Science.gov

Sample records for metal chemical addition

  1. Metal-contaminated soil remediation by means of paper mill sludges addition: chemical and ecotoxicological evaluation.

    PubMed

    Calace, N; Campisi, T; Iacondini, A; Leoni, M; Petronio, B M; Pietroletti, M

    2005-08-01

    Metal pollution of soils is a great environmental problem. The major risks due to metal pollution of soil consist of leaching to groundwater and potential toxicity to plants and/or animals. The objective of this study is to evaluate by means of chemical and ecotoxicological approach the effects of paper mill sludge addition on the mobile metal fraction of polluted metal soils. The study was carried out on acidic soil derived from mining activities and thus polluted with heavy metals, and on two paper mill sludges having different chemical features. The results obtained by leaching experiments showed that the addition of a paper mill sludge, consisting mainly of carbonates, silicates and organic matter, to a heavy-metal polluted soil produces a decrease of available metal forms. The carbonate content seems to play a key role in the chemical stabilisation of metals and consequently in a decrease of toxicity of soil. The leached solutions have a non-toxic effect. The mild remediation by addition of sludge has moreover a lasting effect.

  2. Amorphouslike chemical vapor deposited tungsten diffusion barrier for copper metallization and effects of nitrogen addition

    NASA Astrophysics Data System (ADS)

    Chang, Kow-Ming; Yeh, Ta-Hsun; Deng, I.-Chung; Shih, Chieh-Wen

    1997-08-01

    In this article, we propose an amorphouslike chemical vapor deposited tungsten (CVD-W) thin film as a diffusion barrier for copper metallization. Experimental results gave no evidence of interdiffusion and structural change for Cu/amorphouslike CVD-W/Si samples annealed up to 675 °C for 30 min in N2. At higher temperatures (700 °C), Cu penetration results in the formation of η''-Cu3Si precipitates at the CVD-W/Si interface. This is due to the crystallization of the amorphouslike CVD-W film above 650 °C, rendering the grain-boundary structure and, hence, fast pathways for Cu diffusion. The Cu/amorphouslike CVD-W/p+n diodes, thus, sustain large increases in reverse leakage current. In addition, the effects of nitrogen addition by using an in situ nitridation on the amorphouslike CVD-W film are also discussed. The effectiveness of the nitrided barrier is attributed to the blocking of the grain boundaries in the tungsten film by nitrogen atoms. This slows down Cu diffusion significantly. Physical and chemical analyses indicate that interfaces in the Cu/WNx/W/Si multilayer maintain their integrity while the annealing is carried out at 750 °C. Moreover, the reverse leakage current densities of Cu/WNx/W/p+n diodes remain at 10-7 A/cm2 after 725 °C annealing.

  3. Comparative Study of Alternative Fuel Icing Inhibitor Additive Properties & Chemical Analysis of Metal Speciation in Aviation Fuels

    DTIC Science & Technology

    2010-08-01

    Jet fuels are a mixture of diverse hydrocarbon chemical species that serve as a fuel source for jet aircraft engines. Jet fuels also contain...Figure 14. Freeze points of FSII-water mixtures by DSC, ASTM-D1177 35 Figure 15. Viscosity profile for the coolilng cycle of 10-100...disalicylidene-1,2-propanediamine (MDA). Fuel System Icing Inhibitor Additives: Petroleum is composed of a diverse mixture of hydrocarbons such as

  4. A quantum chemical study of the mechanisms of olefin addition to group 9 transition metal dioxo compounds.

    PubMed

    Ahmed, Issahaku; Tia, Richard; Adei, Evans

    2016-01-01

    The mechanistic aspects of ethylene addition to MO2(CH2)(CH3) (M=Co, Rh, Ir) have been investigated with a Hartree-Fock/DFT hybrid functional at the MO6/LACVP* and B3LYP/LACVP* levels of theory to elucidate the reaction pathways on the singlet, doublet and triplet potential energy surfaces (PES). In the reaction of the IrO2CH2CH3 complex with ethylene, [3 + 2]C,O addition is the most plausible pathway on the singlet PES, the [3 + 2]O,O addition is the most favoured pathway on the doublet surface whiles the stepwise [1 + 1] addition involving the oxygen atom of the complex in the first step and the carbon atom of the complex in the second step is the most plausible pathway on the triplet PES. For the reaction of the RhO2(CH2)(CH3) complex, the [2 + 2]Rh,O addition pathway is the most favoured on the singlet surface, the [2 + 2]Rh,C is the most plausible pathway on the triplet PES and [3 + 2]C,O is the most plausible on the doublet surface. For the reactions of the CoO2(CH2)(CH3) complex, the [1 + 2]O addition is the most plausible on the singlet PES, [3 + 2]C=Co=O cycloaddition to form the five-membered intermediate is the most preferred pathway on the doublet PES, whiles on the triplet PES the preferred pathway is the [3 + 2] addition across the O=Co=O bond of the metal complex. The reactions of olefins with the Co dioxo complex have lower activation barriers for the preferred [3 + 2] and [2 + 2] addition pathways as well as fewer side reactions than those of the rhodium and iridium systems. This could imply that the cobalt dioxo complexes can efficiently and selectively catalyze specific reactions in oxidation of olefins than Rh and Ir oxo complexes will do and therefore Co oxo complexes may be better catalysts for specific oxidation reactions of olefins than Rh and Ir complexes are. The activation barriers for the formation of the four-or five-membered metallacycle intermediates through [2 + 2] or [3 + 2] cyclo-addition are lower on the

  5. Soil stabilization by chemical additives

    NASA Astrophysics Data System (ADS)

    Ghazali, F. M.

    The effects of phosphoric acid and lime additives on the compaction characteristics, the cohesion value, and the angle of friction of soils containing various percentages of Kaolin clay were compared and the applicability of Sherif's procedure for determining the coefficient of lateral earth pressure at rest for chemically stabilized soils was investigated. Both additives were found to increase the cohesion and the angle of friction of compacted sandkaolin clay mixtures. Increments were greater in basic addition than in acidic addition. The increment in the cohesion value is dependent mostly on clay content, water content and dry density while the increment in the angle of friction is mostly dependent on clay content and water content, with the factors of the type and content of the chemical common to both increments. Compaction data indicate that maximum dry density, and optimum water content are dependent on clay content and chemical type and content. The expression proposed by Sherif was found to be applicable for chemically treated cohesive soils.

  6. Removal of strontium and transuranics from Hanford tank waste via addition of metal cations and chemical oxidant: FY 1995 test results

    SciTech Connect

    Orth, R.J.; Zacher, A.H.; Schmidt, A.J.; Elmore, M.R.; Elliott, K.R.; Neuenschwander, G.G.; Gano, S.R.

    1995-09-01

    Chelating organics and some of their degradation products in the Hanford tank waste, such as EDTA, HEDTA, and NTA act to solubilize strontium and transuranics (TRU) in the tank waste supernatant. Displacement of strontium and TRU will facilitate the removal of these radionuclides via precipitation/filtration, ion exchange, or solvent extraction so that low-level waste feed specifications can be met. Pacific Northwest Laboratory has investigated two methods for releasing organic-complexed strontium and TRU components to allow for effective pretreatment of tank waste supernatant: metal cation addition (to promote displacement and flocculation) and chemical oxidant (pennanganate) addition (to promote chelator destruction/defunctionalization and possibly flocculation). These methods, which can be conducted at near-ambient. temperatures and pressures, could be deployed as intank processes.

  7. Metal Additive Manufacturing: A Review

    NASA Astrophysics Data System (ADS)

    Frazier, William E.

    2014-06-01

    This paper reviews the state-of-the-art of an important, rapidly emerging, manufacturing technology that is alternatively called additive manufacturing (AM), direct digital manufacturing, free form fabrication, or 3D printing, etc. A broad contextual overview of metallic AM is provided. AM has the potential to revolutionize the global parts manufacturing and logistics landscape. It enables distributed manufacturing and the productions of parts-on-demand while offering the potential to reduce cost, energy consumption, and carbon footprint. This paper explores the material science, processes, and business consideration associated with achieving these performance gains. It is concluded that a paradigm shift is required in order to fully exploit AM potential.

  8. The Structural Evolution of (Gd, Y)Ba2Cu3Ox Tapes With Zr Addition Made by Metal Organic Chemical Vapor Deposition

    SciTech Connect

    Lei, CH; Galstyan, E; Chen, YM; Shi, T; Liu, YH; Khatri, N; Liu, JF; Xiong, XM; Majkic, G; Selvamanickam, V

    2013-06-01

    Structural analysis of (Gd, Y) Ba2Cu3Ox tapes with Zr addition made by metal organic chemical vapor deposition has been conducted with transmission electron microscopy and X-ray diffraction. Zr content in the films was varied from 0 to 25% in the precursor. In all Zr-doped films, self-assembled nanocolumnar structures of BaZrO3 (BZO) were observed along the c-axis. The amount of BaZrO3 was found to increase steadily with Zr content. Additionally, planar BZO plates were found on the (001) plane of (Gd, Y) Ba2Cu3Ox film. The size and thickness of BZO plates were seen to increase with Zr doping level. Rare-earth copper oxide phases were observed to begin to emerge in the 20% Zr-doped film. Cross-sectional study of the interface between (Gd, Y)Ba2Cu3Ox and LaMnO3 cap layer revealed a thin discrete BZO layer on the LaMnO3 in the 20% Zr doped film.

  9. Large Scale Metal Additive Techniques Review

    SciTech Connect

    Nycz, Andrzej; Adediran, Adeola I; Noakes, Mark W; Love, Lonnie J

    2016-01-01

    In recent years additive manufacturing made long strides toward becoming a main stream production technology. Particularly strong progress has been made in large-scale polymer deposition. However, large scale metal additive has not yet reached parity with large scale polymer. This paper is a review study of the metal additive techniques in the context of building large structures. Current commercial devices are capable of printing metal parts on the order of several cubic feet compared to hundreds of cubic feet for the polymer side. In order to follow the polymer progress path several factors are considered: potential to scale, economy, environment friendliness, material properties, feedstock availability, robustness of the process, quality and accuracy, potential for defects, and post processing as well as potential applications. This paper focuses on current state of art of large scale metal additive technology with a focus on expanding the geometric limits.

  10. Additively Manufactured Metals in Oxygen Systems Project

    NASA Technical Reports Server (NTRS)

    Tylka, Jonathan

    2015-01-01

    Metals produced by additive manufacturing methods, such as Powder Bed Fusion Technology, are now mature enough to be considered for qualification in human spaceflight oxygen systems. The mechanical properties of metals produced through AM processes are being systematically studied. However, it is unknown whether AM metals in oxygen applications may present an increased risk of flammability or ignition as compared to wrought metals of the same metallurgical composition due to increased porosity. Per NASA-STD-6001B materials to be used in oxygen system applications shall be based on flammability and combustion test data, followed by a flammability assessment. Without systematic flammability and ignition testing in oxygen there is no credible method for NASA to accurately evaluate the risk of using AM metals in oxygen systems.

  11. Metal-deactivating additives for liquid fuels

    SciTech Connect

    Boneva, M.I.; Ivanov, S.K.; Kalitchin, Z.D.; Tanielyan, S.K.; Terebenina, A.; Todorova, O.I.

    1995-05-01

    The metal-deactivating and the antioxidant properties of 1-phenyl-3-methylpyrazolone-5 derivatives have been investigated both in the model reaction of low temperature oxidation of ethylbenzene and in gasoline oxidation. The study of the ability of these derivatives to reduce the catalytic effect of copper naphthenate demonstrates that they are promising as metal deactivating additives for light fuels. Some of the pyrazolone compounds appear to be of special interest for the long-term storage of liquid fuels due to their action as multifunctional inhibitors.

  12. OPERATOR BURDEN IN METAL ADDITIVE MANUFACTURING

    SciTech Connect

    Elliott, Amy M; Love, Lonnie J

    2016-01-01

    Additive manufacturing (AM) is an emerging manufacturing process that creates usable machine parts via layer-by-layer joining of a stock material. With this layer-wise approach, high-performance geometries can be created which are impossible with traditional manufacturing methods. Metal AM technology has the potential to significantly reduce the manufacturing burden of developing custom hardware; however, a major consideration in choosing a metal AM system is the required amount of operator involvement (i.e., operator burden) in the manufacturing process. The operator burden not only determines the amount of operator training and specialization required but also the usability of the system in a facility. As operators of several metal AM processes, the Manufacturing Demonstration Facility (MDF) at Oak Ridge National Labs is uniquely poised to provide insight into requirements for operator involvement in each of the three major metal AM processes. The paper covers an overview of each of the three metal AM technologies, focusing on the burden on the operator to complete the build cycle, process the part for final use, and reset the AM equipment for future builds.

  13. Microstructural Control of Additively Manufactured Metallic Materials

    NASA Astrophysics Data System (ADS)

    Collins, P. C.; Brice, D. A.; Samimi, P.; Ghamarian, I.; Fraser, H. L.

    2016-07-01

    In additively manufactured (AM) metallic materials, the fundamental interrelationships that exist between composition, processing, and microstructure govern these materials’ properties and potential improvements or reductions in performance. For example, by using AM, it is possible to achieve highly desirable microstructural features (e.g., highly refined precipitates) that could not otherwise be achieved by using conventional approaches. Simultaneously, opportunities exist to manage macro-level microstructural characteristics such as residual stress, porosity, and texture, the last of which might be desirable. To predictably realize optimal microstructures, it is necessary to establish a framework that integrates processing variables, alloy composition, and the resulting microstructure. Although such a framework is largely lacking for AM metallic materials, the basic scientific components of the framework exist in literature. This review considers these key components and presents them in a manner that highlights key interdependencies that would form an integrated framework to engineer microstructures using AM.

  14. Additively manufactured metallic pentamode meta-materials

    NASA Astrophysics Data System (ADS)

    Hedayati, R.; Leeflang, A. M.; Zadpoor, A. A.

    2017-02-01

    Mechanical metamaterials exhibit unusual mechanical properties that originate from their topological design. Pentamode metamaterials are particularly interesting because they could be designed to possess any thermodynamically admissible elasticity tensor. In this study, we additively manufacture the metallic pentamode metamaterials from a biocompatible and mechanically strong titanium alloy (Ti-6Al-4V) using an energy distribution method developed for the powder bed fusion techniques. The mechanical properties of the developed materials were a few orders of magnitude higher than those of the similar topologies fabricated previously from polymers. Moreover, the elastic modulus and yield stress of the presented pentamode metamaterials were decoupled from their relative density, meaning that the metallic meta-biomaterials with independently tailored elastic and mass transport (permeability) properties could be designed for tissue regeneration purposes.

  15. Metal Additive Manufacturing: A Review of Mechanical Properties (Postprint)

    DTIC Science & Technology

    2016-04-21

    AFRL-RX-WP-JA-2017-0156 METAL ADDITIVE MANUFACTURING : A REVIEW OF MECHANICAL PROPERTIES (POSTPRINT) John J. Lewandowski and...2012 – 19 March 2016 4. TITLE AND SUBTITLE METAL ADDITIVE MANUFACTURING : A REVIEW OF MECHANICAL PROPERTIES (POSTPRINT) 5a. CONTRACT NUMBER...data on the mechanical properties of additively manufactured metallic materials. The additive manufacturing techniques utilized to generate samples

  16. Role of metal oxides in chemical evolution

    NASA Astrophysics Data System (ADS)

    Kamaluddin

    2013-06-01

    Steps of chemical evolution have been designated as formation of biomonomers followed by their polymerization and then to modify in an organized structure leading to the formation of first living cell. Formation of small molecules like amino acids, organic bases, sugar etc. could have occurred in the reducing atmosphere of the primitive Earth. Polymerization of these small molecules could have required some catalyst. In addition to clay, role of metal ions and metal complexes as prebiotic catalyst in the synthesis and polymerization of biomonomers cannot be ruled out. Metal oxides are important constituents of Earth crust and that of other planets. These oxides might have adsorbed organic molecules and catalyzed the condensation processes, which may have led to the formation of first living cell. Different studies were performed in order to investigate the role of metal oxides (especially oxides of iron and manganese) in chemical evolution. Iron oxides (goethite, akaganeite and hematite) as well as manganese oxides (MnO, Mn2O3, Mn3O4 and MnO2) were synthesized and their characterization was done using IR, powder XRD, FE-SEM and TEM. Role of above oxides was studied in the adsorption of ribose nucleotides, formation of nucleobases from formamide and oligomerization of amino acids. Above oxides of iron and manganese were found to have good adsorption affinity towards ribose nucleotides, high catalytic activity in the formation of several nucleobases from formamide and oligomerization of glycine and alanine. Characterization of products was performed using UV, IR, HPLC and ESI-MS techniques. Presence of hematite-water system on Mars has been suggested to be a positive indicator in the chemical evolution on Mars.

  17. Laser Assisted Additively Manufactured Transition Metal Coating on Aluminum

    NASA Astrophysics Data System (ADS)

    Vora, Hitesh D.; Rajamure, Ravi Shanker; Roy, Anurag; Srinivasan, S. G.; Sundararajan, G.; Banerjee, Rajarshi; Dahotre, Narendra B.

    2016-07-01

    Various physical and chemical properties of surface and subsurface regions of Al can be improved by the formation of transition metal intermetallic phases (Al x TM y ) via coating of the transition metal (TM). The lower equilibrium solid solubility of TM in Al (<1 at.%) is a steep barrier to the formation of solid solutions using conventional alloying methods. In contrast, as demonstrated in the present work, surface engineering via a laser-aided additive manufacturing approach can effectively synthesize TM intermetallic coatings on the surface of Al. The focus of the present work included the development of process control to achieve thermodynamic and kinetic conditions necessary for desirable physical, microstructural and compositional attributes. A multiphysics finite element model was developed to predict the temperature profile, cooling rate, melt depth, dilution of W in Al matrix and corresponding micro-hardness in the coating, and the interface between the coating and the base material and the base material.

  18. CONTROL ROD ALLOY CONTAINING NOBLE METAL ADDITIONS

    DOEpatents

    Anderson, W.K.; Ray, W.E.

    1960-05-01

    Silver-base alloys suitable for use in the fabrication of control rods for neutronic reactors are given. The alloy consists of from 0.5 wt.% to about 1.5 wt.% of a noble metal of platinum, ruthenium, rhodium, osmium, or palladium, up to 10 wt.% of cadmium, from 2 to 20 wt.% indium, the balance being silver.

  19. Chemical sensing and imaging with metallic nanorods.

    PubMed

    Murphy, Catherine J; Gole, Anand M; Hunyadi, Simona E; Stone, John W; Sisco, Patrick N; Alkilany, Alaaldin; Kinard, Brian E; Hankins, Patrick

    2008-02-07

    In this Feature Article, we examine recent advances in chemical analyte detection and optical imaging applications using gold and silver nanoparticles, with a primary focus on our own work. Noble metal nanoparticles have exciting physical and chemical properties that are entirely different from the bulk. For chemical sensing and imaging, the optical properties of metallic nanoparticles provide a wide range of opportunities, all of which ultimately arise from the collective oscillations of conduction band electrons ("plasmons") in response to external electromagnetic radiation. Nanorods have multiple plasmon bands compared to nanospheres. We identify four optical sensing and imaging modalities for metallic nanoparticles: (1) aggregation-dependent shifts in plasmon frequency; (2) local refractive index-dependent shifts in plasmon frequency; (3) inelastic (surface-enhanced Raman) light scattering; and (4) elastic (Rayleigh) light scattering. The surface chemistry of the nanoparticles must be tunable to create chemical specificity, and is a key requirement for successful sensing and imaging platforms.

  20. Chemical Shuttle Additives in Lithium Ion Batteries

    SciTech Connect

    Patterson, Mary

    2013-03-31

    than NMC) and the DDB is useful for lithium ion cells with LFP cathodes (potential that is lower than NMC). A 4.5 V class redox shuttle provided by Argonne National Laboratory was evaluated which provides a few cycles of overcharge protection for lithium ion cells containing NMC cathodes but it is not stable enough for consideration. Thus, a redox shuttle with an appropriate redox potential and sufficient chemical and electrochemical stability for commercial use in larger format lithium ion cells with NMC cathodes was not found. Molecular imprinting of the redox shuttle molecule during solid electrolyte interphase (SEI) layer formation likely contributes to the successful reduction of oxidized redox shuttle species at carbon anodes. This helps to understand how a carbon anode covered with an SEI layer, that is supposed to be electrically insulating, can reduce the oxidized form of a redox shuttle.

  1. Casting of metallic fuel containing minor actinide additions

    NASA Astrophysics Data System (ADS)

    Trybus, C. L.; Sanecki, J. E.; Henslee, S. P.

    1993-09-01

    Metallic U-20%Pu-10%Zr (by weight) nuclear fuel was injection cast with the addition of two minor actinides, 2.1% Am and 1.3% Np. Three full length fuel slugs (4.3 mm × 340 mm) were successfully cast incorporating both Np and Am. No unusual macrosegregation of the major constituents was observed. About 60% of the initial Am and 100% of the Np charge was present in the as-cast fuel. Am loss was attributed to volatile contaminants in the feed stock and evaporation at the casting temperature (1465°C). Microstructural and microchemical characterization of the as-cast fuel along with bulk chemical analyses are reported.

  2. The effect of chemical additives on the synthesis of ethanol

    SciTech Connect

    Chuang, S.S.C.

    1989-04-30

    The objective of this research is to elucidate the role of various chemical additives on ethanol synthesis over Rh- and Ni-based catalysts. Chemical additives used for this study will include S, P, Ag, Cu, Mn, and Na which have different electronegativeities. The effect of additives on the surface state of the catalysts, heat of adsorption of reactant molecules, reaction intermediates, reaction pathways, reaction kinetics, and product distributions is/will be investigated by a series of experimental studies of NO adsorption, reactive probing, steady state rate measurement, and transient kinetic study. CO insertion is known to be a key step to the formation of acetaldehyde and ethanol from CO hydrogenation. Reaction of ethylene with syngas is used as a probe to determine CO insertion capabilities of metal catalysts. During the sixth quarter of the project, the mechanism of CO insertion on Ni/SiO{sub 2} was investigated by in-situ infrared spectroscopy. Ni/SiO{sub 2}, a methanation catalyst, has been shown to exhibit CO insertion activity. In situ infrared studies of CO/H{sub 2} and C{sub 2}H{sub 4}/CO/H{sub 2} reactions show that the carbonylation of Ni/SiO{sub 2} to Ni(CO){sub 4} leads to an inhibition of methanation in CO hydrogenation but an enhancement of formation of propionaldehyde in C{sub 2}H{sub 4}/CO/H{sub 2} reaction. The results suggest that the sites for propionaldehyde formation is different from those for methanation.

