extraction is not effective. Therefore, in the case of a mixture of uranium and other metals such as lithium, strontium, cesium, and so on in soil contaminated by fission product leaks from nuclear power plants, we can selectively decontaminate uranium with supercritical carbon dioxide and TBP-HNO 3 Complex