  3. Toxic Industrial Chemical Removal by Isostructural Metal-Organic Frameworks

    DTIC Science & Technology

    2011-01-01

    distance between the MOF -74 metal and the adsorbed hydrogen molecule. In addition, the authors studied the methane storage capabilities of these MOFs and...industrial processes such as gas storage , separations, and catalysis [1-4]. MOFs self-assemble using combinations of metal clusters and organic linking...and organic linkers to achieve better selectivity and activity towards chemicals such as, hydrogen , carbon dioxide, and methane, for gas storage

  4. Chemical resistance guide for metals and alloys

    SciTech Connect

    1998-12-31

    This guide contains data for 29,000 combinations of corrodents vs. metals, metal alloys, and carbon. Features and specifications include: (1) 963 liquid or dry chemicals, gases, lubricants, household fluids, foods, atmospheres, and other environments are covered; (2) 70 chemical trade names are covered; (3) 500 synonyms of covered chemicals, gases, etc. are indexed to page numbers; (4) corrodents are listed in alphabetical order; (5) data are presented in symbolic format (A, B, C, NR); (6) where known chemical resistance varies with concentration and temperature, data are presented in descending order of concentration and temperature; (7) mechanical, physical, and electrical properties data for each metal are provided; (8) a flex thumb index is provided at the right-hand margin of the right-hand pages to facilitate quick access to the desired data; (9) an electromotive or galvanic series list covering 120 metals, alloys, and carbon is included; (10) machinability ratings for most metals, including some specific S.F.M. rates, is included; (11) creep or stress relaxation rates at various levels of stress, temperature, and time are included; and (12) printed on semigloss, 70 pound, plastic-coated bond paper that last through years of reference.

  5. 33 CFR 157.31 - Discharges: Chemical additives.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 33 Navigation and Navigable Waters 2 2013-07-01 2013-07-01 false Discharges: Chemical additives. 157.31 Section 157.31 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY... OIL IN BULK Vessel Operation § 157.31 Discharges: Chemical additives. No person may use a...

  6. 33 CFR 157.31 - Discharges: Chemical additives.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 33 Navigation and Navigable Waters 2 2014-07-01 2014-07-01 false Discharges: Chemical additives. 157.31 Section 157.31 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY... OIL IN BULK Vessel Operation § 157.31 Discharges: Chemical additives. No person may use a...

  7. 33 CFR 157.31 - Discharges: Chemical additives.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 33 Navigation and Navigable Waters 2 2011-07-01 2011-07-01 false Discharges: Chemical additives. 157.31 Section 157.31 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY... OIL IN BULK Vessel Operation § 157.31 Discharges: Chemical additives. No person may use a...

  8. 33 CFR 157.31 - Discharges: Chemical additives.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 33 Navigation and Navigable Waters 2 2010-07-01 2010-07-01 false Discharges: Chemical additives. 157.31 Section 157.31 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY... OIL IN BULK Vessel Operation § 157.31 Discharges: Chemical additives. No person may use a...

  9. 33 CFR 157.31 - Discharges: Chemical additives.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 33 Navigation and Navigable Waters 2 2012-07-01 2012-07-01 false Discharges: Chemical additives. 157.31 Section 157.31 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY... OIL IN BULK Vessel Operation § 157.31 Discharges: Chemical additives. No person may use a...

  10. Quantum chemical treatments of metal clusters.

    PubMed

    Weigend, Florian; Ahlrichs, Reinhart

    2010-03-28

    This work focuses on finding and rationalizing the building principles of clusters with approximately 300 atoms of different types of metals: main group elements (Al, Sn), alkaline earth metals (Mg), transition metals (Pd) and clusters consisting of two different elements (Ir and Pt). Two tools are inevitable for this purpose: (i) quantum chemical methods that are able to treat a given cluster with both sufficient accuracy and efficiency and (ii) algorithms that are able to systematically scan the (3n-6)-dimensional potential surface of an n-atomic cluster for promising isomers. Currently, the only quantum chemical method that can be applied to metal clusters is density functional theory (DFT). Other methods either do not account for the multi-reference character of metal clusters or are too expensive and thus can be applied only to clusters of very few atoms, which usually is not sufficient for studying the building principles. The accuracy of DFT is not known a priori, but extrapolations to bulk values from calculated series of data show satisfying agreement with experimental data. For scans of the potential surface, simulated annealing techniques or genetic algorithms were used for the smaller clusters (approx. 20-30 atoms), and for the larger clusters considerations were restricted to selected packings and shapes. For the mixed-metallic clusters, perturbation theory turned out to be efficient and successful for finding the most promising distributions of the two atom types at the different sites.

  11. View of building 11050, showing metal clad addition on east ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    View of building 11050, showing metal clad addition on east elevation, looking southwest. - Naval Ordnance Test Station Inyokern, China Lake Pilot Plant, Machine Shop, C Street, China Lake, Kern County, CA

  12. A novel high-efficiency methodology for metal additive manufacturing

    NASA Astrophysics Data System (ADS)

    Du, Jun; Wei, Zhengying; Wang, Xin; Fang, Xuewei; Zhao, Guangxi

    2016-11-01

    Metal additive manufacturing (AM) offers unrivalled design freedom with the ability to manufacture complex parts. However, the high capital costs and slow throughput printing have severely restricted its application. In this paper, a new metal AM process, referred to as the "metal fused-coating additive manufacturing (MFCAM)", was developed for highly efficient metal parts production. This new process is the combination of metal fused-coating process and laser surface melting process. A two-dimensional numerical model was established to provide an insight into the primary thermo-physical phenomena occurring in the MFCAM process. Experiments of single-track formation were conducted using MFCAM to validate the feasibility of the proposed process. The good agreement between experimental and simulated results demonstrated the reasonableness of the established models.

  13. Chemical segregation in metallic glass nanowires

    SciTech Connect

    Zhang, Qi; Li, Mo; Li, Qi-Kai

    2014-11-21

    Nanowires made of metallic glass have been actively pursued recently due to the superb and unique properties over those of the crystalline materials. The amorphous nanowires are synthesized either at high temperature or via mechanical disruption using focused ion beam. These processes have potential to cause significant changes in structure and chemical concentration, as well as formation of defect or imperfection, but little is known to date about the possibilities and mechanisms. Here, we report chemical segregation to surfaces and its mechanisms in metallic glass nanowires made of binary Cu and Zr elements from molecular dynamics simulation. Strong concentration deviation are found in the nanowires under the conditions similar to these in experiment via focused ion beam processing, hot imprinting, and casting by rapid cooling from liquid state. Our analysis indicates that non-uniform internal stress distribution is a major cause for the chemical segregation, especially at low temperatures. Extension is discussed for this observation to multicomponent metallic glass nanowires as well as the potential applications and side effects of the composition modulation. The finding also points to the possibility of the mechanical-chemical process that may occur in different settings such as fracture, cavitation, and foams where strong internal stress is present in small length scales.

  14. Chemical Mixture Risk Assessment Additivity-Based Approaches

    EPA Science Inventory

    Powerpoint presentation includes additivity-based chemical mixture risk assessment methods. Basic concepts, theory and example calculations are included. Several slides discuss the use of "common adverse outcomes" in analyzing phthalate mixtures.

  15. Chemical Mixture Risk Assessment Additivity-Based Approaches

    EPA Science Inventory

    Powerpoint presentation includes additivity-based chemical mixture risk assessment methods. Basic concepts, theory and example calculations are included. Several slides discuss the use of "common adverse outcomes" in analyzing phthalate mixtures.

  16. The effect of chemical additives on the synthesis of ethanol

    SciTech Connect

    Chuang, S.S.C.

    1990-07-01

    The objective of this research is to elucidate the role of various chemical additives on ethanol synthesis over Rh- and Ni-based catalysts. Chemical additives used for this study will include S, P, Ag, Cu, Mn, and Na which have different electronegativities. The effect of additives on the surface state of the catalysts, heat of adsorption of reactant molecules, reaction intermediates, reaction pathways, reaction kinetics, and product distributions is/will be investigated by a series of experimental studies of NO adsorption, reaction probing, study state rate measurement, and transient kinetic study. A better understanding of the role of additive on the synthesis reaction may allow us to use chemical additives to manipulate the catalytic properties of Rh- and Ni-based catalysts for producing high yields of ethanol from syngas.

  17. A review of selected chemical additives in cosmetic products.

    PubMed

    Juhász, Margit Lai Wun; Marmur, Ellen S

    2014-01-01

    The addition of chemical additives to consumer cosmetic products is a common practice to increase cosmetic effectiveness, maintain cosmetic efficacy, and produce a longer-lasting, more viable product. Recently, manufacturers have come under attack for the addition of chemicals including dioxane, formaldehyde, lead/lead acetate, parabens, and phthalate, as these additives may prove harmful to consumer health. Although reports show that these products may indeed adversely affect human health, these studies are conducted using levels of the aforementioned chemicals at much higher levels of exposure than those found in cosmetic products. When cosmeceuticals are used as per manufacturer's instructions, it is estimated that the levels of harmful additives found in these products are considerably lower than reported toxic concentrations. © 2014 Wiley Periodicals, Inc.

  18. The effect of chemical additives on the synthesis of ethanol

    SciTech Connect

    Chuang, S.S.C.

    1990-04-09

    The objective of this research is to elucidate the role of various chemical additives on ethanol synthesis over Rh- and Ni-based catalysts. Chemical additives used for this study will include S, P, Ag, Cu, Mn, and Na which have different electronegativities. The effect of additives on the surface state of the catalysts, heat of adsorption of reactant molecules, reaction intermediates, reaction pathways, reaction kinetics, and product distributions is/will be investigated by a series of experimental studies of NO adsorption, reaction probing, study state rate measurement, and transient kinetic study. A better understanding of the role of additive on the synthesis reaction may allow us to use chemical additives to manipulate the catalytic properties of Rh- and Ni-based catalysts for producing high yields of ethanol from syngas.

  19. Epitaxy and Microstructure Evolution in Metal Additive Manufacturing

    NASA Astrophysics Data System (ADS)

    Basak, Amrita; Das, Suman

    2016-07-01

    Metal additive manufacturing (AM) works on the principle of incremental layer-by-layer material consolidation, facilitating the fabrication of objects of arbitrary complexity through the controlled melting and resolidification of feedstock materials by using high-power energy sources. The focus of metal AM is to produce complex-shaped components made of metals and alloys to meet demands from various industrial sectors such as defense, aerospace, automotive, and biomedicine. Metal AM involves a complex interplay between multiple modes of energy and mass transfer, fluid flow, phase change, and microstructural evolution. Understanding the fundamental physics of these phenomena is a key requirement for metal AM process development and optimization. The effects of material characteristics and processing conditions on the resulting epitaxy and microstructure are of critical interest in metal AM. This article reviews various metal AM processes in the context of fabricating metal and alloy parts through epitaxial solidification, with material systems ranging from pure-metal and prealloyed to multicomponent materials. The aim is to cover the relationships between various AM processes and the resulting microstructures in these material systems.

  20. Chemical vapor deposition of group IIIB metals

    DOEpatents

    Erbil, Ahmet

    1989-01-01

    Coatings of Group IIIB metals and compounds thereof are formed by chemical vapor deposition, in which a heat decomposable organometallic compound of the formula (I) ##STR1## where M is a Group IIIB metal, such as lanthanum or yttrium and R is a lower alkyl or alkenyl radical containing from 2 to about 6 carbon atoms, with a heated substrate which is above the decomposition temperature of the organometallic compound. The pure metal is obtained when the compound of the formula I is the sole heat decomposable compound present and deposition is carried out under nonoxidizing conditions. Intermetallic compounds such as lanthanum telluride can be deposited from a lanthanum compound of formula I and a heat decomposable tellurium compound under nonoxidizing conditions.

  1. Chemical vapor deposition of group IIIB metals

    DOEpatents

    Erbil, A.

    1989-11-21

    Coatings of Group IIIB metals and compounds thereof are formed by chemical vapor deposition, in which a heat decomposable organometallic compound of the formula given in the patent where M is a Group IIIB metal, such as lanthanum or yttrium and R is a lower alkyl or alkenyl radical containing from 2 to about 6 carbon atoms, with a heated substrate which is above the decomposition temperature of the organometallic compound. The pure metal is obtained when the compound of the formula 1 is the sole heat decomposable compound present and deposition is carried out under nonoxidizing conditions. Intermetallic compounds such as lanthanum telluride can be deposited from a lanthanum compound of formula 1 and a heat decomposable tellurium compound under nonoxidizing conditions.

  2. Applications of Metal Additive Manufacturing in Veterinary Orthopedic Surgery

    NASA Astrophysics Data System (ADS)

    Harrysson, Ola L. A.; Marcellin-Little, Denis J.; Horn, Timothy J.

    2015-03-01

    Veterinary medicine has undergone a rapid increase in specialization over the last three decades. Veterinarians now routinely perform joint replacement, neurosurgery, limb-sparing surgery, interventional radiology, radiation therapy, and other complex medical procedures. Many procedures involve advanced imaging and surgical planning. Evidence-based medicine has also become part of the modus operandi of veterinary clinicians. Modeling and additive manufacturing can provide individualized or customized therapeutic solutions to support the management of companion animals with complex medical problems. The use of metal additive manufacturing is increasing in veterinary orthopedic surgery. This review describes and discusses current and potential applications of metal additive manufacturing in veterinary orthopedic surgery.

  3. Metal-Catalyzed Asymmetric Michael Addition in Natural Product Synthesis.

    PubMed

    Hui, Chunngai; Pu, Fan; Xu, Jing

    2016-12-19

    Asymmetric catalysis for chiral compound synthesis is a rapidly growing field in modern organic chemistry. Asymmetric catalytic processes have been indispensable for the synthesis of enantioselective materials to meet demands from various fields. Michael addition has been used extensively for the construction of C-C bonds under mild conditions. With the discovery and development of organo- and metal-catalyzed asymmetric Michael additions, the synthesis of enantioselective and/or diastereoselective Michael adducts has become possible and increasingly prevalent in the literature. In particular, metal-catalyzed asymmetric Michael addition has been employed as a key reaction in natural product synthesis for the construction of contiguous quaternary stereogenic center(s), which is still a difficult task in organic synthesis. Previously reported applications of metal-catalyzed asymmetric Michael additions in natural product synthesis are presented here and discussed in depth.

  4. Modeling of additive manufacturing processes for metals: Challenges and opportunities

    DOE PAGES

    Francois, Marianne M.; Sun, Amy; King, Wayne E.; ...

    2017-01-09

    Here, with the technology being developed to manufacture metallic parts using increasingly advanced additive manufacturing processes, a new era has opened up for designing novel structural materials, from designing shapes and complex geometries to controlling the microstructure (alloy composition and morphology). The material properties used within specific structural components are also designable in order to meet specific performance requirements that are not imaginable with traditional metal forming and machining (subtractive) techniques.

  5. Metal-Ion Additives Reduce Thermal Expansion Of Polyimides

    NASA Technical Reports Server (NTRS)

    Stoakley, Diane M.; St. Clair, Anne K.; Emerson, Burt R., Jr.; Willis, George L.

    1994-01-01

    Polyimides widely used as high-performance polymers because of their excellent thermal stability and toughness. However, their coefficients of thermal expansion (CTE's) greater than those of metals, ceramics, and glasses. Decreasing CTE's of polyimides increase usefulness for aerospace and electronics applications in which dimensional stability required. Additives containing metal ions reduce coefficients of thermal expansion of polyimides. Reductions range from 11 to over 100 percent.

  6. Chemical enhancement of metallized zinc anode performance

    SciTech Connect

    Bennett, J.

    1998-12-31

    Galvanic current delivered to reinforced concrete by a metallized zinc anode was studied relative to the humidity of its environment and periodic direct wetting. Current decreased quickly at low humidity to values unlikely to meet accepted cathodic protection criteria, but could be easily restored by direct wetting of the anode. Thirteen chemicals were screened for their ability to enhance galvanic current. Such chemicals, when applied to the exterior surface of the anode, are easily transported by capillary action to the anode-concrete interface where they serve to maintain the interface conductive and the zinc electrochemically active. The most effective chemicals were potassium and lithium bromide, acetate, chloride and nitrate, which increased galvanic current by a factor of 2--15, depending on relative humidity and chloride contamination of the concrete. This new technique is expected to greatly expand the number of concrete structures which can be protected by simple galvanic cathodic protection, The use of lithium-based chemicals together with metallized zinc anode is also proposed for mitigation of existing problems due to ASR. In this case, lithium which prevents or inhibits expansion due to ASR can be readily injected into the concrete. A new process, electrochemical maintenance of concrete (EMC), is also proposed to benefit reinforced concrete structures suffering from chloride-induced corrosion.

  7. Partial Exemption of Certain Chemical Substances from Reporting Additional Chemical Data

    EPA Pesticide Factsheets

    This Federal Register notice amends the list of chemical substances that are partially exempt from reporting additional information by adding six chemicals in response to a petition the Agency received.

  8. Low coefficient of thermal expansion polyimides containing metal ion additives

    NASA Technical Reports Server (NTRS)

    Stoakley, D. M.; St. Clair, A. K.

    1992-01-01

    Polyimides have become widely used as high performance polymers as a result of their excellent thermal stability and toughness. However, lowering their coefficient of thermal expansion (CTE) would increase their usefulness for aerospace and electronic applications where dimensional stability is a requirement. The incorporation of metal ion-containing additives into polyimides, resulting in significantly lowered CTE's, has been studied. Various metal ion additives have been added to both polyamic acid resins and soluble polyimide solutions in the concentration range of 4-23 weight percent. The incorporation of these metal ions has resulted in reductions in the CTE's of the control polyimides of 12 percent to over 100 percent depending on the choice of additive and its concentration.

  9. Low coefficient of thermal expansion polyimides containing metal ion additives

    NASA Technical Reports Server (NTRS)

    Stoakley, D. M.; St. Clair, A. K.

    1992-01-01

    Polyimides have become widely used as high performance polymers as a result of their excellent thermal stability and toughness. However, lowering their coefficient of thermal expansion (CTE) would increase their usefulness for aerospace and electronic applications where dimensional stability is a requirement. The incorporation of metal ion-containing additives into polyimides, resulting in significantly lowered CTE's, has been studied. Various metal ion additives have been added to both polyamic acid resins and soluble polyimide solutions in the concentration range of 4-23 weight percent. The incorporation of these metal ions has resulted in reductions in the CTE's of the control polyimides of 12 percent to over 100 percent depending on the choice of additive and its concentration.

  10. The effect of chemical additives on the synthesis of ethanol

    SciTech Connect

    Chuang, S.S.C.

    1990-11-01

    The objective of this research is to elucidate the role of additives on the ethanol synthesis over Rh- and Ni-based catalysts. Chemical additives used for this study will include S, P, Ag, Cu, Mn, and Na which have different electronegativities. The effect of additives on the surface state of the catalysts, heat of adsorption of reactant molecules, reaction intermediates, reaction pathways, reaction kinetics, and product distributions is/will be investigated by a series of experimental studies of NO adsorption, reaction probing, study state rate measurement, and transient kinetic study. A better understanding of the role of additive on the synthesis reaction may allow them to use chemical additives to manipulate the catalytic properties of Rh- and Ni-based catalysts for producing high yields of ethanol from syngas. 49 refs., 6 figs., 3 tabs.

  11. THE USE OF CHEMICALS AS SOIL ADDITIVES. AGRICULTURAL CHEMICALS TECHNOLOGY, NUMBER 3.

    ERIC Educational Resources Information Center

    Ohio State Univ., Columbus. Center for Vocational and Technical Education.

    THE PURPOSE OF THIS GUIDE IS TO ASSIST TEACHERS IN PREPARING POST-SECONDARY STUDENTS FOR AGRICULTURAL CHEMICAL OCCUPATIONS. IT IS ONE OF A SERIES OF MODULES DEVELOPED BY A NATIONAL TASK FORCE ON THE BASIS OF STATE STUDY DATA. SECTIONS ARE (1) PHYSICAL AND CHEMICAL ALTERATION OF SOIL WITH CHEMICAL ADDITIVES, (2) TERMINOLOGY AND COMPUTATIONS, (3)…

  12. Decontamination of metals using chemical etching

    DOEpatents

    Lerch, Ronald E.; Partridge, Jerry A.

    1980-01-01

    The invention relates to chemical etching process for reclaiming contaminated equipment wherein a reduction-oxidation system is included in a solution of nitric acid to contact the metal to be decontaminated and effect reduction of the reduction-oxidation system, and includes disposing a pair of electrodes in the reduced solution to permit passage of an electrical current between said electrodes and effect oxidation of the reduction-oxidation system to thereby regenerate the solution and provide decontaminated equipment that is essentially radioactive contamination-free.

  13. Disclosure of hydraulic fracturing fluid chemical additives: analysis of regulations.

    PubMed

    Maule, Alexis L; Makey, Colleen M; Benson, Eugene B; Burrows, Isaac J; Scammell, Madeleine K

    2013-01-01

    Hydraulic fracturing is used to extract natural gas from shale formations. The process involves injecting into the ground fracturing fluids that contain thousands of gallons of chemical additives. Companies are not mandated by federal regulations to disclose the identities or quantities of chemicals used during hydraulic fracturing operations on private or public lands. States have begun to regulate hydraulic fracturing fluids by mandating chemical disclosure. These laws have shortcomings including nondisclosure of proprietary or "trade secret" mixtures, insufficient penalties for reporting inaccurate or incomplete information, and timelines that allow for after-the-fact reporting. These limitations leave lawmakers, regulators, public safety officers, and the public uninformed and ill-prepared to anticipate and respond to possible environmental and human health hazards associated with hydraulic fracturing fluids. We explore hydraulic fracturing exemptions from federal regulations, as well as current and future efforts to mandate chemical disclosure at the federal and state level.

  14. Porosity Measurements and Analysis for Metal Additive Manufacturing Process Control

    PubMed Central

    Slotwinski, John A; Garboczi, Edward J; Hebenstreit, Keith M

    2014-01-01

    Additive manufacturing techniques can produce complex, high-value metal parts, with potential applications as critical metal components such as those found in aerospace engines and as customized biomedical implants. Material porosity in these parts is undesirable for aerospace parts - since porosity could lead to premature failure - and desirable for some biomedical implants - since surface-breaking pores allows for better integration with biological tissue. Changes in a part’s porosity during an additive manufacturing build may also be an indication of an undesired change in the build process. Here, we present efforts to develop an ultrasonic sensor for monitoring changes in the porosity in metal parts during fabrication on a metal powder bed fusion system. The development of well-characterized reference samples, measurements of the porosity of these samples with multiple techniques, and correlation of ultrasonic measurements with the degree of porosity are presented. A proposed sensor design, measurement strategy, and future experimental plans on a metal powder bed fusion system are also presented. PMID:26601041

  15. Porosity Measurements and Analysis for Metal Additive Manufacturing Process Control.

    PubMed

    Slotwinski, John A; Garboczi, Edward J; Hebenstreit, Keith M

    2014-01-01

    Additive manufacturing techniques can produce complex, high-value metal parts, with potential applications as critical metal components such as those found in aerospace engines and as customized biomedical implants. Material porosity in these parts is undesirable for aerospace parts - since porosity could lead to premature failure - and desirable for some biomedical implants - since surface-breaking pores allows for better integration with biological tissue. Changes in a part's porosity during an additive manufacturing build may also be an indication of an undesired change in the build process. Here, we present efforts to develop an ultrasonic sensor for monitoring changes in the porosity in metal parts during fabrication on a metal powder bed fusion system. The development of well-characterized reference samples, measurements of the porosity of these samples with multiple techniques, and correlation of ultrasonic measurements with the degree of porosity are presented. A proposed sensor design, measurement strategy, and future experimental plans on a metal powder bed fusion system are also presented.

  16. Accelerating Industrial Adoption of Metal Additive Manufacturing Technology

    NASA Astrophysics Data System (ADS)

    Vartanian, Kenneth; McDonald, Tom

    2016-03-01

    While metal additive manufacturing (AM) technology has clear benefits, there are still factors preventing its adoption by industry. These factors include the high cost of metal AM systems, the difficulty for machinists to learn and operate metal AM machines, the long approval process for part qualification/certification, and the need for better process controls; however, the high AM system cost is the main barrier deterring adoption. In this paper, we will discuss an America Makes-funded program to reduce AM system cost by combining metal AM technology with conventional computerized numerical controlled (CNC) machine tools. Information will be provided on how an Optomec-led team retrofitted a legacy CNC vertical mill with laser engineered net shaping (LENS®—LENS is a registered trademark of Sandia National Labs) AM technology, dramatically lowering deployment cost. The upgraded system, dubbed LENS Hybrid Vertical Mill, enables metal additive and subtractive operations to be performed on the same machine tool and even on the same part. Information on the LENS Hybrid system architecture, learnings from initial system deployment and continuing development work will also be provided to help guide further development activities within the materials community.

  17. Characterization of Metal Powders Used for Additive Manufacturing.

    PubMed

    Slotwinski, J A; Garboczi, E J; Stutzman, P E; Ferraris, C F; Watson, S S; Peltz, M A

    2014-01-01

    Additive manufacturing (AM) techniques can produce complex, high-value metal parts, with potential applications as critical parts, such as those found in aerospace components. The production of AM parts with consistent and predictable properties requires input materials (e.g., metal powders) with known and repeatable characteristics, which in turn requires standardized measurement methods for powder properties. First, based on our previous work, we assess the applicability of current standardized methods for powder characterization for metal AM powders. Then we present the results of systematic studies carried out on two different powder materials used for additive manufacturing: stainless steel and cobalt-chrome. The characterization of these powders is important in NIST efforts to develop appropriate measurements and standards for additive materials and to document the property of powders used in a NIST-led additive manufacturing material round robin. An extensive array of characterization techniques was applied to these two powders, in both virgin and recycled states. The physical techniques included laser diffraction particle size analysis, X-ray computed tomography for size and shape analysis, and optical and scanning electron microscopy. Techniques sensitive to structure and chemistry, including X-ray diffraction, energy dispersive analytical X-ray analysis using the X-rays generated during scanning electron microscopy, and X-Ray photoelectron spectroscopy were also employed. The results of these analyses show how virgin powder changes after being exposed to and recycled from one or more Direct Metal Laser Sintering (DMLS) additive manufacturing build cycles. In addition, these findings can give insight into the actual additive manufacturing process.

  18. Characterization of Metal Powders Used for Additive Manufacturing

    PubMed Central

    Slotwinski, JA; Garboczi, EJ; Stutzman, PE; Ferraris, CF; Watson, SS; Peltz, MA

    2014-01-01

    Additive manufacturing (AM) techniques1 can produce complex, high-value metal parts, with potential applications as critical parts, such as those found in aerospace components. The production of AM parts with consistent and predictable properties requires input materials (e.g., metal powders) with known and repeatable characteristics, which in turn requires standardized measurement methods for powder properties. First, based on our previous work, we assess the applicability of current standardized methods for powder characterization for metal AM powders. Then we present the results of systematic studies carried out on two different powder materials used for additive manufacturing: stainless steel and cobalt-chrome. The characterization of these powders is important in NIST efforts to develop appropriate measurements and standards for additive materials and to document the property of powders used in a NIST-led additive manufacturing material round robin. An extensive array of characterization techniques was applied to these two powders, in both virgin and recycled states. The physical techniques included laser diffraction particle size analysis, X-ray computed tomography for size and shape analysis, and optical and scanning electron microscopy. Techniques sensitive to structure and chemistry, including X-ray diffraction, energy dispersive analytical X-ray analysis using the X-rays generated during scanning electron microscopy, and X-Ray photoelectron spectroscopy were also employed. The results of these analyses show how virgin powder changes after being exposed to and recycled from one or more Direct Metal Laser Sintering (DMLS) additive manufacturing build cycles. In addition, these findings can give insight into the actual additive manufacturing process. PMID:26601040

  19. The metallurgy and processing science of metal additive manufacturing

    DOE PAGES

    Sames, William J.; List, III, Frederick Alyious; Pannala, Sreekanth; ...

    2016-03-07

    Here, additive Manufacturing (AM), widely known as 3D printing, is a method of manufacturing that forms parts from powder, wire, or sheets in a process that proceeds layer-by-layer.Many techniques (using many different names) have been developed to accomplish this via melting or solid - state joining. In this review, these techniques for producing metal parts are explored, with a focus on the science of metal AM: processing defects, heat transfer, solidification, solid- state precipitation, mechanical properties, and post-processing metallurgy. The various metal AM techniques are compared, with analysis of the strengths and limitations of each. Few alloys have been developedmore » for commercial production, but recent development efforts are presented as a path for the ongoing development of new materials for AM processes.« less

  20. Developing gradient metal alloys through radial deposition additive manufacturing.

    PubMed

    Hofmann, Douglas C; Roberts, Scott; Otis, Richard; Kolodziejska, Joanna; Dillon, R Peter; Suh, Jong-ook; Shapiro, Andrew A; Liu, Zi-Kui; Borgonia, John-Paul

    2014-06-19

    Interest in additive manufacturing (AM) has dramatically expanded in the last several years, owing to the paradigm shift that the process provides over conventional manufacturing. Although the vast majority of recent work in AM has focused on three-dimensional printing in polymers, AM techniques for fabricating metal alloys have been available for more than a decade. Here, laser deposition (LD) is used to fabricate multifunctional metal alloys that have a strategically graded composition to alter their mechanical and physical properties. Using the technique in combination with rotational deposition enables fabrication of compositional gradients radially from the center of a sample. A roadmap for developing gradient alloys is presented that uses multi-component phase diagrams as maps for composition selection so as to avoid unwanted phases. Practical applications for the new technology are demonstrated in low-coefficient of thermal expansion radially graded metal inserts for carbon-fiber spacecraft panels.

  1. The metallurgy and processing science of metal additive manufacturing

    SciTech Connect

    Sames, William J.; List, III, Frederick Alyious; Pannala, Sreekanth; Dehoff, Ryan R.; Babu, Sudarsanam Suresh

    2016-03-07

    Here, additive Manufacturing (AM), widely known as 3D printing, is a method of manufacturing that forms parts from powder, wire, or sheets in a process that proceeds layer-by-layer.Many techniques (using many different names) have been developed to accomplish this via melting or solid - state joining. In this review, these techniques for producing metal parts are explored, with a focus on the science of metal AM: processing defects, heat transfer, solidification, solid- state precipitation, mechanical properties, and post-processing metallurgy. The various metal AM techniques are compared, with analysis of the strengths and limitations of each. Few alloys have been developed for commercial production, but recent development efforts are presented as a path for the ongoing development of new materials for AM processes.

  2. Developing Gradient Metal Alloys through Radial Deposition Additive Manufacturing

    PubMed Central

    Hofmann, Douglas C.; Roberts, Scott; Otis, Richard; Kolodziejska, Joanna; Dillon, R. Peter; Suh, Jong-ook; Shapiro, Andrew A.; Liu, Zi-Kui; Borgonia, John-Paul

    2014-01-01

    Interest in additive manufacturing (AM) has dramatically expanded in the last several years, owing to the paradigm shift that the process provides over conventional manufacturing. Although the vast majority of recent work in AM has focused on three-dimensional printing in polymers, AM techniques for fabricating metal alloys have been available for more than a decade. Here, laser deposition (LD) is used to fabricate multifunctional metal alloys that have a strategically graded composition to alter their mechanical and physical properties. Using the technique in combination with rotational deposition enables fabrication of compositional gradients radially from the center of a sample. A roadmap for developing gradient alloys is presented that uses multi-component phase diagrams as maps for composition selection so as to avoid unwanted phases. Practical applications for the new technology are demonstrated in low-coefficient of thermal expansion radially graded metal inserts for carbon-fiber spacecraft panels. PMID:24942329

  3. In situ combustion with metallic additives SUPRI TR 87

    SciTech Connect

    Holt, R.J.

    1992-07-01

    In-situ combustion is the most energy efficient of the thermal oil recovery methods. In this process, a portion of a reservoir`s oil is burned in-situ as fuel to drive the recovery process. In light oil reservoirs, too little fuel may be deposited, making sustained combustion difficult. In heavy oil reservoirs, too much fuel may be deposited leading to high air injection requirements and unfavorable economics. This study has been designed to attack these problems. Water soluble metallic additives are investigated as agents to modify fuel deposition and combustion performance. This report describes seven combustion tube runs using two cradle oils and two metallic additives. The oils are 12{degrees} and 34{degrees} API, both from Cymric (California). The metallic additives tested are ionic nitrate (Fe(NO{sub 3}){sub 3}9H{sub 2}O) and zinc nitrate (Zn(NO{sub 3}){sub 2}6H{sub 2}O). Iron and tin additives improved the combustion efficiency in all cases. Fluctuations in the produced gas compositions were observed in all control runs, but nearly disappeared with the iron and tin additives. The combustion front velocities were also increased by iron and tin. Changes were also observed in the apparent hydrogen to carbon (H/C) ratio of the fuel, heat of combustion, air requirements, and amount of fuel deposited. Iron and tin caused increases in fuel concentration while causing a decrease in air requirement. The increase in fuel concentration varied between the oils, however, tin and iron were consistently more effective than zinc. A particularly interesting result occurred with the Cymric light oil. In the control runs, a sustained combustion front was not achieved, while in the iron additive runs, stable, sustained combustion was achieved. Iron and tin salts are suitable additives to increase fuel deposition when that is needed. Additives suitable for use as a fuel reducing agent have not yet been found. 26 refs., 23 figs, 6 tabs.

  4. In situ combustion with metallic additives SUPRI TR 87

    SciTech Connect

    Holt, R.J.

    1992-07-01

    In-situ combustion is the most energy efficient of the thermal oil recovery methods. In this process, a portion of a reservoir's oil is burned in-situ as fuel to drive the recovery process. In light oil reservoirs, too little fuel may be deposited, making sustained combustion difficult. In heavy oil reservoirs, too much fuel may be deposited leading to high air injection requirements and unfavorable economics. This study has been designed to attack these problems. Water soluble metallic additives are investigated as agents to modify fuel deposition and combustion performance. This report describes seven combustion tube runs using two cradle oils and two metallic additives. The oils are 12{degrees} and 34{degrees} API, both from Cymric (California). The metallic additives tested are ionic nitrate (Fe(NO{sub 3}){sub 3}9H{sub 2}O) and zinc nitrate (Zn(NO{sub 3}){sub 2}6H{sub 2}O). Iron and tin additives improved the combustion efficiency in all cases. Fluctuations in the produced gas compositions were observed in all control runs, but nearly disappeared with the iron and tin additives. The combustion front velocities were also increased by iron and tin. Changes were also observed in the apparent hydrogen to carbon (H/C) ratio of the fuel, heat of combustion, air requirements, and amount of fuel deposited. Iron and tin caused increases in fuel concentration while causing a decrease in air requirement. The increase in fuel concentration varied between the oils, however, tin and iron were consistently more effective than zinc. A particularly interesting result occurred with the Cymric light oil. In the control runs, a sustained combustion front was not achieved, while in the iron additive runs, stable, sustained combustion was achieved. Iron and tin salts are suitable additives to increase fuel deposition when that is needed. Additives suitable for use as a fuel reducing agent have not yet been found. 26 refs., 23 figs, 6 tabs.

  5. Aerosol chemical vapor deposition of metal oxide films

    DOEpatents

    Ott, Kevin C.; Kodas, Toivo T.

    1994-01-01

    A process of preparing a film of a multicomponent metal oxide including: forming an aerosol from a solution comprised of a suitable solvent and at least two precursor compounds capable of volatilizing at temperatures lower than the decomposition temperature of said precursor compounds; passing said aerosol in combination with a suitable oxygen-containing carrier gas into a heated zone, said heated zone having a temperature sufficient to evaporate the solvent and volatilize said precursor compounds; and passing said volatilized precursor compounds against the surface of a substrate, said substrate having a sufficient temperature to decompose said volatilized precursor compounds whereby metal atoms contained within said volatilized precursor compounds are deposited as a metal oxide film upon the substrate is disclosed. In addition, a coated article comprising a multicomponent metal oxide film conforming to the surface of a substrate selected from the group consisting of silicon, magnesium oxide, yttrium-stabilized zirconium oxide, sapphire, or lanthanum gallate, said multicomponent metal oxide film characterized as having a substantially uniform thickness upon said FIELD OF THE INVENTION The present invention relates to the field of film coating deposition techniques, and more particularly to the deposition of multicomponent metal oxide films by aerosol chemical vapor deposition. This invention is the result of a contract with the Department of Energy (Contract No. W-7405-ENG-36).

  6. Additives initiate selective production of chemicals from biomass pyrolysis.

    PubMed

    Leng, Shuai; Wang, Xinde; Wang, Lei; Qiu, Huizhe; Zhuang, Guilin; Zhong, Xing; Wang, Jianguo; Ma, Fengyun; Liu, Jingmei; Wang, Qiang

    2014-03-01

    To improve chemicals selectivity under low temperature, a new method that involves the injection of additives into biomass pyrolysis is introduced. This method allows biomass pyrolysis to achieve high selectivity to chemicals under low temperature (300°C), while nothing was obtained in typical pyrolysis under 300°C. However, by using the new method, the first liquid drop emerged at the interval between 140°C and 240°C. Adding methanol to mushroom scrap pyrolysis obtained high selectivity to acetic acid (98.33%), while adding ethyl acetate gained selectivity to methanol (65.77%) in bagasse pyrolysis and to acetone (72.51%) in corncob pyrolysis. Apart from basic chemicals, one high value-added chemical (2,3-dihydrobenzofuran) was also detected, which obtained the highest selectivity (10.33%) in corncob pyrolysis through the addition of ethyl acetate. Comparison of HZSM-5 and CaCO3 catalysis showed that benzene emerged in the liquid because of the larger degree of cracking and hydrodeoxygenation over HZSM-5.

  7. Structural, optical and charge generation properties of chalcostibite and tetrahedrite copper antimony sulfide thin films prepared from metal xanthates† †Electronic supplementary information (ESI) available: Chemical structures of the used metal xanthates, additional XRD, SEM-EDX and UV-vis data. See DOI: 10.1039/c5ta05777a Click here for additional data file.

    PubMed Central

    MacLachlan, Andrew J.; Brown, Michael D.

    2015-01-01

    Herein, we report on a solution based approach for the preparation of thin films of copper antimony sulfide, an emerging absorber material for third generation solar cells. In this work, copper and antimony xanthates are used as precursor materials for the formation of two different copper antimony sulfide phases: chalcostibite (CuSbS2) and tetrahedrite (Cu12Sb4S13). Both phases were thoroughly investigated regarding their structural and optical properties. Moreover, thin films of chalcostibite and tetrahedrite were prepared on mesoporous TiO2 layers and photoinduced charge transfer in these metal sulfide/TiO2 heterojunctions was studied via transient absorption spectroscopy. Photoinduced charge transfer was detected in both the chalcostibite as well as the tetrahedrite sample, which is an essential property in view of applying these materials as light-harvesting agents in semiconductor sensitized solar cells. PMID:27019713

  8. Applications for Gradient Metal Alloys Fabricated Using Additive Manufacturing

    NASA Technical Reports Server (NTRS)

    Hofmann, Douglas C.; Borgonia, John Paul C.; Dillon, Robert P.; Suh, Eric J.; Mulder, jerry L.; Gardner, Paul B.

    2013-01-01

    Recently, additive manufacturing (AM) techniques have been developed that may shift the paradigm of traditional metal production by allowing complex net-shaped hardware to be built up layer-by-layer, rather than being machined from a billet. The AM process is ubiquitous with polymers due to their low melting temperatures, fast curing, and controllable viscosity, and 3D printers are widely available as commercial or consumer products. 3D printing with metals is inherently more complicated than with polymers due to their higher melting temperatures and reactivity with air, particularly when heated or molten. The process generally requires a high-power laser or other focused heat source, like an electron beam, for precise melting and deposition. Several promising metal AM techniques have been developed, including laser deposition (also called laser engineered net shaping or LENS® and laser deposition technology (LDT)), direct metal laser sintering (DMLS), and electron beam free-form (EBF). These machines typically use powders or wire feedstock that are melted and deposited using a laser or electron beam. Complex net-shape parts have been widely demonstrated using these (and other) AM techniques and the process appears to be a promising alternative to machining in some cases. Rather than simply competing with traditional machining for cost and time savings, the true advantage of AM involves the fabrication of hardware that cannot be produced using other techniques. This could include parts with "blind" features (like foams or trusses), parts that are difficult to machine conventionally, or parts made from materials that do not exist in bulk forms. In this work, the inventors identify that several AM techniques can be used to develop metal parts that change composition from one location in the part to another, allowing for complete control over the mechanical or physical properties. This changes the paradigm for conventional metal fabrication, which relies on an

  9. Calculation of laser absorption by metal powders in additive manufacturing.

    PubMed

    Boley, C D; Khairallah, S A; Rubenchik, A M

    2015-03-20

    We have calculated the absorption of laser light by a powder of metal spheres, typical of the powder employed in laser powder-bed fusion additive manufacturing. Using ray-trace simulations, we show that the absorption is significantly larger than its value for normal incidence on a flat surface, due to multiple scattering. We investigate the dependence of absorption on powder content (material, size distribution, and geometry) and on beam size.

  10. Chemical Sensors Based on Metal Oxide Nanostructures

    NASA Technical Reports Server (NTRS)

    Hunter, Gary W.; Xu, Jennifer C.; Evans, Laura J.; VanderWal, Randy L.; Berger, Gordon M.; Kulis, Mike J.; Liu, Chung-Chiun

    2006-01-01

    This paper is an overview of sensor development based on metal oxide nanostructures. While nanostructures such as nanorods show significan t potential as enabling materials for chemical sensors, a number of s ignificant technical challenges remain. The major issues addressed in this work revolve around the ability to make workable sensors. This paper discusses efforts to address three technical barriers related t o the application of nanostructures into sensor systems: 1) Improving contact of the nanostructured materials with electrodes in a microse nsor structure; 2) Controling nanostructure crystallinity to allow co ntrol of the detection mechanism; and 3) Widening the range of gases that can be detected by using different nanostructured materials. It is concluded that while this work demonstrates useful tools for furt her development, these are just the beginning steps towards realizati on of repeatable, controlled sensor systems using oxide based nanostr uctures.

  11. Metal Additive Manufacturing: A Review of Mechanical Properties

    NASA Astrophysics Data System (ADS)

    Lewandowski, John J.; Seifi, Mohsen

    2016-07-01

    This article reviews published data on the mechanical properties of additively manufactured metallic materials. The additive manufacturing techniques utilized to generate samples covered in this review include powder bed fusion (e.g., EBM, SLM, DMLS) and directed energy deposition (e.g., LENS, EBF3). Although only a limited number of metallic alloy systems are currently available for additive manufacturing (e.g., Ti-6Al-4V, TiAl, stainless steel, Inconel 625/718, and Al-Si-10Mg), the bulk of the published mechanical properties information has been generated on Ti-6Al-4V. However, summary tables for published mechanical properties and/or key figures are included for each of the alloys listed above, grouped by the additive technique used to generate the data. Published values for mechanical properties obtained from hardness, tension/compression, fracture toughness, fatigue crack growth, and high cycle fatigue are included for as-built, heat-treated, and/or HIP conditions, when available. The effects of test orientation/build direction on properties, when available, are also provided, along with discussion of the potential source(s) (e.g., texture, microstructure changes, defects) of anisotropy in properties. Recommendations for additional work are also provided.

  12. Cleaning Process Development for Metallic Additively Manufactured Parts

    NASA Technical Reports Server (NTRS)

    Tramel, Terri L.; Welker, Roger; Lowery, Niki; Mitchell, Mark

    2014-01-01

    Additive Manufacturing of metallic components for aerospace applications offers many advantages over traditional manufacturing techniques. As a new technology, many aspects of its widespread utilization remain open to investigation. Among these are the cleaning processes that can be used for post finishing of parts and measurements to verify effectiveness of the cleaning processes. Many cleaning and drying processes and measurement methods that have been used for parts manufactured using conventional techniques are candidates that may be considered for cleaning and verification of additively manufactured parts. Among these are vapor degreasing, ultrasonic immersion and spray cleaning, followed by hot air drying, vacuum baking and solvent displacement drying. Differences in porosity, density, and surface finish of additively manufactured versus conventionally manufactured parts may introduce new considerations in the selection of cleaning and drying processes or the method used to verify their effectiveness. This presentation will review the relative strengths and weaknesses of different candidate cleaning and drying processes as they may apply to additively manufactured metal parts for aerospace applications. An ultrasonic cleaning technique for exploring the cleanability of parts will be presented along with an example using additively manufactured Inconel 718 test specimens to illustrate its use. The data analysis shows that this ultrasonic cleaning approach results in a well-behaved ultrasonic cleaning/extraction behavior. That is, it does not show signs of accelerated cavitation erosion of the base material, which was later confirmed by neutron imaging. In addition, the analysis indicated that complete cleaning would be achieved by ultrasonic immersion cleaning at approximately 5 minutes, which was verified by subsequent cleaning of additional parts.

  13. Complex metallic alloys as new materials for additive manufacturing.

    PubMed

    Kenzari, Samuel; Bonina, David; Marie Dubois, Jean; Fournée, Vincent

    2014-04-01

    Additive manufacturing processes allow freeform fabrication of the physical representation of a three-dimensional computer-aided design (CAD) data model. This area has been expanding rapidly over the last 20 years. It includes several techniques such as selective laser sintering and stereolithography. The range of materials used today is quite restricted while there is a real demand for manufacturing lighter functional parts or parts with improved functional properties. In this article, we summarize recent work performed in this field, introducing new composite materials containing complex metallic alloys. These are mainly Al-based quasicrystalline alloys whose properties differ from those of conventional alloys. The use of these materials allows us to produce light-weight parts consisting of either metal-matrix composites or of polymer-matrix composites with improved properties. Functional parts using these alloys are now commercialized.

  14. Complex metallic alloys as new materials for additive manufacturing

    NASA Astrophysics Data System (ADS)

    Kenzari, Samuel; Bonina, David; Dubois, Jean Marie; Fournée, Vincent

    2014-04-01

    Additive manufacturing processes allow freeform fabrication of the physical representation of a three-dimensional computer-aided design (CAD) data model. This area has been expanding rapidly over the last 20 years. It includes several techniques such as selective laser sintering and stereolithography. The range of materials used today is quite restricted while there is a real demand for manufacturing lighter functional parts or parts with improved functional properties. In this article, we summarize recent work performed in this field, introducing new composite materials containing complex metallic alloys. These are mainly Al-based quasicrystalline alloys whose properties differ from those of conventional alloys. The use of these materials allows us to produce light-weight parts consisting of either metal-matrix composites or of polymer-matrix composites with improved properties. Functional parts using these alloys are now commercialized.

  15. [Chemical hazards induced by heavy metals refining processes].

    PubMed

    Gaweda, Ewa

    2003-01-01

    Processes of refining heavy metals consist in removing impurities, which can be found in metals produced on industrial scale. People involved in heavy metals refining processes are primarily exposed to metals (Pb, Cd, Cu), metalloids (As, Se) and metal compounds. Exposure to dusts (from 2 to 50% SiO2) and sulfuric acid is an additional hazard. The air concentrations of harmful chemical agents at heavy metals refining stations in two Polish Plants are presented. Several tens of workers employed in the processes of copper, lead, nickel sulfate, zinc, cadmium and silver production were examined. Concentrations of Cd, Ni, Se, Cu, Pb, Ag, As and Sb were determined by atomic absorption spectrometry (AAS) with a graphite tube, whereas Fe, ZnO oxide (as Zn), MgO (as Mg) and CaO (as Ca) by AAS with air-acetylene flame, and sulfuric acid by method described in PN-91/Z-04056/02. Lead concentrations in the samples collected in both Plants were often high (significantly exceeding Polish MAC values at some workstations). Arsenic concentrations ranged from very low in all processes in one Plant to very high, exceeding Polish MAC values, at some workstations in the other. In general, air concentrations of other agents were not high (fraction of MAC). The occurrence of antimony and magnesium oxide was not determined. The risk created by metals and metalloids at the workstations in two Plants was diversified. There is no need to determine Sb and MgO in further studies. Lead should be determined at all workstations, other agents can be determined at workstations with concentrations exceeding the determinability of relevant methods.

  16. Chemical composition variations in shielded metal arc welds

    SciTech Connect

    Bracarense, A.Q.; Liu, S. . Center for Welding and Joining Research)

    1993-12-01

    The use of shielded metal arc (SMA) welding can result in chemical composition variations along the weld length. Manganese and silicon, commonly found in low-carbon steel welds, change in composition with weld position. This research was performed to better characterize the composition variations observed in structural steel welds and to understand the controlling factors that determine the extent of these composition changes. Single bead-on-plate and multipass welds were performed and analyzed. Manganese, silicon, and oxygen contents showed significant variation along the weld length. To determine the cause of such composition variations, additional experiments were carried out with the welding arc established between the electrode and a water-cooled copper pipe. The individual metal droplets were collected in water and processed using standard particulate materials processing techniques to remove the slag covering. The droplet size distribution was determined and related to the composition variation and position along the weld length.

  17. Additive Manufacturing of Metal Structures at the Micrometer Scale.

    PubMed

    Hirt, Luca; Reiser, Alain; Spolenak, Ralph; Zambelli, Tomaso

    2017-05-01

    Currently, the focus of additive manufacturing (AM) is shifting from simple prototyping to actual production. One driving factor of this process is the ability of AM to build geometries that are not accessible by subtractive fabrication techniques. While these techniques often call for a geometry that is easiest to manufacture, AM enables the geometry required for best performance to be built by freeing the design process from restrictions imposed by traditional machining. At the micrometer scale, the design limitations of standard fabrication techniques are even more severe. Microscale AM thus holds great potential, as confirmed by the rapid success of commercial micro-stereolithography tools as an enabling technology for a broad range of scientific applications. For metals, however, there is still no established AM solution at small scales. To tackle the limited resolution of standard metal AM methods (a few tens of micrometers at best), various new techniques aimed at the micrometer scale and below are presently under development. Here, we review these recent efforts. Specifically, we feature the techniques of direct ink writing, electrohydrodynamic printing, laser-assisted electrophoretic deposition, laser-induced forward transfer, local electroplating methods, laser-induced photoreduction and focused electron or ion beam induced deposition. Although these methods have proven to facilitate the AM of metals with feature sizes in the range of 0.1-10 µm, they are still in a prototype stage and their potential is not fully explored yet. For instance, comprehensive studies of material availability and material properties are often lacking, yet compulsory for actual applications. We address these items while critically discussing and comparing the potential of current microscale metal AM techniques. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Inhibition of hot salt corrosion by metallic additives

    NASA Technical Reports Server (NTRS)

    Deadmore, D. L.; Lowell, C. E.

    1978-01-01

    The effectiveness of several potential fuel additives in reducing the effects of sodium sulfate-induced hot corrosion was evaluated in a cyclic Mach 0.3 burner rig. The potential inhibitors examined were salts of Al, Si, Cr, Fe, Zn, Mg, Ca, and Ba. The alloys tested were IN-100, U-700, IN-738, IN-792, Mar M-509, and 304 stainless steel. Each alloy was exposed for 100 cycles of 1 hour each at 900 C in combustion gases doped with the corrodant and inhibitor salts and the extent of attack was determined by measuring maximum metal thickness loss. The most effective and consistent inhibitor additive was Ba (NO3)2 which reduced the hot corrosion attack to nearly that of simple oxidation.

  19. Targeted Structural Optimization with Additive Manufacturing of Metals

    NASA Technical Reports Server (NTRS)

    Burt, Adam; Hull, Patrick

    2015-01-01

    The recent advances in additive manufacturing (AM) of metals have now improved the state-of-the-art such that traditionally non-producible parts can be readily produced in a cost-effective way. Because of these advances in manufacturing technology, structural optimization techniques are well positioned to supplement and advance this new technology. The goal of this project is to develop a structural design, analysis, and optimization framework combined with AM to significantly light-weight the interior of metallic structures while maintaining the selected structural properties of the original solid. This is a new state-of-the-art capability to significantly reduce mass, while maintaining the structural integrity of the original design, something that can only be done with AM. In addition, this framework will couple the design, analysis, and fabrication process, meaning that what has been designed directly represents the produced part, thus closing the loop on the design cycle and removing human iteration between design and fabrication. This fundamental concept has applications from light-weighting launch vehicle components to in situ resource fabrication.

  20. Simulation of metal additive manufacturing microstructures using kinetic Monte Carlo

    DOE PAGES

    Rodgers, Theron M.; Madison, Jonathan D.; Tikare, Veena

    2017-04-19

    Additive manufacturing (AM) is of tremendous interest given its ability to realize complex, non-traditional geometries in engineered structural materials. But, microstructures generated from AM processes can be equally, if not more, complex than their conventionally processed counterparts. While some microstructural features observed in AM may also occur in more traditional solidification processes, the introduction of spatially and temporally mobile heat sources can result in significant microstructural heterogeneity. While grain size and shape in metal AM structures are understood to be highly dependent on both local and global temperature profiles, the exact form of this relation is not well understood. Wemore » implement an idealized molten zone and temperature-dependent grain boundary mobility in a kinetic Monte Carlo model to predict three-dimensional grain structure in additively manufactured metals. In order to demonstrate the flexibility of the model, synthetic microstructures are generated under conditions mimicking relatively diverse experimental results present in the literature. Simulated microstructures are then qualitatively and quantitatively compared to their experimental complements and are shown to be in good agreement.« less

  1. TSCA Chemical Data Reporting Fact Sheet: Reporting Manufactured Chemical Substances from Metal Mining and Related Activities

    EPA Pesticide Factsheets

    This fact sheet provides guidance on the Chemical Data Reporting (CDR) rule requirements related to the reporting of mined metals, intermediates, and byproducts manufactured during metal mining and related activities.

  2. Metal-assisted chemical etching of silicon: a review.

    PubMed

    Huang, Zhipeng; Geyer, Nadine; Werner, Peter; de Boor, Johannes; Gösele, Ulrich

    2011-01-11

    This article presents an overview of the essential aspects in the fabrication of silicon and some silicon/germanium nanostructures by metal-assisted chemical etching. First, the basic process and mechanism of metal-assisted chemical etching is introduced. Then, the various influences of the noble metal, the etchant, temperature, illumination, and intrinsic properties of the silicon substrate (e.g., orientation, doping type, doping level) are presented. The anisotropic and the isotropic etching behaviors of silicon under various conditions are presented. Template-based metal-assisted chemical etching methods are introduced, including templates based on nanosphere lithography, anodic aluminum oxide masks, interference lithography, and block-copolymer masks. The metal-assisted chemical etching of other semiconductors is also introduced. A brief introduction to the application of Si nanostructures obtained by metal-assisted chemical etching is given, demonstrating the promising potential applications of metal-assisted chemical etching. Finally, some open questions in the understanding of metal-assisted chemical etching are compiled.

  3. Metal reduction at bulk chemical filtration

    NASA Astrophysics Data System (ADS)

    Umeda, Toru; Daikoku, Shusaku; Tsuzuki, Shuichi; Murakami, Tetsuya

    2017-03-01

    OK73 thinner and cyclohexanone, both of which were spiked with metals were passed through Nylon 6,6 filter, varying flow rate, which include the conditions of both point-of-use and bulk filtrations. The influent and effluent metal concentrations were measured using ICP-MS for metal removal efficiency of the filtration. As a result, removal efficiency for some metals descended depending on the flow rate, while others maintained. Slower flow rate is recommended to maintain low metal concentration in bulk filtration based on the result. Metals in cyclohexanone were reduced at higher efficiency than in OK73 thinner, agrees with a metal removal model of hydrophilic adsorbent in organic solvent, evidenced in our previous paper. Further, metal reduction on 300 mm φ Si wafer after coating organic solvents with Nylon 6,6 filtration was evidenced with TREX analysis.

  4. Additives

    NASA Technical Reports Server (NTRS)

    Smalheer, C. V.

    1973-01-01

    The chemistry of lubricant additives is discussed to show what the additives are chemically and what functions they perform in the lubrication of various kinds of equipment. Current theories regarding the mode of action of lubricant additives are presented. The additive groups discussed include the following: (1) detergents and dispersants, (2) corrosion inhibitors, (3) antioxidants, (4) viscosity index improvers, (5) pour point depressants, and (6) antifouling agents.

  5. Additives

    NASA Technical Reports Server (NTRS)

    Smalheer, C. V.

    1973-01-01

    The chemistry of lubricant additives is discussed to show what the additives are chemically and what functions they perform in the lubrication of various kinds of equipment. Current theories regarding the mode of action of lubricant additives are presented. The additive groups discussed include the following: (1) detergents and dispersants, (2) corrosion inhibitors, (3) antioxidants, (4) viscosity index improvers, (5) pour point depressants, and (6) antifouling agents.

  6. Metal ion adsorption to complexes of humic acid and metal oxides: Deviations from the additivity rule

    SciTech Connect

    Vermeer, A.W.P.; McCulloch, J.K.; Van Riemsdijk, W.H.; Koopal, L.K.

    1999-11-01

    The adsorption of cadmium ions to a mixture of Aldrich humic acid and hematite is investigated. The actual adsorption to the humic acid-hematite complex is compared with the sum of the cadmium ion adsorptivities to each of the isolated components. It is shown that the sum of the cadmium ion adsorptivities is not equal to the adsorption to the complex. In general, the adsorption of a specific metal ion to the complex can be understood and qualitatively predicted using the adsorptivities to each of the pure components and taking into account the effect of the pH on the interaction between humic acid and iron oxide on the metal ion adsorption. Due to the interaction between the negatively charged humic acid and the positively charged iron oxide, the adsorption of metal ions on the mineral oxide in the complex will increase as compared to that on the isolated oxide, whereas the adsorption to the humic acid will decrease as compared to that on the isolated humic acid. As a result, the overall adsorption of a specific metal ion to the complex will be smaller than predicted by the additivity rule when this metal ion has a more pronounced affinity for the humic acid than for the mineral oxide, whereas it will be larger than predicted by the additivity rule when the metal ion has a higher affinity for the oxide than for the humic acid.

  7. Metal Big Area Additive Manufacturing: Process Modeling and Validation

    SciTech Connect

    Simunovic, Srdjan; Nycz, Andrzej; Noakes, Mark W; Chin, Charlie; Oancea, Victor

    2017-01-01

    Metal Big Area Additive Manufacturing (mBAAM) is a new additive manufacturing (AM) technology for printing large-scale 3D objects. mBAAM is based on the gas metal arc welding process and uses a continuous feed of welding wire to manufacture an object. An electric arc forms between the wire and the substrate, which melts the wire and deposits a bead of molten metal along the predetermined path. In general, the welding process parameters and local conditions determine the shape of the deposited bead. The sequence of the bead deposition and the corresponding thermal history of the manufactured object determine the long range effects, such as thermal-induced distortions and residual stresses. Therefore, the resulting performance or final properties of the manufactured object are dependent on its geometry and the deposition path, in addition to depending on the basic welding process parameters. Physical testing is critical for gaining the necessary knowledge for quality prints, but traversing the process parameter space in order to develop an optimized build strategy for each new design is impractical by pure experimental means. Computational modeling and optimization may accelerate development of a build process strategy and saves time and resources. Because computational modeling provides these opportunities, we have developed a physics-based Finite Element Method (FEM) simulation framework and numerical models to support the mBAAM process s development and design. In this paper, we performed a sequentially coupled heat transfer and stress analysis for predicting the final deformation of a small rectangular structure printed using the mild steel welding wire. Using the new simulation technologies, material was progressively added into the FEM simulation as the arc weld traversed the build path. In the sequentially coupled heat transfer and stress analysis, the heat transfer was performed to calculate the temperature evolution, which was used in a stress analysis to

  8. Complex metallic alloys as new materials for additive manufacturing

    PubMed Central

    Kenzari, Samuel; Bonina, David; Marie Dubois, Jean; Fournée, Vincent

    2014-01-01

    Additive manufacturing processes allow freeform fabrication of the physical representation of a three-dimensional computer-aided design (CAD) data model. This area has been expanding rapidly over the last 20 years. It includes several techniques such as selective laser sintering and stereolithography. The range of materials used today is quite restricted while there is a real demand for manufacturing lighter functional parts or parts with improved functional properties. In this article, we summarize recent work performed in this field, introducing new composite materials containing complex metallic alloys. These are mainly Al-based quasicrystalline alloys whose properties differ from those of conventional alloys. The use of these materials allows us to produce light-weight parts consisting of either metal–matrix composites or of polymer–matrix composites with improved properties. Functional parts using these alloys are now commercialized. PMID:27877661

  9. Chemical Abstracts Service Chemical Registry System. 11. Substance-related statistics: update and additions.

    PubMed

    Stobaugh, R E

    1988-11-01

    Statistics are updated for types of substances, ring systems, and elemental composition that have been determined for the Chemical Abstracts Service Registry Structure File at different points in time. This paper reports the updated figures and in addition some new statistics and offers some comparisons to show various shifts in file characteristics.

  10. Non-essential metals in chemical biology.

    PubMed

    Dyson, Paul J

    2011-01-01

    Metal ions and compounds are essential to life and many people routinely take them as food supplements in the form of vitamin and mineral pills. Most non-essential metals are considered to be toxic, nevertheless, many are widely used in imaging, diagnostics and medicine. This short review provides an overview from selected examples of the on-going research within my laboratory that uses metal compounds to either understand biological processes or that exhibit therapeutic properties overcoming the limitations of existing chemotherapies.

  11. Metallic Taste from Electrical and Chemical Stimulation

    PubMed Central

    Lawless, Harry T.; Stevens, David A.; Chapman, Kathryn W.; Kurtz, Anne

    2005-01-01

    A series of three experiments investigated the nature of metallic taste reports after stimulation with solutions of metal salts and after stimulation with metals and electric currents. To stimulate with electricity, a device was fabricated consisting of a small battery affixed to a plastic handle with the anode side exposed for placement on the tongue or oral tissues. Intensity of taste from metals and batteries was dependent upon the voltage and was more robust in areas dense in fungiform papillae. Metallic taste was reported from stimulation with ferrous sulfate solutions, from metals and from electric stimuli. However, reports of metallic taste were more frequent when the word ‘metallic’ was presented embedded in a list of choices, as opposed to simple free-choice labeling. Intensity decreased for ferrous sulfate when the nose was occluded, consistent with a decrease in retronasal smell, as previously reported. Intensity of taste evoked by copper metal, bimetallic stimuli (zinc/copper) or small batteries (1.5-3 V) was not affected by nasal occlusion. This difference suggests two distinct mechanisms for evocation of metallic taste reports, one dependent upon retronasal smell and a second mediated by oral chemoreceptors. PMID:15741603

  12. Chemically Modified Metal Oxide Nanostructure for Photoelectrochemical Water Splitting

    NASA Astrophysics Data System (ADS)

    Wang, Gongming

    Hydrogen gas is chemical fuel with high energy density, and represents a clean, renewable and carbon-free burning fuel, which has the potential to solve the more and more urgent energy crisis in today's society. Inspired by natural photosynthesis, artificial photosynthesis to generate hydrogen energy has attracted a lot of attentions in the field of chemistry, physics and material. Photoelectrochemical water splitting based on semiconductors represents a green and low cost method to generate hydrogen fuel. However, the current overall efficiency of solar to hydrogen is quite low, due to some intrinsic limitations such as bandgap, diffusion distance, carrier lifetime and photostability of semiconductors. Although nanostructured semiconductors can improve their photoelectrochemical water splitting performance to some extent, by increasing electrolyte accessible area and shortening minority carrier diffusion distance, nanostructure engineering cannot change their intrinsic electronic properties. Recent development in chemically modified nanostructures such as surface catalyst decoration, element doping, plasmonic modification and interfacial hetero-junction design have led to significant advancement in the photoelectrochemical water splitting, by improving surface reaction kinetics and charge separation, transportation and collection efficiency. In this thesis, I will give a detailed discussion on the chemically modified metal oxide nanostructures for photoelectrocemical hydrogen generation, with a focus on the element doping, hydrogen treatment and catalyst modification. I have demonstrated nitrogen doping on ZnO and Ti doping on hematite can improve their photoelectrochemical performance. In addition, we found hydrogen treatment is a general and effective method to improve the photocatalytic performance, by increasing their carrier desities. Hydrogen treatment has been demonstrated on TiO2, WO3 and BiVO4. In the end, we also used electrochemical catalyt to modify

  13. NMR characterization of cellulose acetate: chemical shift assignments, substituent effects, and chemical shift additivity.

    PubMed

    Kono, Hiroyuki; Hashimoto, Hisaho; Shimizu, Yuuichi

    2015-03-15

    A series of cellulose acetates (CA) with degrees of substitution (DS) ranging from 2.92-0.92 dissolved in dimethylsulfoxide (DMSO)-d6 and cellulose dissolved in tetrabutylammonium fluoride (TBAF)/DMSO-d6 were investigated by two-dimensional NMR spectroscopy. The NMR spectroscopic analysis allowed the determination of the (1)H and (13)C NMR chemical shifts of the eight anhydroglucose units (AGUs) that contain CA: 2,3,6-tri-, 2,3-di-, 2,6-di-, 3,6-di-, 2-mono-, 3-mono-, 6-mono-, and unacetylated AGUs. A comparative analysis of the chemical shift data revealed the substituent effect of acetyl groups at the 2-, 3-, and 6-positions on the (1)H and (13)C nuclei in the same AGU. In addition, chemical shift additivity could be applied to the (1)H and (13)C chemical shifts of CA because the chemical shifts of the diacetylated and triacetylated AGUs could be almost completely explained by the acetyl substituent effects at the 2-, 3-, and 6-positions.

  14. AFCATT (Anti-Fouling Chemical Additive Test Tower)

    SciTech Connect

    Philpot, E.F.; Newton, M.T.; Noble, R.T.

    1995-06-01

    Polyvinylchloride (PVC) film-type cellular fill is the fill of choice in replacing cement asbestos board fill in existing cooling towers and in new cooling towers because of its high thermal performance, ease of installation, and low initial cost. However, PVC fill has been found to foul quickly with biological and sediment material, significantly reducing tower performance and the fill`s useful life. The Anti-Fouling Chemical Additives Test Tower (AFCATT) has been build to study accumulation rates of fouling deposits in corrugated PVC film fill and to study methods of cleaning and preventing the fouling deposits. This small mechanical draft cooling tower is located next to the Unit 4 natural draft cooling tower at Georgia Power Company`s Plant Bowen. The once-through mechanical draft tower receives hot water from the condenser and returns the cold water to the basin of the host tower. The pilot tower is divided into four chambers allowing for three different treatment programs and one control to be run simultaneously. PVC fill packs are suspended from load cells to allow the weight of the fill packs to be measured continuously. Six vendors participated in the summer 1993 test program. Each proposed different methods of cleaning the fouled fill and were given the opportunity to try their proposed method of fill cleaning. To determine the success of these different treatment programs, statistical analyses were performed on the collected data and the changes in the accumulation rates compared.

  15. Complexed metals in hazardous waste: Limitations of conventional chemical oxidation

    SciTech Connect

    Diel, B.N.; Kuchynka, D.J.; Borchert, J.

    1994-12-31

    In the management of hazardous waste, more is known regarding the treatment of metals than about the fixation, destruction and/or immobilization of any other hazardous constituent group. Metals are the only hazardous constituents which cannot be destroyed, and so must be converted to their least soluble and/or reactive form to prevent reentry into the environment. The occurrence of complexed metals, e.g., metallocyanides, and/or chelated metals, e.g., M{center_dot}EDTA in hazardous waste streams presents formidable challenges to conventional waste treatment practices. This paper presents the results of extensive research into the destruction (chemical oxidation) of metallocyanides and metal-chelates, defines the utility and limitations of conventional chemical oxidation approaches, illustrates some of the waste management difficulties presented by such species, and presents preliminary data on the UV/H{sub 2}O{sub 2} photodecomposition of chelated metals.

  16. Electronic and chemical structure of metal-silicon interfaces

    NASA Technical Reports Server (NTRS)

    Grunthaner, P. J.; Grunthaner, F. J.

    1984-01-01

    This paper reviews our current understanding of the near-noble metal silicides and the interfaces formed with Si(100). Using X-ray photoemission spectroscopy, we compare the chemical composition and electronic structure of the room temperature metal-silicon and reacted silicide-silicon interfaces. The relationship between the interfacial chemistry and the Schottky barrier heights for this class of metals on silicon is explored.

  17. Flow characteristics of metallic powder grains for additive manufacturing

    NASA Astrophysics Data System (ADS)

    Peters, Bernhard; Pozzetti, Gabriele

    2017-06-01

    Directed energy deposition technologies for additive manufacturing such as laser selective melting (SLM) or electron beam melting (EBM) is a fast growing technique mainly due to its flexibility in product design. However, the process is a complex interaction of multi-physics on multiple length scales that are still not entirely understood. A particular challenging task are the flow characteristics of metallic powder ejected as jets from a nozzle and shielded by an inert turbulent gas flow. Therefore, the objective is to describe numerically the complex interaction between turbulent flow and powder grains. In order to include both several physical processes and length scales an Euler-Lagrange technology is applied. Within this framework powder is treated by the Discrete-Element-Method, while gas flow is described by Euler approaches as found in classical Computational Fluid Dynamics (CFD). The described method succeeded in delivering more accuracy and consistency than a standard approach based on the volume averaging technique and therefore, is suited for the solution of problems within an engineering framework.

  18. Laser-shocked energetic materials with metal additives: evaluation of chemistry and detonation performance.

    PubMed

    Gottfried, Jennifer L; Bukowski, Eric J

    2017-01-20

    A focused, nanosecond-pulsed laser has been used to ablate, atomize, ionize, and excite milligram quantities of metal-doped energetic materials that undergo exothermic reactions in the laser-induced plasma. The subsequent shock wave expansion in the air above the sample has been monitored using high-speed schlieren imaging in a recently developed technique, laser-induced air shock from energetic materials (LASEM). The method enables the estimation of detonation velocities based on the measured laser-induced air-shock velocities and has previously been demonstrated for organic military explosives. Here, the LASEM technique has been extended to explosive formulations with metal additives. A comparison of the measured laser-induced air-shock velocities for TNT, RDX, DNTF, and LLM-172 doped with Al or B to the detonation velocities predicted by the thermochemical code CHEETAH for inert or active metal participation demonstrates that LASEM has potential for predicting the early time (<10  μs) participation of metal additives in detonation events. The LASEM results show that while Al is mostly inert at early times in the detonation event (confirmed from large-scale detonation testing), B is active-and reducing the amount of hydrogen present during the early chemical reactions increases the resulting estimated detonation velocities.

  19. Workshop Report on Additive Manufacturing for Large-Scale Metal Components - Development and Deployment of Metal Big-Area-Additive-Manufacturing (Large-Scale Metals AM) System

    SciTech Connect

    Babu, Sudarsanam Suresh; Love, Lonnie J.; Peter, William H.; Dehoff, Ryan

    2016-05-01

    Additive manufacturing (AM) is considered an emerging technology that is expected to transform the way industry can make low-volume, high value complex structures. This disruptive technology promises to replace legacy manufacturing methods for the fabrication of existing components in addition to bringing new innovation for new components with increased functional and mechanical properties. This report outlines the outcome of a workshop on large-scale metal additive manufacturing held at Oak Ridge National Laboratory (ORNL) on March 11, 2016. The charter for the workshop was outlined by the Department of Energy (DOE) Advanced Manufacturing Office program manager. The status and impact of the Big Area Additive Manufacturing (BAAM) for polymer matrix composites was presented as the background motivation for the workshop. Following, the extension of underlying technology to low-cost metals was proposed with the following goals: (i) High deposition rates (approaching 100 lbs/h); (ii) Low cost (<$10/lbs) for steel, iron, aluminum, nickel, as well as, higher cost titanium, (iii) large components (major axis greater than 6 ft) and (iv) compliance of property requirements. The above concept was discussed in depth by representatives from different industrial sectors including welding, metal fabrication machinery, energy, construction, aerospace and heavy manufacturing. In addition, DOE’s newly launched High Performance Computing for Manufacturing (HPC4MFG) program was reviewed. This program will apply thermo-mechanical models to elucidate deeper understanding of the interactions between design, process, and materials during additive manufacturing. Following these presentations, all the attendees took part in a brainstorming session where everyone identified the top 10 challenges in large-scale metal AM from their own perspective. The feedback was analyzed and grouped in different categories including, (i) CAD to PART software, (ii) selection of energy source, (iii

  20. Hematite Surface Activation by Chemical Addition of Tin Oxide Layer.

    PubMed

    Carvalho, Waldemir M; Souza, Flavio L

    2016-09-05

    In this study, the effect of tin (Sn(4+) ) modification on the surface of hematite electrodes synthesized by an aqueous solution route at different times (2, 5, 10, 18, and 24 h) is investigated. As confirmed from X-ray diffraction results, the as-synthesized electrode exhibits an oxyhydroxide phase, which is converted into a pure hematite phase after being subjected to additional thermal treatment at 750 °C for 30 min. The tin-modified hematite electrode is prepared by depositing a solution of Sn(4+) precursor on the as-synthesized electrode, followed by thermal treatment under the same abovementioned conditions. This modification results in an enhancement of the photocurrent response for all hematite electrodes investigated and attains the highest values of around 1.62 and 2.3 mA cm(-2) at 1.23 and 1.4 V versus RHE, respectively, for electrodes obtained in short synthesis times (2 h). Contact angle measurements suggest that the deposition of Sn(4+) on the hematite electrode provides a more hydrophilic surface, which favors a chemical reaction at the interface between the electrode and electrolyte. This result generates new perspectives for understanding the deposition of Sn(4+) on the hematite electrode surface, which is in contrast with several studies previously reported; these studies state that the enhancement in photocurrent density is related to either the induction of an increased donor charge density or shift in the flat-band potential, which favors charge separation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Additive Manufacturing of Functional Elements on Sheet Metal

    NASA Astrophysics Data System (ADS)

    Schaub, Adam; Ahuja, Bhrigu; Butzhammer, Lorenz; Osterziel, Johannes; Schmidt, Michael; Merklein, Marion

    Laser Beam Melting (LBM) process with its advantages of high design flexibility and free form manufacturing methodology is often applied limitedly due to its low productivity and unsuitability for mass production compared to conventional manufacturing processes. In order to overcome these limitations, a hybrid manufacturing methodology is developed combining the additive manufacturing process of laser beam melting with sheet forming processes. With an interest towards aerospace and medical industry, the material in focus is Ti-6Al-4V. Although Ti-6Al-4V is a commercially established material and its application for LBM process has been extensively investigated, the combination of LBM of Ti-6Al-4V with sheet metal still needs to be researched. Process dynamics such as high temperature gradients and thermally induced stresses lead to complex stress states at the interaction zone between the sheet and LBM structure. Within the presented paper mechanical characterization of hybrid parts will be performed by shear testing. The association of shear strength with process parameters is further investigated by analyzing the internal structure of the hybrid geometry at varying energy inputs during the LBM process. In order to compare the hybrid manufacturing methodology with conventional fabrication, the conventional methodologies subtractive machining and state of the art Laser Beam Melting is evaluated within this work. These processes will be analyzed for their mechanical characteristics and productivity by determining the build time and raw material consumption for each case. The paper is concluded by presenting the characteristics of the hybrid manufacturing methodology compared to alternative manufacturing technologies.

  2. Chemical characterization and metal abundance in Sri Lankan serpentine soils

    NASA Astrophysics Data System (ADS)

    Vithanage, M. S.; Rajapaksha, A. U.; Ok, Y. S.; Oze, C.

    2012-12-01

    Chemical weathering of ultramafic rocks and their related soils provide localized sources of metal contamination. In Sri Lanka, rural communities live in close proximity to these rocks and soils and utilize associated groundwaters where human intake of these high metal sources may have adverse human health effects. This study investigates metal abundances and variations in Sri Lankan serpentine soils to begin evaluating potential human health hazards. Specifically, we examine serpentinite occurrences at Ussangoda, Wasgamuwa, Ginigalpelessa, and Indikolapelessa located at the geological boundary between the Highland and Vijayan Complexes. The pH of the soils are near neutral (6.26 to 7.69) with soil electrical conductivities (EC) ranging from 33.5 to 129.9 μS cm-1, a range indicative of relatively few dissolved salts and/or major dissolved inorganic solutes. The highest EC is from the Ussangoda soil which may be due to the atmospheric deposition of salt spray from the sea. Organic carbon contents of the soils range from 1.09% to 2.58%. The highest organic carbon percentage is from the Wasgamuwa soil which is located in a protected preserve. X-ray fluorescence (XRF) spectrometry and total metal digestion results show that all serpentine soils are Fe-, Cr-, and Ni-rich with abundant aluminosilicate minerals. Nickel is highest in the Ussangoda soil (6,459 mg kg-1), while Cr (>10,000 mg kg-1), Co (441 mg kg-1) and Mn (2,263 mg kg-1) are highest in the Wasgamuwa serpentine soil. Additionally, Mn (2,200 mg kg-1) and Co (400 mg kg-1) are present at high concentrations in the Wasgamuwa and Ginigalpelessa soils respectively. Electron microprobe mapping demonstrates that these heavy metals are not homogeneously distributed where Cr is specifically associated with Al and Fe phases. Metal speciation of these serpentine soils are currently being investigated using X-ray absorption spectroscopy (XAS) to provide better constraints with regards to their mobility and toxicity.

  3. Heavy metal pollutants and chemical ecology: exploring new frontiers.

    PubMed

    Boyd, Robert S

    2010-01-01

    Heavy metals are an important class of pollutants with both lethal and sublethal effects on organisms. The latter are receiving increased attention, as these may have harmful ecological outcomes. For example, recent explorations of heavy metals in freshwater habitats reveal that they can modify chemical communication between individuals, resulting in "info-disruption" that can impact ecological relationships within and between species. Info-disruption can affect animal behavior and social structure, which in turn can modify both intraspecies and interspecies interactions. In terrestrial habitats, info-disruption by metals is not well studied, but recent demonstrations of chemical signaling between plants via both roots and volatile organic molecules provide potential opportunities for info-disruption. Metals in terrestrial habitats also can form elemental plant defenses, in which they can defend a plant against natural enemies. For example, hyperaccumulation of metals by terrestrial plants has been shown to provide defensive benefits, although in almost all known cases the metals are not anthropogenic pollutants but are naturally present in soils inhabited by these plants. Info-disruption among microbes is another arena in which metal pollutants may have ecological effects, as recent discoveries regarding quorum sensing in bacteria provide an avenue for metals to affect interactions among bacteria or between bacteria and other organisms. Metal pollutants also may influence immune responses of organisms, and thus affect pathogen/host relationships. Immunomodulation (modification of immune system function) has been tied to some metal pollutants, although specific metals may boost or reduce immune system function depending on dose. Finally, the study of metal pollutants is complicated by their frequent occurrence as mixtures, either with other metals or with organic pollutants. Most studies of metal pollutants focus on single metals and therefore oversimplify complex

  4. 15 CFR 714.3 - Advance declaration requirements for additionally planned production of Schedule 3 chemicals.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... additionally planned production of Schedule 3 chemicals. 714.3 Section 714.3 Commerce and Foreign Trade... COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 3 CHEMICALS § 714.3 Advance declaration requirements for additionally planned production of Schedule 3 chemicals. (a)...

  5. Metal nano-film resistivity chemical sensor.

    PubMed

    Podešva, Pavel; Foret, František

    2016-02-01

    In this work, we present a study on reusable thin metal film resistivity-based sensor for direct measurement of binding of thiol containing molecules in liquid samples. While in bulk conductors the DC current is not influenced by the surface events to a measureable degree in a thin metal layer the electrons close to the surface conduct a significant part of electricity and are influenced by the surface interactions. In this study, the thickness of the gold layer was kept below 100 nm resulting in easily measureable resistivity changes of the metal element upon a surface SH-groups binding. No further surface modifications were necessary. Thin film gold layers deposited on a glass substrate by vacuum sputtering were photolithographically structured into four sensing elements arranged in a Wheatstone bridge to compensate for resistance fluctuations due to the temperature changes. Concentrations as low 100 pM provided measureable signals. The surface after the measurement could be electrolytically regenerated for next measurements. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. An effects addition model based on bioaccumulation of metals from exposure to mixtures of metals can predict chronic mortality in the aquatic invertebrate Hyalella azteca.

    PubMed

    Norwood, Warren P; Borgmann, Uwe; Dixon, D George

    2013-07-01

    Chronic toxicity tests of mixtures of 9 metals and 1 metalloid (As, Cd, Co, Cr, Cu, Mn, Ni, Pb, Tl, and Zn) at equitoxic concentrations over an increasing concentration range were conducted with the epibenthic, freshwater amphipod Hyalella azteca. The authors conducted 28-d, water-only tests. The bioaccumulation trends changed for 8 of the elements in exposures to mixtures of the metals compared with individual metal exposures. The bioaccumulation of Co and Tl were affected the most. These changes may be due to interactions between all the metals as well as interactions with waterborne ligands. A metal effects addition model (MEAM) is proposed as a more accurate method to assess the impact of mixtures of metals and to predict chronic mortality. The MEAM uses background-corrected body concentration to predict toxicity. This is important because the chemical characteristics of different waters can greatly alter the bioavailability and bioaccumulation of metals, and interactions among metals for binding at the site of action within the organism can affect body concentration. The MEAM accurately predicted toxicity in exposures to mixtures of metals, and predicted results were within a factor of 1.1 of the observed data, using 24-h depurated body concentrations. The traditional concentration addition model overestimated toxicity by a factor of 2.7.

  7. Chemical Reactivity Perspective into the Group 2B Metals Halides.

    PubMed

    Özen, Alimet Sema; Akdeniz, Zehra

    2016-06-30

    Chemical reactivity descriptors within the conceptual density functional theory can be used to understand the nature of the interactions between two monomers of the Group 2B metal halides. This information might be valuable in the development of adequate force law parameters for simulations in the liquid state. In this study, MX2 monomers and dimers, where M = Zn, Cd, Hg and X = F, Cl, Br, I, were investigated in terms of chemical reactivity descriptors. Relativistic effects were taken into account using the effective core potential (ECP) approach. Correlations were produced between global and local reactivity descriptors and dimerization energies. Results presented in this work represent the first systematic investigation of Group 2B metal halides in the literature from a combined point of view of both relativistic effects and chemical reactivity descriptors. Steric effects were found to be responsible for the deviation from the chemical reactivity principles. They were introduced into the chemical reactivity descriptors such as local softness.

  8. Systems and Methods for Fabricating Objects Including Amorphous Metal Using Techniques Akin to Additive Manufacturing

    NASA Technical Reports Server (NTRS)

    Hofmann, Douglas (Inventor)

    2017-01-01

    Systems and methods in accordance with embodiments of the invention fabricate objects including amorphous metals using techniques akin to additive manufacturing. In one embodiment, a method of fabricating an object that includes an amorphous metal includes: applying a first layer of molten metallic alloy to a surface; cooling the first layer of molten metallic alloy such that it solidifies and thereby forms a first layer including amorphous metal; subsequently applying at least one layer of molten metallic alloy onto a layer including amorphous metal; cooling each subsequently applied layer of molten metallic alloy such that it solidifies and thereby forms a layer including amorphous metal prior to the application of any adjacent layer of molten metallic alloy; where the aggregate of the solidified layers including amorphous metal forms a desired shape in the object to be fabricated; and removing at least the first layer including amorphous metal from the surface.

  9. Contamination and galvanic corrosion in metal chemical-mechanical planarization

    NASA Astrophysics Data System (ADS)

    Zhang, Liming

    Chemical mechanical planarization (CMP) of metals is a critical process in the manufacturing of ultra-large scale integrated (ULSI) circuit devices. The overall success of a CMP process requires minimal particulate and metallic contamination of the structures subjected to CMP. The objective of this study was to investigate alumina particle contamination during tungsten CMP, copper contamination in copper CMP, and galvanic corrosion between metal films and adhesion layers during the final stages of tungsten and copper CMP. Particular attention was paid to the use of short chain organic carboxylic acids in reducing the contamination. Both electrokinetic and uptake measurements showed that citric acid and malonic acid interact with alumina particles by electrostatic as well as specific adsorption forces. Systematic immersion contamination and polishing experiments were carried out to demonstrate the effectiveness of the acids in controlling alumina particulate contamination on wafer surfaces. The difference in the surface cleanliness was interpreted using the electrokinetic data and the calculated interaction energy between alumina particles and the wafer surface. Electrochemical tests showed no severe attack on tungsten films by the acids. Copper ions were found to adsorb onto the silicon dioxide surface, leading to copper contamination levels of upto 1013 atoms/cm 2. The extent of copper contamination was found to depend on the solution pH and the presence of additives such as hydrogen peroxide. Both electrokinetic measurements and immersion contamination experiments showed that citric acid can reduce the copper contamination on the silicon dioxide surface. TiN is more noble than tungsten in the solutions containing oxidants used in tungsten CMP slurries. The most significant corrosion of tungsten was found in the presence of hydrogen peroxide. Copper was found to be more noble than tantalum in acidic solutions. However, in alkaline ammonium hydroxide solutions, the

  10. Chemical abundances in metal-poor stars in Dwarf Galaxies

    NASA Astrophysics Data System (ADS)

    Venn, Kim; Norris, John; Shetrone, Matthew

    2015-08-01

    Stars in low-mass dwarf galaxies show a larger range in their chemical properties than those in the Milky Way halo. Not only are alpha-poor stars found at lower metallicities, but also r-process challenged stars, and a disparate fraction of carbon-enhanced metal-poor stars. A more pristine and chemically inhomogeneous interstellar medium, combined with stoichastic star formation in a metal-poor environment, is thought to cause these detectable differences in the early SN II contributions. We are also now finding stars in dwarf galaxies that appear to be iron-enhanced, i.e., stars that have formed in pockets of SN Ia enriched gas. A comparison of their chemical abundances with individual SN Ia models can provide unique constraints on the SN Ia progenitors.

  11. Enhancement of Platinum Cathode Catalysis by Addition of Transition Metals

    ERIC Educational Resources Information Center

    Duong, Hung Tuan

    2009-01-01

    The sluggish kinetics of oxygen reduction reaction (ORR) contributes significantly to the loss of cathode overpotential in fuel cells, thus requiring high loadings of platinum (Pt), which is an expensive metal with limited supply. However, Pt and Pt-based alloys are still the best available electrocatalysts for ORR thus far. The research presented…

  12. Enhancement of Platinum Cathode Catalysis by Addition of Transition Metals

    ERIC Educational Resources Information Center

    Duong, Hung Tuan

    2009-01-01

    The sluggish kinetics of oxygen reduction reaction (ORR) contributes significantly to the loss of cathode overpotential in fuel cells, thus requiring high loadings of platinum (Pt), which is an expensive metal with limited supply. However, Pt and Pt-based alloys are still the best available electrocatalysts for ORR thus far. The research presented…

  13. Exposure to chemical additives from polyvinyl chloride polymer extrusion processing

    SciTech Connect

    Lamb, C.S.

    1989-12-01

    The report presents a model to predict worker inhalation exposure due to off-gassing of additives during polyvinyl chloride (PVC) extrusion processing. Data on off-gassing of additives were reviewed in the literature, the off-gassing at normal PVC processing temperatures was studied in the laboratory, process variables were estimated from an equipment manufacturer survey, and worker-activities and possible exposure sources were observed in an industrial survey. The purpose of the study was to develop a theoretical model to predict worker inhalation exposure to additives used during PVC extrusion processing. A model to estimate the generation rate of the additive from the polymer extrudate was derived from the mass transport equations governing diffusion. The mass flow rate, initial additive volatile weight fraction, off-gassing time, diffusivity, and slab thickness are required to determine the generation rate from the model.

  14. Sequential aldol condensation-transition metal-catalyzed addition reactions of aldehydes, methyl ketones, and arylboronic acids.

    PubMed

    Liao, Yuan-Xi; Xing, Chun-Hui; Israel, Matthew; Hu, Qiao-Sheng

    2011-04-15

    Sequential aldol condensation of aldehydes with methyl ketones followed by transition metal-catalyzed addition reactions of arylboronic acids to form β-substituted ketones is described. By using the 1,1'-spirobiindane-7,7'-diol (SPINOL)-based phosphite, an asymmetric version of this type of sequential reaction, with up to 92% ee, was also realized. Our study provided an efficient method to access β-substituted ketones and might lead to the development of other sequential/tandem reactions with transition metal-catalyzed addition reactions as the key step. © 2011 American Chemical Society

  15. Effects of toxic metals and chemicals on biofilm and biocorrosion.

    PubMed

    Fang, Herbert H P; Xu, Li-Chong; Chan, Kwong-Yu

    2002-11-01

    Microbes in marine biofilms aggregated into clusters and increased the production of extracellular polymeric substances (EPS), by over 100% in some cases, when the seawater media containing toxic metals and chemicals, such as Cd(II), Cu(II), Pb(II), Zn(II), AI(III), Cr(III), glutaraldehyde, and phenol. The formation of microbial cluster and the increased production of EPS, which contained 84-92% proteins and 8-16% polysaccharides, accelerated the corrosion of the mild steel. However, there was no quantitative relationship between the degree of increased corrosion and the toxicity of metals/chemicals towards sulfate-reducing bacteria, or the increased EPS production.

  16. Chemical compatibility of structural materials in alkali metals

    SciTech Connect

    Natesan, K.; Rink, D.L.; Haglund, R.

    1995-04-01

    The objectives of this task are to (a) evaluate the chemical compatibility of structural alloys such as V-5 wt.%Cr-5 wt.%Ti alloy and Type 316 stainless steel for application in liquid alkali metals such as lithium and sodium-78 wt.% potassium (NaK) at temperatures in the range that are of interest for International Thermonuclear Experimental Reactor (ITER); (b) evaluate the transfer of nonmetallic elements such as oxygen, nitrogen, carbon, and hydrogen between structural materials and liquid metals; and (c) evaluate the effects of such transfers on the mechanical and microstructural characteristics of the materials for long-term service in liquid-metal-environments.

  17. Flue gas desulfurization/denitrification using metal-chelate additives

    DOEpatents

    Harkness, J.B.L.; Doctor, R.D.; Wingender, R.J.

    1985-08-05

    A method of simultaneously removing SO/sub 2/ and NO from oxygen-containing flue gases resulting from the combustion of carbonaceous material by contacting the flue gas with an aqueous scrubber solution containing an aqueous sulfur dioxide sorbent and an active metal chelating agent which promotes a reaction between dissolved SO/sub 2/ and dissolved NO to form hydroxylamine N-sulfonates. The hydroxylamine sulfonates are then separated from the scrubber solution which is recycled. 3 figs.

  18. Flue gas desulfurization/denitrification using metal-chelate additives

    DOEpatents

    Harkness, John B. L.; Doctor, Richard D.; Wingender, Ronald J.

    1986-01-01

    A method of simultaneously removing SO.sub.2 and NO from oxygen-containing flue gases resulting from the combustion of carbonaceous material by contacting the flue gas with an aqueous scrubber solution containing an aqueous sulfur dioxide sorbent and an active metal chelating agent which promotes a reaction between dissolved SO.sub.2 and dissolved NO to form hydroxylamine N-sulfonates. The hydroxylamine sulfonates are then separated from the scrubber solution which is recycled.

  19. Metal accumulation by stream bryophytes, related to chemical speciation.

    PubMed

    Tipping, E; Vincent, C D; Lawlor, A J; Lofts, S

    2008-12-01

    Metal accumulation by aquatic bryophytes was investigated using data for headwater streams of differing chemistry. The Windermere Humic Aqueous Model (WHAM) was applied to calculate chemical speciation, including competitive proton and metal interactions with external binding sites on the plants. The speciation modelling approach gives smaller deviations between observed and predicted bryophyte contents of Cu, Zn, Cd and Pb than regressions based on total filtered metal concentrations. If all four metals, and Ni, are considered together, the WHAM predictions are superior at the 1% level. Optimised constants for bryophyte binding by the trace metals are similar to those for humic substances and simple carboxylate ligands. Bryophyte contents of Na, Mg and Ca are approximately explained by binding at external sites, while most of the K is intracellular. Oxide phases account for some of the Al, and most of the Mn, Fe and Co.

  20. Metal-organic frameworks for the removal of toxic industrial chemicals and chemical warfare agents.

    PubMed

    Bobbitt, N Scott; Mendonca, Matthew L; Howarth, Ashlee J; Islamoglu, Timur; Hupp, Joseph T; Farha, Omar K; Snurr, Randall Q

    2017-06-06

    Owing to the vast diversity of linkers, nodes, and topologies, metal-organic frameworks can be tailored for specific tasks, such as chemical separations or catalysis. Accordingly, these materials have attracted significant interest for capture and/or detoxification of toxic industrial chemicals and chemical warfare agents. In this paper, we review recent experimental and computational work pertaining to the capture of several industrially-relevant toxic chemicals, including NH3, SO2, NO2, H2S, and some volatile organic compounds, with particular emphasis on the challenging issue of designing materials that selectively adsorb these chemicals in the presence of water. We also examine recent research on the capture and catalytic degradation of chemical warfare agents such as sarin and sulfur mustard using metal-organic frameworks.

  1. Using magnetic and chemical measurements to detect atmospherically-derived metal pollution in artificial soils and metal uptake in plants.

    PubMed

    Sapkota, B; Cioppa, M T

    2012-11-01

    Quantification of potential effects of ambient atmospheric pollution on magnetic and chemical properties of soils and plants requires precise experimental studies. A controlled growth experiment assessing magnetic and chemical parameters was conducted within (controls) and outside (exposed) a greenhouse setting. Magnetic susceptibility (MS) measurements showed that while initial MS values were similar for the sample sets, the overall MS value of exposed soil was significantly greater than in controls, suggesting an additional input of Fe-containing particles. Scanning electron microscope images of the exposed soils revealed numerous angular magnetic particles and magnetic spherules typical of vehicular exhaust and combustion processes, respectively. Similarly, chemical analysis of plant roots showed that plants grown in the exposed soil had higher concentrations of Fe and heavy (toxic) metals than controls. This evidence suggests that atmospheric deposition contributed to the MS increase in exposed soils and increased metal uptake by plants grown in this soil. Copyright © 2012 Elsevier Ltd. All rights reserved.

  2. Metal ion sorption by untreated and chemically treated biomass

    SciTech Connect

    Kilbane, J.J.; Xie, J.

    1992-12-31

    The metal-binding ability of biosorbents is well known; however, in comparison with commercial ion-exchange resins the capacity of biosorbents is low. The purpose of this research was to examine chemically modified biosorbents and biosorbents prepared from microorganisms isolated from extreme environments to determine if significant improvements in metal-binding capacity or biosorbents with unique capabilities could be produced. Chemical treatments examined included acid, alkali, carbon disulfide, phosphorus oxychloride, anhydrous formamide, sodium thiosulfate, sodium chloroacetic acid, and phenylsulfonate. Biosorbents were prepared from microorganisms isolated from pristine and acid mine drainage impacted sites and included heterotrophs, methanotrophs, algae, and sulfate reducers. Chemical modification with carbon disulfide, phosphorous oxychloride, and sodium thiosulfate yielded biosorbents with such as much as 74%, 133%, and 155% improvements, respectively, in metal-binding capacity, but the performance of these chemically modified biosorbents deteriorated upon repeated use. A culture isolated from an acid mine drainage impacted site, IGTM17, exhibits about 3-fold higher metal-binding capacity in comparison with other biosorbents examined in this study. IGTM17 also exhibits superior metal-binding ability at decreased pH or in the presence of interfering common cations in comparison with other biosorbents or some commercially available cation exchange resins. Some biosorbents, such as IGTM5, can bind anions. To our knowledge this is the first demonstration of the ability of biosorbents to bind anions. Moreover, preliminary data indicate that the chemical modification of biosorbents may be capable of imparting the ability to selectively bind certain anions. Further research is needed to optimize conditions for the chemical modification and stabilization of biosorbents.

  3. Catalytic activity of noble metals for metal-assisted chemical etching of silicon

    PubMed Central

    2012-01-01

    Metal-assisted chemical etching of silicon is an electroless method that can produce porous silicon by immersing metal-modified silicon in a hydrofluoric acid solution without electrical bias. We have been studying the metal-assisted hydrofluoric acid etching of silicon using dissolved oxygen as an oxidizing agent. Three major factors control the etching reaction and the porous silicon structure: photoillumination during etching, oxidizing agents, and metal particles. In this study, the influence of noble metal particles, silver, gold, platinum, and rhodium, on this etching is investigated under dark conditions: the absence of photogenerated charges in the silicon. The silicon dissolution is localized under the particles, and nanopores are formed whose diameters resemble the size of the metal nanoparticles. The etching rate of the silicon and the catalytic activity of the metals for the cathodic reduction of oxygen in the hydrofluoric acid solution increase in the order of silver, gold, platinum, and rhodium. PMID:22738277

  4. Microstructure-controllable Laser Additive Manufacturing Process for Metal Products

    NASA Astrophysics Data System (ADS)

    Huang, Wei-Chin; Chuang, Chuan-Sheng; Lin, Ching-Chih; Wu, Chih-Hsien; Lin, De-Yau; Liu, Sung-Ho; Tseng, Wen-Peng; Horng, Ji-Bin

    Controlling the cooling rate of alloy during solidification is the most commonly used method for varying the material microstructure. However, the cooling rate of selective laser melting (SLM) production is constrained by the optimal parameter settings for a dense product. This study proposes a method for forming metal products via the SLM process with electromagnetic vibrations. The electromagnetic vibrations change the solidification process for a given set of SLM parameters, allowing the microstructure to be varied via magnetic flux density. This proposed method can be used for creating microstructure-controllable bio-implant products with complex shapes.

  5. The effect of chemical additives on the synthesis of ethanol

    SciTech Connect

    Chuang, S.S.C.

    1992-03-06

    The objective of this research was to investigate the reaction mechanism of higher alcohol and aldehyde synthesis from syngas and the role of additives in the synthesis. An in situ IR reaction system and probe molecule technique were developed to study adsorbed species, active sites, and reaction pathway during reaction. The catalysts used for this study included silica-supported Rh, Ru, and Ni. (VC)

  6. Direct conversion of radioactive and chemical waste containing metals, ceramics, amorphous solids, and organics to glass

    SciTech Connect

    Forsberg, C.W.; Beahm, E.C.; Parker, G.W.

    1994-05-02

    The Glass Material Oxidation and Dissolution System (CMODS) is a new process for direct conversion of radioactive, mixed, and chemical wastes to glass. The wastes can be in the chemical forms of metals, ceramics, amorphous solids, and organics. GMODS destroys organics and it incorporates heavy metals and radionuclides into a glass. Processable wastes may include miscellaneous spent fuels (SF), SF hulls and hardware, plutonium wastes in different forms, high-efficiency particulate air (HEPA) filters, ion-exchange resins, failed equipment, and laboratory wastes. Thermodynamic calculations indicate theoretical feasibility. Small-scale laboratory experiments (< 100 g per test) have demonstrated chemical laboratory feasibility for several metals. Additional work is needed to demonstrate engineering feasibility.

  7. Automatic Submerged ARC Welding With Metal Power Additions to Increase Productivity and Maintain Quality

    DTIC Science & Technology

    1986-06-01

    Manager of Welding Engineering PROPOSAL WELDING OF CARBON STEEL AND HY80 UTILIZING THE BULK WELDING PROCESS May 9, 1983 PREPARED BY: NEWPORT NEwS...12 joints with carbon steel and 12 with HY80 , utilizing three The joints will requirements of Benefits 1. Deposition times that different size double...of Joint Variations and Deposition Rates Filler Metal/Base Material Chemical Analyses; Carbon Steel /HIS Filler Metal/Base Material Chemical Analyses

  8. The chemical form of metallic debris in tissues surrounding metal-on-metal hips with unexplained failure.

    PubMed

    Hart, Alister J; Quinn, Paul D; Sampson, Barry; Sandison, Ann; Atkinson, Kirk D; Skinner, John A; Powell, Jonathan J; Mosselmans, J Fred W

    2010-11-01

    Implant-derived material from metal-on-metal (MOM) hip arthroplasties may be responsible for an unexplained tissue inflammatory response. The chemical form of the metal species in the tissues is predominantly chromium (Cr), but the currently used techniques have not been able to determine whether this is Cr(III) phosphate or Cr(III) oxide. The analytical challenge must overcome the fact that the metal in the tissues is at a relatively low concentration and tissue preparation or the microscopy beam used can affect the results. Microfocus X-ray spectroscopy using a synchrotron beam is useful in addressing both these issues. Using this technique we compared tissue from failed MOM hips with: (1) tissue from metal-on-polyethylene (MOP) hips; (2) chemical standards; (3) metal discs cut from MOM hips. The most abundant implant-related species in all MOM hip tissues contained Cr. Comparison with standards revealed the chemical form was Cr(III) phosphate, which did not vary with manufacturer type (four types analysed) or level of blood metal ions. Cobalt (Co) and molybdenum (Mo) were occasionally present in areas of high Cr. Co was normally found in a metallic state in the tissue, while Mo was found in an oxidized state. The variety of metallic species may have arisen from corrosion, wear or a combination of both. No evidence of Cr(VI) was seen in the tissues examined.

  9. Metal-air cell with performance enhancing additive

    DOEpatents

    Friesen, Cody A; Buttry, Daniel

    2015-11-10

    Systems and methods drawn to an electrochemical cell comprising a low temperature ionic liquid comprising positive ions and negative ions and a performance enhancing additive added to the low temperature ionic liquid. The additive dissolves in the ionic liquid to form cations, which are coordinated with one or more negative ions forming ion complexes. The electrochemical cell also includes an air electrode configured to absorb and reduce oxygen. The ion complexes improve oxygen reduction thermodynamics and/or kinetics relative to the ionic liquid without the additive.

  10. Metal Organic-Chemical Vapor Deposition fabrication of semiconductor lasers

    NASA Astrophysics Data System (ADS)

    Thomas, C.

    1980-08-01

    The metal organic chemical vapor deposition (MO-CVD) process was studied and implemented in detail. Single crystal GaAs, and Ga(x)Al(1-x)As films were grown on GaAs by depositing metal organic alkyl gallium compounds in the presence of an arsine mixture. The metal organic chemical vapor deposition process allowed formation of the semiconductor compound directly on the heated substrate in only one hot temperature zone. With MO-CVD, semiconductor films can be efficiently produced by a more economical, less complicated process which will lend itself more easily than past fabrication procedures, to high quantity, high quality reproduction techniques of semiconductor lasers. Clearly MO-CVD is of interest to the communication industry where semiconductor lasers are used extensively in fiber optic communication systems, and similarly to the solar energy business where GaAs substrates are used as photoelectric cells.

  11. 75 FR 33824 - Pharmaceutical Products and Chemical Intermediates, Fourth Review: Advice Concerning the Addition...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-06-15

    ... COMMISSION Pharmaceutical Products and Chemical Intermediates, Fourth Review: Advice Concerning the Addition of Certain Products to the Pharmaceutical Appendix to the HTS AGENCY: United States International... (Commission) instituted investigation No. 332-520, Pharmaceutical Products and Chemical Intermediates, Fourth...

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

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

    NASA Astrophysics Data System (ADS)

    Patridge, Christopher James

    different individual beta'-Cu xV2O5 nanowires vary widely. Using scanning transmission X-ray microspectroscopy of individual beta'-CuxV2O 5 nanowires, correlations appear to exist between MIT characteristics and the markedly different orbital hybridization of vanadium and oxygen at the O K and V L absorption edges. These comprehensive nanostructure studies hint at the possibility of approaching the incredibly important realm of single-domain measurements which are needed to understand and exploit the intrinsic physical properties of materials. In addition to the bronze MIT studies, the classical MIT material vanadium dioxide, VO2, also shows new properties when scaling down to nanoscale dimensions as well as incorporation of substitutional dopants such as tungsten. X-ray absorption spectroscopy of the dopant local structure suggests an increased symmetry and depairing of V4+-V 4+, which is critical for transition to the lower temperature insulating phase thereby super-cooling the metallic phase to temperatures as low as 254 K. Mechanistic insight and structural changes associated with the intercalation of Li+ are key aspects in understanding and designing useful secondary Li ion batteries. In similarity to the MxV2O 5 studies, another metal vanadate, Ag2VO2PO 4, undergoes phase transformations due to introduction of Li and the vacancy of Ag ions. Employing a comprehensive study on Ag2VO 2PO4 using X-ray absorption spectroscopy, information about chemical state changes and rehybridization of frontier orbitals allows for a more precise understanding of how the material discharges, what, if any, intermediate phases exist during the process, and provides evidence for the posited structural stability at high depths of discharge.

  14. Oxidative addition of C--H bonds in organic molecules to transition metal centers

    SciTech Connect

    Bergman, R.G.

    1989-04-01

    Alkanes are among the most chemically inert organic molecules. They are reactive toward a limited range of reagents, such as highly energetic free radicals and strongly electrophilic and oxidizing species. This low reactivity is a consequence of the C--H bond energies in most saturated hydrocarbons. These values range from 90 to 98 kcal/mole for primary and secondary C--H bonds; in methane, the main constituent of natural gas, the C--H bond energy is 104 kcal/mole. This makes methane one of the most common but least reactive organic molecules in nature. This report briefly discusses the search for metal complexes capable of undergoing the C--H oxidative addition process allowing alkane chemistry to be more selective than that available using free radical reagents. 14 refs.

  15. Secondary metallicity in analytic models of chemical evolution of galaxies

    NASA Technical Reports Server (NTRS)

    Clayton, D. D.; Pantelaki, I.

    1986-01-01

    Analytic models of the chemical evolution of galactic regions that grow in mass owing to the continuous infall of matter are characterized, emphasizing the solutions for secondary nuclei (defined as those nuclei whose stellar yields are proportional to the abundance of a primary seed nucleus) in the families of models described by Clayton (1984 and 1985). Wide variations in time dependence of both primary and secondary nuclei as well as in the ratio of secondary to primary are displayed by these model families, confirming again the usefulness of these families as interpretive guides if galaxies do in fact evolve with substantial infall. Additionally, analytic solutions are presented for two other possible interesting systems: the evolution of abundances if the primary metallicity in the infall is increasing in time, and the evolution of abundances if the primary yield changes linearly with time owing to continuous changes in the stellar mass function, the opacity, or other astrophysical agents. Finally, test evaluations of the instantaneous recycling approximation on which these analytic models rely are presented.

  16. Secondary metallicity in analytic models of chemical evolution of galaxies

    NASA Astrophysics Data System (ADS)

    Clayton, D. D.; Pantelaki, I.

    1986-08-01

    Analytic models of the chemical evolution of galactic regions that grow in mass owing to the continuous infall of matter are characterized, emphasizing the solutions for secondary nuclei (defined as those nuclei whose stellar yields are proportional to the abundance of a primary seed nucleus) in the families of models described by Clayton (1984 and 1985). Wide variations in time dependence of both primary and secondary nuclei as well as in the ratio of secondary to primary are displayed by these model families, confirming again the usefulness of these families as interpretive guides if galaxies do in fact evolve with substantial infall. Additionally, analytic solutions are presented for two other possible interesting systems: the evolution of abundances if the primary metallicity in the infall is increasing in time, and the evolution of abundances if the primary yield changes linearly with time owing to continuous changes in the stellar mass function, the opacity, or other astrophysical agents. Finally, test evaluations of the instantaneous recycling approximation on which these analytic models rely are presented.

  17. Additive Manufacturing of Metal Cellular Structures: Design and Fabrication

    NASA Astrophysics Data System (ADS)

    Yang, Li; Harrysson, Ola; Cormier, Denis; West, Harvey; Gong, Haijun; Stucker, Brent

    2015-03-01

    With the rapid development of additive manufacturing (AM), high-quality fabrication of lightweight design-efficient structures no longer poses an insurmountable challenge. On the other hand, much of the current research and development with AM technologies still focuses on material and process development. With the design for additive manufacturing in mind, this article explores the design issue for lightweight cellular structures that could be efficiently realized via AM processes. A unit-cell-based modeling approach that combines experimentation and limited-scale simulation was demonstrated, and it was suggested that this approach could potentially lead to computationally efficient design optimizations with the lightweight structures in future applications.

  18. Evaluation of alternative chemical additives for high-level waste vitrification feed preparation processing

    SciTech Connect

    Seymour, R.G.

    1995-06-07

    During the development of the feed processing flowsheet for the Defense Waste Processing Facility (DWPF) at the Savannah River Site (SRS), research had shown that use of formic acid (HCOOH) could accomplish several processing objectives with one chemical addition. These objectives included the decomposition of tetraphenylborate, chemical reduction of mercury, production of acceptable rheological properties in the feed slurry, and controlling the oxidation state of the glass melt pool. However, the DEPF research had not shown that some vitrification slurry feeds had a tendency to evolve hydrogen (H{sub 2}) and ammonia (NH{sub 3}) as the result of catalytic decomposition of CHOOH with noble metals (rhodium, ruthenium, palladium) in the feed. Testing conducted at Pacific Northwest Laboratory and later at the Savannah River Technical Center showed that the H{sub 2} and NH{sub 3} could evolve at appreciable rates and quantities. The explosive nature of H{sub 2} and NH{sub 3} (as ammonium nitrate) warranted significant mitigation control and redesign of both facilities. At the time the explosive gas evolution was discovered, the DWPF was already under construction and an immediate hardware fix in tandem with flowsheet changes was necessary. However, the Hanford Waste Vitrification Plant (HWVP) was in the design phase and could afford to take time to investigate flowsheet manipulations that could solve the problem, rather than a hardware fix. Thus, the HWVP began to investigate alternatives to using HCOOH in the vitrification process. This document describes the selection, evaluation criteria, and strategy used to evaluate the performance of the alternative chemical additives to CHOOH. The status of the evaluation is also discussed.

  19. Part height control of laser metal additive manufacturing process

    NASA Astrophysics Data System (ADS)

    Pan, Yu-Herng

    Laser Metal Deposition (LMD) has been used to not only make but also repair damaged parts in a layer-by-layer fashion. Parts made in this manner may produce less waste than those made through conventional machining processes. However, a common issue of LMD involves controlling the deposition's layer thickness. Accuracy is important, and as it increases, both the time required to produce the part and the material wasted during the material removal process (e.g., milling, lathe) decrease. The deposition rate is affected by multiple parameters, such as the powder feed rate, laser input power, axis feed rate, material type, and part design, the values of each of which may change during the LMD process. Using a mathematical model to build a generic equation that predicts the deposition's layer thickness is difficult due to these complex parameters. In this thesis, we propose a simple method that utilizes a single device. This device uses a pyrometer to monitor the current build height, thereby allowing the layer thickness to be controlled during the LMD process. This method also helps the LMD system to build parts even with complex parameters and to increase material efficiency.

  20. Use of negative chemical ionization mass spectrometry for the trace analysis of metals.

    PubMed Central

    Risby, T H

    1980-01-01

    The synthesis of various volatile and thermally stable derivatives of metals ions has permitted the use of conventional mass spectrometry for trace metal analysis. This paper reviews the development of the field using electron impact and chemical ionization mass spectrometry. This latter methodology produces simple mass spectra that enable complex mixtures to be analyzed. In addition the use of negative ion detection has produced selective ionization since many metal chelates contain heteroatoms which are electronegative. A discussion of the use of this general methodology for trace metal analysis is included, together with its applications to the analysis of ruthenium in automobile exhaust emissions and iron in red blood cells from laboratory rats. The future use of this methodology is expected to be for the monitoring of stable metal isotopes. This procedure could be used to follow these tracers in clinical and environmental studies and it is expected that their use will replace radioactive isotopes in most studies. PMID:7000514

  1. Destruction of chemical warfare agents using metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Mondloch, Joseph E.; Katz, Michael J.; Isley, William C., III; Ghosh, Pritha; Liao, Peilin; Bury, Wojciech; Wagner, George W.; Hall, Morgan G.; Decoste, Jared B.; Peterson, Gregory W.; Snurr, Randall Q.; Cramer, Christopher J.; Hupp, Joseph T.; Farha, Omar K.

    2015-05-01

    Chemical warfare agents containing phosphonate ester bonds are among the most toxic chemicals known to mankind. Recent global military events, such as the conflict and disarmament in Syria, have brought into focus the need to find effective strategies for the rapid destruction of these banned chemicals. Solutions are needed for immediate personal protection (for example, the filtration and catalytic destruction of airborne versions of agents), bulk destruction of chemical weapon stockpiles, protection (via coating) of clothing, equipment and buildings, and containment of agent spills. Solid heterogeneous materials such as modified activated carbon or metal oxides exhibit many desirable characteristics for the destruction of chemical warfare agents. However, low sorptive capacities, low effective active site loadings, deactivation of the active site, slow degradation kinetics, and/or a lack of tailorability offer significant room for improvement in these materials. Here, we report a carefully chosen metal-organic framework (MOF) material featuring high porosity and exceptional chemical stability that is extraordinarily effective for the degradation of nerve agents and their simulants. Experimental and computational evidence points to Lewis-acidic ZrIV ions as the active sites and to their superb accessibility as a defining element of their efficacy.

  2. Destruction of chemical warfare agents using metal-organic frameworks.

    PubMed

    Mondloch, Joseph E; Katz, Michael J; Isley, William C; Ghosh, Pritha; Liao, Peilin; Bury, Wojciech; Wagner, George W; Hall, Morgan G; DeCoste, Jared B; Peterson, Gregory W; Snurr, Randall Q; Cramer, Christopher J; Hupp, Joseph T; Farha, Omar K

    2015-05-01

    Chemical warfare agents containing phosphonate ester bonds are among the most toxic chemicals known to mankind. Recent global military events, such as the conflict and disarmament in Syria, have brought into focus the need to find effective strategies for the rapid destruction of these banned chemicals. Solutions are needed for immediate personal protection (for example, the filtration and catalytic destruction of airborne versions of agents), bulk destruction of chemical weapon stockpiles, protection (via coating) of clothing, equipment and buildings, and containment of agent spills. Solid heterogeneous materials such as modified activated carbon or metal oxides exhibit many desirable characteristics for the destruction of chemical warfare agents. However, low sorptive capacities, low effective active site loadings, deactivation of the active site, slow degradation kinetics, and/or a lack of tailorability offer significant room for improvement in these materials. Here, we report a carefully chosen metal-organic framework (MOF) material featuring high porosity and exceptional chemical stability that is extraordinarily effective for the degradation of nerve agents and their simulants. Experimental and computational evidence points to Lewis-acidic Zr(IV) ions as the active sites and to their superb accessibility as a defining element of their efficacy.

  3. Overview of Materials Qualification Needs for Metal Additive Manufacturing

    NASA Astrophysics Data System (ADS)

    Seifi, Mohsen; Salem, Ayman; Beuth, Jack; Harrysson, Ola; Lewandowski, John J.

    2016-03-01

    This overview highlights some of the key aspects regarding materials qualification needs across the additive manufacturing (AM) spectrum. AM technology has experienced considerable publicity and growth in the past few years with many successful insertions for non-mission-critical applications. However, to meet the full potential that AM has to offer, especially for flight-critical components (e.g., rotating parts, fracture-critical parts, etc.), qualification and certification efforts are necessary. While development of qualification standards will address some of these needs, this overview outlines some of the other key areas that will need to be considered in the qualification path, including various process-, microstructure-, and fracture-modeling activities in addition to integrating these with lifing activities targeting specific components. Ongoing work in the Advanced Manufacturing and Mechanical Reliability Center at Case Western Reserve University is focusing on fracture and fatigue testing to rapidly assess critical mechanical properties of some titanium alloys before and after post-processing, in addition to conducting nondestructive testing/evaluation using micro-computerized tomography at General Electric. Process mapping studies are being conducted at Carnegie Mellon University while large area microstructure characterization and informatics (EBSD and BSE) analyses are being conducted at Materials Resources LLC to enable future integration of these efforts via an Integrated Computational Materials Engineering approach to AM. Possible future pathways for materials qualification are provided.

  4. Metal transport and chemical heterogeneity in early star forming systems

    NASA Astrophysics Data System (ADS)

    Ritter, Jeremy S.; Sluder, Alan; Safranek-Shrader, Chalence; Milosavljević, Miloš; Bromm, Volker

    2015-08-01

    To constrain the properties of the first stars with the chemical abundance patterns observed in metal-poor stars, one must identify any non-trivial effects that the hydrodynamics of metal dispersal can imprint on the abundances. We use realistic cosmological hydrodynamic simulations to quantify the distribution of metals resulting from one Population III supernova and from a small number of such supernovae exploding in close succession. Overall, supernova ejecta are highly inhomogeneously dispersed throughout the simulations. When the supernova bubbles collapse, quasi-virialized metal-enriched clouds, fed by fallback from the bubbles and by streaming of metal-free gas from the cosmic web, grow in the centres of the dark matter haloes. Partial turbulent homogenization on scales resolved in the simulation is observed only in the densest clouds where the vortical time-scales are short enough to ensure true homogenization on subgrid scales. However, the abundances in the clouds differ from the gross yields of the supernovae. Continuing the simulations until the cloud have gone into gravitational collapse, we predict that the abundances in second-generation stars will be deficient in the innermost mass shells of the supernova (if only one has exploded) or in the ejecta of the latest supernovae (when multiple have exploded). This indicates that hydrodynamics gives rise to biases complicating the identification of nucleosynthetic sources in the chemical abundance spaces of the surviving stars.

  5. Metal-assisted chemical etch porous silicon formation method

    DOEpatents

    Li, Xiuling; Bohn, Paul W.; Sweedler, Jonathan V.

    2004-09-14

    A thin discontinuous layer of metal such as Au, Pt, or Au/Pd is deposited on a silicon surface. The surface is then etched in a solution including HF and an oxidant for a brief period, as little as a couple seconds to one hour. A preferred oxidant is H.sub.2 O.sub.2. Morphology and light emitting properties of porous silicon can be selectively controlled as a function of the type of metal deposited, Si doping type, silicon doping level, and/or etch time. Electrical assistance is unnecessary during the chemical etching of the invention, which may be conducted in the presence or absence of illumination.

  6. Spontaneous grafting of diazonium salts: chemical mechanism on metallic surfaces.

    PubMed

    Mesnage, Alice; Lefèvre, Xavier; Jégou, Pascale; Deniau, Guy; Palacin, Serge

    2012-08-14

    The spontaneous reaction of diazonium salts on various substrates has been widely employed since it consists of a simple immersion of the substrate in the diazonium salt solution. As electrochemical processes involving the same diazonium salts, the spontaneous grafting is assumed to give covalently poly(phenylene)-like bonded films. Resistance to solvents and to ultrasonication is commonly accepted as indirect proof of the existence of a covalent bond. However, the most relevant attempts to demonstrate a metal-C interface bond have been obtained by an XPS investigation of spontaneously grafted films on copper. Similarly, our experiments give evidence of such a bond in spontaneously grafted films on nickel substrates in acetonitrile. In the case of gold substrates, the formation of a spontaneous film was unexpected but reported in the literature in parallel to our observations. Even if no interfacial bond was observed, formation of the films was explained by grafting of aryl cations or radicals on the surface arising from dediazoniation, the film growing later by azo coupling, radical addition, or cationic addition on the grafted phenyl layer. Nevertheless, none of these mechanisms fits our experimental results showing the presence of an Au-N bond. In this work, we present a fine spectroscopic analysis of the coatings obtained on gold and nickel substrates that allow us to propose a chemical structure of such films, in particular, their interface with the substrates. After testing the most probable mechanisms, we have concluded in favor of the involvement of two complementary mechanisms which are the direct reaction of diazonium salts with the gold surface that accounts for the observed Au-N interfacial bonds as well as the formation of aryl cations able to graft on the substrate through Au-C linkages.

  7. Metal-Organic Frameworks for CO2 Chemical Transformations.

    PubMed

    He, Hongming; Perman, Jason A; Zhu, Guangshan; Ma, Shengqian

    2016-12-01

    Carbon dioxide (CO2 ), as the primary greenhouse gas in the atmosphere, triggers a series of environmental and energy related problems in the world. Therefore, there is an urgent need to develop multiple methods to capture and convert CO2 into useful chemical products, which can significantly improve the environment and promote sustainable development. Over the past several decades, metal-organic frameworks (MOFs) have shown outstanding heterogeneous catalytic activity due in part to their high internal surface area and chemical functionalities. These properties and the ability to synthesize MOF platforms allow experiments to test structure-function relationships for transforming CO2 into useful chemicals. Herein, recent developments are highlighted for MOFs participating as catalysts for the chemical fixation and photochemical reduction of CO2 . Finally, opportunities and challenges facing MOF catalysts are discussed in this ongoing research area.

  8. 15 CFR 714.3 - Advance declaration requirements for additionally planned production of Schedule 3 chemicals.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... additionally planned production of Schedule 3 chemicals. 714.3 Section 714.3 Commerce and Foreign Trade Regulations Relating to Commerce and Foreign Trade (Continued) BUREAU OF INDUSTRY AND SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 3 CHEMICALS § 714.3 Advance...

  9. 15 CFR 714.3 - Advance declaration requirements for additionally planned production of Schedule 3 chemicals.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... additionally planned production of Schedule 3 chemicals. 714.3 Section 714.3 Commerce and Foreign Trade Regulations Relating to Commerce and Foreign Trade (Continued) BUREAU OF INDUSTRY AND SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 3 CHEMICALS § 714.3 Advance...

  10. 15 CFR 714.3 - Advance declaration requirements for additionally planned production of Schedule 3 chemicals.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... additionally planned production of Schedule 3 chemicals. 714.3 Section 714.3 Commerce and Foreign Trade Regulations Relating to Commerce and Foreign Trade (Continued) BUREAU OF INDUSTRY AND SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 3 CHEMICALS § 714.3 Advance...

  11. 15 CFR 714.3 - Advance declaration requirements for additionally planned production of Schedule 3 chemicals.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... additionally planned production of Schedule 3 chemicals. 714.3 Section 714.3 Commerce and Foreign Trade Regulations Relating to Commerce and Foreign Trade (Continued) BUREAU OF INDUSTRY AND SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 3 CHEMICALS § 714.3 Advance...

  12. Electrochemical study on metal corrosion in chemical mechanical planarization process

    NASA Astrophysics Data System (ADS)

    Kondo, Seiichi; Ichige, Yasuhiro; Otsuka, Yuya

    2017-07-01

    Typical metal corrosions caused by the chemical mechanical planarization (CMP) process are discussed in this review paper. By categorizing them into seven kinds of corrosion, namely, chemical corrosion, crevice corrosion, crystal-orientation-dependent corrosion, narrow trench corrosion, photocorrosion, galvanic corrosion, and electrostatic-charge induced corrosion, we discuss their mechanisms and how to suppress them on the basis of electrochemical studies. Moreover, we demonstrate the usefulness of three-dimensional pH-potential diagrams for predicting corrosion issues in an actual CMP process.

  13. More accurate depiction of adsorption energy on transition metals using work function as one additional descriptor.

    PubMed

    Shen, Xiaochen; Pan, Yanbo; Liu, Bin; Yang, Jinlong; Zeng, Jie; Peng, Zhenmeng

    2017-05-24

    The reaction mechanism and properties of a catalytic process are primarily determined by the interactions between reacting species and catalysts. However, the interactions are often challenging to be experimentally measured, especially for unstable intermediates. Therefore, it is of significant importance to establish an exact relationship between chemical-catalyst interactions and catalyst parameters, which will allow calculation of these interactions and thus advance their mechanistic understanding. Herein we report the description of adsorption energy on transition metals by considering both ionic bonding and covalent bonding contributions and introduce the work function as one additional responsible parameter. We find that the adsorption energy can be more accurately described using a two-dimensional (2D) polynomial model, which shows a significant improvement compared with the current adsorption energy-d-band center linear correlation. We also demonstrate the utilization of this new 2D polynomial model to calculate oxygen binding energy of different transition metals to help understand their catalytic properties in oxygen reduction reactions.

  14. Solidification and solid-state transformation sciences in metals additive manufacturing

    DOE PAGES

    Kirka, Michael M.; Nandwana, Peeyush; Lee, Yousub; ...

    2017-02-11

    Additive manufacturing (AM) of metals is rapidly emerging as an established manufacturing process for metal components. Unlike traditional metals fabrication processes, metals fabricated via AM undergo localized thermal cycles during fabrication. As a result, AM presents the opportunity to control the liquid-solid phase transformation, i.e. material texture. But, thermal cycling presents challenges from the standpoint of solid-solid phase transformations. We will discuss the opportunities and challenges in metals AM in the context of texture control and associated solid-solid phase transformations in Ti-6Al-4V and Inconel 718.

  15. Silicon nanowire photodetectors made by metal-assisted chemical etching

    NASA Astrophysics Data System (ADS)

    Xu, Ying; Ni, Chuan; Sarangan, Andrew

    2016-09-01

    Silicon nanowires have unique optical effects, and have potential applications in photodetectors. They can exhibit simple optical effects such as anti-reflection, but can also produce quantum confined effects. In this work, we have fabricated silicon photodetectors, and then post-processed them by etching nanowires on the incident surface. These nanowires were produced by a wet-chemical etching process known as the metal-assisted-chemical etching, abbreviated as MACE. N-type silicon substrates were doped by thermal diffusion from a solid ceramic source, followed by etching, patterning and contact metallization. The detectors were first tested for functionality and optical performance. The nanowires were then made by depositing an ultra-thin film of gold below its percolation thickness to produce an interconnected porous film. This was then used as a template to etch high aspect ratio nanowires into the face of the detectors with a HF:H2O2 mixture.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  17. Optimization of soil mixing technology through metallic iron addition.

    SciTech Connect

    Moos, L. P.

    1999-01-15

    Enhanced soil mixing is a process used to remove volatile organic compounds (VOCs) from soil. In this process, also known as soil mixing with thermally enhanced soil vapor extraction, or SM/TESVE, a soil mixing apparatus breaks up and mixes a column of soil up to 9 m (30 ft) deep; simultaneously, hot air is blown through the soil. The hot air carries the VOCs to the surface where they are collected and safely disposed of. This technology is cost effective at high VOC concentrations, but it becomes cost prohibitive at low concentrations. Argonne National Laboratory-East conducted a project to evaluate ways of improving the effectiveness of this system. The project investigated the feasibility of integrating the SM/TESVE process with three soil treatment processes--soil vapor extraction, augmented indigenous biodegradation, and zero-valent iron addition. Each of these technologies was considered a polishing treatment designed to remove the contaminants left behind by enhanced soil mixing. The experiment was designed to determine if the overall VOC removal effectiveness and cost-effectiveness of the SM/TESVE process could be improved by integrating this approach with one of the polishing treatment systems.

  18. Strategy for Texture Management in Metals Additive Manufacturing

    NASA Astrophysics Data System (ADS)

    Kirka, M. M.; Lee, Y.; Greeley, D. A.; Okello, A.; Goin, M. J.; Pearce, M. T.; Dehoff, R. R.

    2017-03-01

    Additive manufacturing (AM) technologies have long been recognized for their ability to fabricate complex geometric components directly from models conceptualized through computers, allowing for complicated designs and assemblies to be fabricated at lower costs, with shorter time to market, and improved function. Lacking behind the design complexity aspect is the ability to fully exploit AM processes for control over texture within AM components. Currently, standard heat-fill strategies utilized in AM processes result in largely columnar grain structures. Proposed in this work is a point heat source fill for the electron beam melting (EBM) process through which the texture in AM materials can be controlled. Through this point heat source strategy, the ability to form either columnar or equiaxed grain structures upon solidification through changes in the process parameters associated with the point heat source fill is demonstrated for the nickel-base superalloy, Inconel 718. Mechanically, the material is demonstrated to exhibit either anisotropic properties for the columnar-grained material fabricated through using the standard raster scan of the EBM process or isotropic properties for the equiaxed material fabricated using the point heat source fill.

  19. Strategy for Texture Management in Metals Additive Manufacturing

    DOE PAGES

    Kirka, Michael M.; Lee, Yousub; Greeley, Duncan A.; ...

    2017-01-31

    Additive manufacturing (AM) technologies have long been recognized for their ability to fabricate complex geometric components directly from models conceptualized through computers, allowing for complicated designs and assemblies to be fabricated at lower costs, with shorter time to market, and improved function. Lacking behind the design complexity aspect is the ability to fully exploit AM processes for control over texture within AM components. Currently, standard heat-fill strategies utilized in AM processes result in largely columnar grain structures. Here, we propose a point heat source fill for the electron beam melting (EBM) process through which the texture in AM materials canmore » be controlled. Using this point heat source strategy, the ability to form either columnar or equiaxed grain structures upon solidification through changes in the process parameters associated with the point heat source fill is demonstrated for the nickel-base superalloy, Inconel 718. Mechanically, the material is demonstrated to exhibit either anisotropic properties for the columnar-grained material fabricated through using the standard raster scan of the EBM process or isotropic properties for the equiaxed material fabricated using the point heat source fill.« less

  20. Nanostructured Metal Oxides for Stoichiometric Degradation of Chemical Warfare Agents.

    PubMed

    Štengl, Václav; Henych, Jiří; Janoš, Pavel; Skoumal, Miroslav

    2016-01-01

    Metal oxides have very important applications in many areas of chemistry, physics and materials science; their properties are dependent on the method of preparation, the morphology and texture. Nanostructured metal oxides can exhibit unique characteristics unlike those of the bulk form depending on their morphology, with a high density of edges, corners and defect surfaces. In recent years, methods have been developed for the preparation of metal oxide powders with tunable control of the primary particle size as well as of a secondary particle size: the size of agglomerates of crystallites. One of the many ways to take advantage of unique properties of nanostructured oxide materials is stoichiometric degradation of chemical warfare agents (CWAs) and volatile organic compounds (VOC) pollutants on their surfaces.

  1. Are delta-aminolevulinate dehydratase inhibition and metal concentrations additional factors for the age-related cognitive decline?

    PubMed

    Baierle, Marília; Charão, Mariele F; Göethel, Gabriela; Barth, Anelise; Fracasso, Rafael; Bubols, Guilherme; Sauer, Elisa; Campanharo, Sarah C; Rocha, Rafael C C; Saint'Pierre, Tatiana D; Bordignon, Suelen; Zibetti, Murilo; Trentini, Clarissa M; Avila, Daiana S; Gioda, Adriana; Garcia, Solange C

    2014-10-17

    Aging is often accompanied by cognitive impairments and influenced by oxidative status and chemical imbalances. Thus, this study was conducted to examine whether age-related cognitive deficit is associated with oxidative damage, especially with inhibition of the enzyme delta-aminolevulinate dehydratase (ALA-D), as well as to verify the influence of some metals in the enzyme activity and cognitive performance. Blood ALA-D activity, essential (Fe, Zn, Cu, Se) and non-essential metals (Pb, Cd, Hg, As, Cr, Ni, V) were measured in 50 elderly and 20 healthy young subjects. Cognitive function was assessed by tests from Consortium to Establish a Registry for Alzheimer's Disease (CERAD) battery and other. The elderly group presented decreased ALA-D activity compared to the young group. The index of ALA-D reactivation was similar to both study groups, but negatively associated with metals. The mean levels of essential metals were within the reference values, while the most toxic metals were above them in both groups. Cognitive function impairments were observed in elderly group and were associated with decreased ALA-D activity, with lower levels of Se and higher levels of toxic metals (Hg and V). Results suggest that the reduced ALA-D activity in elderly can be an additional factor involved in cognitive decline, since its inhibition throughout life could lead to accumulation of the neurotoxic compound ALA. Toxic metals were found to contribute to cognitive decline and also to influence ALA-D reactivation.

  2. Are Delta-Aminolevulinate Dehydratase Inhibition and Metal Concentrations Additional Factors for the Age-Related Cognitive Decline?

    PubMed Central

    Baierle, Marília; Charão, Mariele F.; Göethel, Gabriela; Barth, Anelise; Fracasso, Rafael; Bubols, Guilherme; Sauer, Elisa; Campanharo, Sarah C.; Rocha, Rafael C. C.; Saint’Pierre, Tatiana D.; Bordignon, Suelen; Zibetti, Murilo; Trentini, Clarissa M.; Ávila, Daiana S.; Gioda, Adriana; Garcia, Solange C.

    2014-01-01

    Aging is often accompanied by cognitive impairments and influenced by oxidative status and chemical imbalances. Thus, this study was conducted to examine whether age-related cognitive deficit is associated with oxidative damage, especially with inhibition of the enzyme delta-aminolevulinate dehydratase (ALA-D), as well as to verify the influence of some metals in the enzyme activity and cognitive performance. Blood ALA-D activity, essential (Fe, Zn, Cu, Se) and non-essential metals (Pb, Cd, Hg, As, Cr, Ni, V) were measured in 50 elderly and 20 healthy young subjects. Cognitive function was assessed by tests from Consortium to Establish a Registry for Alzheimer’s Disease (CERAD) battery and other. The elderly group presented decreased ALA-D activity compared to the young group. The index of ALA-D reactivation was similar to both study groups, but negatively associated with metals. The mean levels of essential metals were within the reference values, while the most toxic metals were above them in both groups. Cognitive function impairments were observed in elderly group and were associated with decreased ALA-D activity, with lower levels of Se and higher levels of toxic metals (Hg and V). Results suggest that the reduced ALA-D activity in elderly can be an additional factor involved in cognitive decline, since its inhibition throughout life could lead to accumulation of the neurotoxic compound ALA. Toxic metals were found to contribute to cognitive decline and also to influence ALA-D reactivation. PMID:25329536

  3. Chemically Reversible Reactions of Hydrogen Sulfide with Metal Phthalocyanines

    PubMed Central

    2015-01-01

    Hydrogen sulfide (H2S) is an important signaling molecule that exerts action on various bioinorganic targets. Despite this importance, few studies have investigated the differential reactivity of the physiologically relevant H2S and HS– protonation states with metal complexes. Here we report the distinct reactivity of H2S and HS– with zinc(II) and cobalt(II) phthalocyanine (Pc) complexes and highlight the chemical reversibility and cyclability of each metal. ZnPc reacts with HS–, but not H2S, to generate [ZnPc-SH]−, which can be converted back to ZnPc by protonation. CoPc reacts with HS–, but not H2S, to form [CoIPc]−, which can be reoxidized to CoPc by air. Taken together, these results demonstrate the chemically reversible reaction of HS– with metal phthalocyanine complexes and highlight the importance of H2S protonation state in understanding the reactivity profile of H2S with biologically relevant metal scaffolds. PMID:24785654

  4. Tattoo inks: legislation, pigments, metals and chemical analysis.

    PubMed

    Prior, Gerald

    2015-01-01

    Legal limits for chemical substances require that they are linked to clearly defined analytical methods. Present limits for certain chemicals in tattoo and permanent make-up inks do not mention analytical methods for the detection of metals, polycyclic aromatic hydrocarbons or forbidden colourants. There is, therefore, no established method for the determination of the quantities of these chemicals in tattoo and permanent make-up inks. Failing to provide an appropriate method may lead to unqualified and questionable results which often cause legal disputes that are ultimately resolved by a judge with regard to the method that should have been applied. Analytical methods are tuned to exactly what is to be found and what causes the health problems. They are extremely specific. Irrespective of which is the correct method for detecting metals in tattoo inks, the focus should be on the actual amounts of ink in the skin. CTL® has conducted experiments to determine these amounts and these experiments are crucial for toxicological evaluations and for setting legal limits. When setting legal limits, it is essential to also incorporate factors such as daily consumption, total uptake and frequency of use. A tattoo lasts for several decades; therefore, the limits that have been established for heavy metals used in drinking water or soap are not relevant. Drinking water is consumed on a daily basis and soap is used several times per week, while tattooing only occurs once.

  5. The Coupled Photothermal Reaction and Transport in a Laser Additive Metal Nanolayer Simultaneous Synthesis and Pattering for Flexible Electronics.

    PubMed

    Tsai, Song-Ling; Liu, Yi-Kai; Pan, Heng; Liu, Chien-Hung; Lee, Ming-Tsang

    2016-01-08

    The Laser Direct Synthesis and Patterning (LDSP) technology has advantages in terms of processing time and cost compared to nanomaterials-based laser additive microfabrication processes. In LDSP, a scanning laser on the substrate surface induces chemical reactions in the reactive liquid solution and selectively deposits target material in a preselected pattern on the substrate. In this study, we experimentally investigated the effect of the processing parameters and type and concentration of the additive solvent on the properties and growth rate of the resulting metal film fabricated by this LDSP technology. It was shown that reactive metal ion solutions with substantial viscosity yield metal films with superior physical properties. A numerical analysis was also carried out the first time to investigate the coupled opto-thermo-fluidic transport phenomena and the effects on the metal film growth rate. To complete the simulation, the optical properties of the LDSP deposited metal film with a variety of thicknesses were measured. The characteristics of the temperature field and the thermally induced flow associated with the moving heat source are discussed. It was shown that the processing temperature range of the LDSP is from 330 to 390 K. A semi-empirical model for estimating the metal film growth rate using this process was developed based on these results. From the experimental and numerical results, it is seen that, owing to the increased reflectivity of the silver film as its thickness increases, the growth rate decreases gradually from about 40 nm at initial to 10 nm per laser scan after ten scans. This self-controlling effect of LDSP process controls the thickness and improves the uniformity of the fabricated metal film. The growth rate and resulting thickness of the metal film can also be regulated by adjustment of the processing parameters, and thus can be utilized for controllable additive nano/microfabrication.

  6. The Coupled Photothermal Reaction and Transport in a Laser Additive Metal Nanolayer Simultaneous Synthesis and Pattering for Flexible Electronics

    PubMed Central

    Tsai, Song-Ling; Liu, Yi-Kai; Pan, Heng; Liu, Chien-Hung; Lee, Ming-Tsang

    2016-01-01

    The Laser Direct Synthesis and Patterning (LDSP) technology has advantages in terms of processing time and cost compared to nanomaterials-based laser additive microfabrication processes. In LDSP, a scanning laser on the substrate surface induces chemical reactions in the reactive liquid solution and selectively deposits target material in a preselected pattern on the substrate. In this study, we experimentally investigated the effect of the processing parameters and type and concentration of the additive solvent on the properties and growth rate of the resulting metal film fabricated by this LDSP technology. It was shown that reactive metal ion solutions with substantial viscosity yield metal films with superior physical properties. A numerical analysis was also carried out the first time to investigate the coupled opto-thermo-fluidic transport phenomena and the effects on the metal film growth rate. To complete the simulation, the optical properties of the LDSP deposited metal film with a variety of thicknesses were measured. The characteristics of the temperature field and the thermally induced flow associated with the moving heat source are discussed. It was shown that the processing temperature range of the LDSP is from 330 to 390 K. A semi-empirical model for estimating the metal film growth rate using this process was developed based on these results. From the experimental and numerical results, it is seen that, owing to the increased reflectivity of the silver film as its thickness increases, the growth rate decreases gradually from about 40 nm at initial to 10 nm per laser scan after ten scans. This self-controlling effect of LDSP process controls the thickness and improves the uniformity of the fabricated metal film. The growth rate and resulting thickness of the metal film can also be regulated by adjustment of the processing parameters, and thus can be utilized for controllable additive nano/microfabrication.

  7. Metals Additive ManufacturingGreat Promise in Mitigating Shortages but Some Risks Remain

    DTIC Science & Technology

    2016-12-01

    Defense AT&L: November-December 2016 38 Metals Additive Manufacturing Great Promise in Mitigating Shortages but Some Risks Remain Drew Miller n...initiatives such as establishing “Amer- ica Makes”—the National Additive Manufacturing Innovation Institute—and funding some AM-related Manufacturing Tech...NIST) is funding research to pro- vide quality assurance of AM parts. The DoD Metals Additive Manufacturing Qualification and Certification Working

  8. Transition-Metal Additives For Long-Life Na/NiCI(2) Cells

    NASA Technical Reports Server (NTRS)

    Bugga, Ratnakumar V.; Surampudi, Subbarao; Halpert, Gerald

    1995-01-01

    Transition-metal additives in cathodes of Na/NiCI(2) high-temperature, rechargeable electrochemical cells found to slow premature fading of charge/discharge capacity. Decline in capacity of cell attributed to agglomeration of Ni particles at cathode: this agglomeration reduces electrochemical area of cathode. Depending on choice of transition-metal additive for particular cell, additive might even participate in desired electrochemical reactions in cell, contributing to specific energy of cell.

  9. Effects of Metal Powder Addition in Ni-Sheathed PIT MgB2 Tapes

    NASA Astrophysics Data System (ADS)

    Tachikawa, K.; Yamada, Y.; Katagiri, K.; Kumakura, H.; Iwamoto, A.; Watanabe, K.

    2004-06-01

    The effect of different metal powder additions on the transport current and stress/strain performance of ex-situ processed MgB2 tapes with Ni sheath has been studied. The metal powder added to the core exhibits elongated morphology after the fabrication. The addition of low melting point metal powder, e.g. In and Sn, produces an appreciable increase in the Jc of MgB2 core. An addition of 10 vol% In enhances Jc by a factor of 6 to 7 after the combination of rolling and annealing at 200 °C, up to the order of 105 A/cm2 at 0.5 T and 4.2 K. An addition of 10 vol% Sn enhances Jc by a factor of ˜ 3. The In and Sn additions also appreciably increase the n-value of the current-voltage transition. Both In and Sn metals infiltrate into gaps between MgB2 grains, improving the linkage of the grains. Current may transfer through the impregnated metal by the proximity effect. Furthermore, the metal powder addition appreciably improves the strain tolerance in MgB2 tapes. The low melting point metal powder addition is a relatively simple and easy approach to yield better transport current and stress/strain performance in ex-situ MgB2 tapes.

  10. Experimental study of combustion characteristics of nanoscale metal and metal oxide additives in biofuel (ethanol)

    PubMed Central

    2011-01-01

    An experimental investigation of the combustion behavior of nano-aluminum (n-Al) and nano-aluminum oxide (n-Al2O3) particles stably suspended in biofuel (ethanol) as a secondary energy carrier was conducted. The heat of combustion (HoC) was studied using a modified static bomb calorimeter system. Combustion element composition and surface morphology were evaluated using a SEM/EDS system. N-Al and n-Al2O3 particles of 50- and 36-nm diameters, respectively, were utilized in this investigation. Combustion experiments were performed with volume fractions of 1, 3, 5, 7, and 10% for n-Al, and 0.5, 1, 3, and 5% for n-Al2O3. The results indicate that the amount of heat released from ethanol combustion increases almost linearly with n-Al concentration. N-Al volume fractions of 1 and 3% did not show enhancement in the average volumetric HoC, but higher volume fractions of 5, 7, and 10% increased the volumetric HoC by 5.82, 8.65, and 15.31%, respectively. N-Al2O3 and heavily passivated n-Al additives did not participate in combustion reactively, and there was no contribution from Al2O3 to the HoC in the tests. A combustion model that utilized Chemical Equilibrium with Applications was conducted as well and was shown to be in good agreement with the experimental results. PMID:21711760

  11. Effect of metal spiking on different chemical pools and chemically extractable fractions of heavy metals in sewage sludge.

    PubMed

    Kandpal, Geeta; Ram, Bali; Srivastava, P C; Singh, S K

    2004-01-30

    A laboratory experiment was conducted to study the effect of metal spiking and incubation on some properties and sequentially extractable chemical pools of some heavy metals (F1, two extractions with 0.1 M Sr(NO3)2; F2, one extraction with 1 M NaOAc (pH 5.0); F3, three extractions with 5% NaOCl (pH 8.5) at 90-95 degrees C; F4, three extractions with 0.2 M oxalic acid + 0.2 M ammonium oxalate + 0.1 M ascorbic acid (pH 3.0); and F5, dissolution of sample residue in HF-HClO4 (residual fraction,) and also 1 M CaCl2 and 0.005 M DTPA extractable heavy metals in sewage sludge. Metal spiking and incubation decreased pH and easily oxidizable organic C content of sludge but increased electrical conductivity. Metal spiking and incubation increased F1 fraction of all heavy metals, F2 fraction of Ni, Pb, Cu, and Cd, F3 fraction of Pb, Cu, and Cd, F4 or reducible fraction of Ni, Cu, and Cd and residual fraction of Zn and Pb, but decreased F2 fraction of Zn, F3 of Zn and Ni, F4 fraction of Zn and F5 fraction of Ni, Cu, and Cd. Metal spiking and incubation increased 1 M CaCl2 and 0.005 M DTPA extractable amounts of all heavy metals in sludge except for 0.005 M DTPA extractable Zn, which registered only very marginal decrease.

  12. Chemical mutagenesis--a promising technique to increase metal concentration and extraction in sunflowers.

    PubMed

    Nehnevajova, Erika; Herzig, Rolf; Federer, Guido; Erismann, Karl-Hans; Schwitzguébel, Jean-Paul

    2007-01-01

    Since most of the metal-hyperaccumulating wild plants only produce very low biomass and many high-yielding crops accumulate only moderate amounts of metals, the current research is mainly focused on overcoming these limitations and the optimization of metal phytoextraction. The main goal of the present study was the improvement of metal concentration and extraction properties of Helianthus annuus L by chemical mutagenesis (the non-GMO approach). Sunflowers--hybrid cultivar Salut and inbred lines-were treated with the chemical mutagen ethyl methanesulfonate (EMS). The effect of chemical mutagenesis on metal concentration in and extraction by new sunflower M1 and M2 mutants was directly assessed on a metal-contaminated field in Raft, Switzerland. Mutants of the M2 generation showed a 2-3 times higher metal shoot concentration than the control plants. The best M2 sunflower "giant mutant" 14/185/04 showed a significantly enhanced metal extraction ability: 7.5 times for Cd, 9.2 times for Zn, and 8.2 times for Pb in aboveground parts, as compared to the control plants. Theoretical calculations for the phytoextraction potential of new sunflower variants note that the best sunflower mutant can produce up to 26 t dry matter per hectare and remove 13.3 kg Zn per hectare and year at the sewage sludge contaminated site of Raft; that is a gain factor of 9 compared to Zn extraction by sunflower controls. Furthermore, the use of sunflower oil and biomass for technical purposes (lubricants, biodiesel, biogas) should produce an additional value and improve the economical balance of phytoextraction.

  13. Colloidal metal oxide nanocrystal catalysis by sustained chemically driven ligand displacement.

    PubMed

    De Roo, Jonathan; Van Driessche, Isabel; Martins, José C; Hens, Zeger

    2016-05-01

    Surface chemistry is a key enabler for colloidal nanocrystal applications. In this respect, metal oxide nanocrystals (NCs) stand out from other NCs as carboxylic acid ligands adsorb on their surface by dissociation to carboxylates and protons, the latter proving essential in electron transfer reactions. Here, we show that this binding motif sets the stage for chemically driven ligand displacement where the binding of amines or alcohols to HfO2 NCs is promoted by the conversion of a bound carboxylic acid into a non-coordinating amide or ester. Furthermore, the sustained ligand displacement, following the addition of excess carboxylic acid, provides a catalytic pathway for ester formation, whereas the addition of esters leads to NC-catalysed transesterification. Because sustained, chemically driven ligand displacement leaves the NCs-including their surface composition-unchanged and preserves colloidal stability, metal oxide nanocrystals are thus turned into effective nanocatalysts that bypass the tradeoff between colloidal stability and catalytic activity.

  14. Colloidal metal oxide nanocrystal catalysis by sustained chemically driven ligand displacement

    NASA Astrophysics Data System (ADS)

    de Roo, Jonathan; van Driessche, Isabel; Martins, José C.; Hens, Zeger

    2016-05-01

    Surface chemistry is a key enabler for colloidal nanocrystal applications. In this respect, metal oxide nanocrystals (NCs) stand out from other NCs as carboxylic acid ligands adsorb on their surface by dissociation to carboxylates and protons, the latter proving essential in electron transfer reactions. Here, we show that this binding motif sets the stage for chemically driven ligand displacement where the binding of amines or alcohols to HfO2 NCs is promoted by the conversion of a bound carboxylic acid into a non-coordinating amide or ester. Furthermore, the sustained ligand displacement, following the addition of excess carboxylic acid, provides a catalytic pathway for ester formation, whereas the addition of esters leads to NC-catalysed transesterification. Because sustained, chemically driven ligand displacement leaves the NCs--including their surface composition--unchanged and preserves colloidal stability, metal oxide nanocrystals are thus turned into effective nanocatalysts that bypass the tradeoff between colloidal stability and catalytic activity.

  15. Metal-enhanced chemiluminescence: Radiating plasmons generated from chemically induced electronic excited states

    NASA Astrophysics Data System (ADS)

    Chowdhury, Mustafa H.; Aslan, Kadir; Malyn, Stuart N.; Lakowicz, Joseph R.; Geddes, Chris D.

    2006-04-01

    In this letter, we report the observation of metal-enhanced chemiluminescence. Silver Island films, in close proximity to chemiluminescence species, can significantly enhance luminescence intensities; a 20-fold increase in chemiluminescence intensity was observed as compared to an identical control sample containing no silver. This suggests the use of silver nanostructures in the chemiluminescence-based immunoassays used in the biosciences today, to improve signal and therefore analyte detectability. In addition, this finding suggests that surface plasmons can be directly excited by chemically induced electronically excited luminophores, a significant finding toward our understanding of fluorophore-metal interactions and the generation of surface plasmons.

  16. Seeded growth of metal-doped plasmonic oxide heterodimer nanocrystals and their chemical transformation.

    PubMed

    Ye, Xingchen; Reifsnyder Hickey, Danielle; Fei, Jiayang; Diroll, Benjamin T; Paik, Taejong; Chen, Jun; Murray, Christopher B

    2014-04-02

    We have developed a generalized seeded-growth methodology for the synthesis of monodisperse metal-doped plasmonic oxide heterodimer nanocrystals (NCs) with a near-unity morphological yield. Using indium-doped cadmium oxide (ICO) as an example, we show that a wide variety of preformed metal NCs (Au, Pt, Pd, FePt, etc.) can serve as the seeds for the tailored synthesis of metal-ICO heterodimers with exquisite size, shape, and composition control, facilitated by the delayed nucleation mechanism of the CdO phase. The metal-ICO heterodimers exhibit broadly tunable near-infrared localized surface plasmon resonances, and dual plasmonic bands are observed for Au-ICO heterodimers. We further demonstrate that the oxide domain of the Au-ICO heterodimers can be selectively and controllably transformed into a series of partially and completely hollow cadmium chalcogenide nanoarchitectures with unprecedented structural complexity, leaving the metal domain intact. Our work not only represents an exciting addition to the rapidly expanding library of chemical reactions that produce colloidal hybrid NCs, but it also provides a general route for the bottom-up chemical design of multicomponent metal-oxide-semiconductor NCs in a rational and sequential manner.

  17. Electroactive Nanoporous Metal Oxides and Chalcogenides by Chemical Design

    PubMed Central

    2017-01-01

    The archetypal silica- and aluminosilicate-based zeolite-type materials are renowned for wide-ranging applications in heterogeneous catalysis, gas-separation and ion-exchange. Their compositional space can be expanded to include nanoporous metal chalcogenides, exemplified by germanium and tin sulfides and selenides. By comparison with the properties of bulk metal dichalcogenides and their 2D derivatives, these open-framework analogues may be viewed as three-dimensional semiconductors filled with nanometer voids. Applications exist in a range of molecule size and shape discriminating devices. However, what is the electronic structure of nanoporous metal chalcogenides? Herein, materials modeling is used to describe the properties of a homologous series of nanoporous metal chalcogenides denoted np-MX2, where M = Si, Ge, Sn, Pb, and X = O, S, Se, Te, with Sodalite, LTA and aluminum chromium phosphate-1 structure types. Depending on the choice of metal and anion their properties can be tuned from insulators to semiconductors to metals with additional modification achieved through doping, solid solutions, and inclusion (with fullerene, quantum dots, and hole transport materials). These systems form the basis of a new branch of semiconductor nanochemistry in three dimensions. PMID:28572706

  18. Feasibility Study on 3-D Printing of Metallic Structural Materials with Robotized Laser-Based Metal Additive Manufacturing

    NASA Astrophysics Data System (ADS)

    Ding, Yaoyu; Kovacevic, Radovan

    2016-07-01

    Metallic structural materials continue to open new avenues in achieving exotic mechanical properties that are naturally unavailable. They hold great potential in developing novel products in diverse industries such as the automotive, aerospace, biomedical, oil and gas, and defense. Currently, the use of metallic structural materials in industry is still limited because of difficulties in their manufacturing. This article studied the feasibility of printing metallic structural materials with robotized laser-based metal additive manufacturing (RLMAM). In this study, two metallic structural materials characterized by an enlarged positive Poisson's ratio and a negative Poisson's ratio were designed and simulated, respectively. An RLMAM system developed at the Research Center for Advanced Manufacturing of Southern Methodist University was used to print them. The results of the tensile tests indicated that the printed samples successfully achieved the corresponding mechanical properties.

  19. Late Chondritic Additions and Planet and Planetesimal Growth: Evaluation of Physical and Chemical Mechanisms

    NASA Technical Reports Server (NTRS)

    Righter, Kevin

    2013-01-01

    Studies of terrestrial peridotite and martian and achondritic meteorites have led to the conclusion that addition of chondritic material to growing planets or planetesimals, after core formation, occurred on Earth, Mars, asteroid 4 Vesta, and the parent body of the angritic meteorites [1-4]. One study even proposed that this was a common process in the final stages of growth [5]. These conclusions are based almost entirely on the highly siderophile elements (HSE; Re, Au, Pt, Pd, Rh, Ru, Ir, Os). The HSE are a group of eight elements that have been used to argue for late accretion of chondritic material to the Earth after core formation was complete (e.g., [6]). This idea was originally proposed because the D(metal/silicate) values for the HSE are so high, yet their concentration in the mantle is too high to be consistent with such high Ds. The HSE also are present in chondritic relative abundances and hence require similar Ds if this is the result of core-mantle equilibration. Since the work of [6] there has been a realization that core formation at high PT conditions can explain the abundances of many siderophile elements in the mantle (e.g., [7]), but such detailed high PT partitioning data are lacking for many of the HSE to evaluate whether such ideas are viable for all four bodies. Consideration of other chemical parameters reveals larger problems that are difficult to overcome, but must be addressed in any scenario which calls on the addition of chondritic material to a reduced mantle. Yet these problems are rarely discussed or emphasized, making the late chondritic (or late veneer) addition hypothesis suspect.

  20. Bulk micromachining of Si by metal-assisted chemical etching.

    PubMed

    Kim, Sang-Mi; Khang, Dahl-Young

    2014-09-24

    Bulk micromachining of Si is demonstrated by the well-known metal-assisted chemical etching (MaCE). Si microstructures, having lateral dimension from 5 μm up to millimeters, are successfully sculpted deeply into Si substrate, as deep as >100 μm. The key ingredient of this success is found to be the optimizations of catalyst metal type and its morphology. Combining the respective advantages of Ag and Au in the MaCE as a Ag/Au bilayer configuration leads to quite stable etch reaction upon a prolonged etch duration up to >5 h. Further, the permeable nature of the optimized Ag/Au bilayer metal catalyst enables the etching of pattern features having very large lateral dimension. Problems such as the generation of micro/nanostructures and chemical attacks on the top of pattern surface are successfully overcome by process optimizations such as post-partum sonication treatment and etchant formulation control. The method can also be successful to vertical micromachining of Si substrate having other crystal orientations than Si(100), such as Si(110) and Si(111). The simple, easy, and low-cost nature of present approach may be a great help in bulk micromachining of Si for various applications such as microelectromechanical system (MEMS), micro total analysis system (μTAS), and so forth. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Reduction of spalling in mixed metal oxide desulfurization sorbents by addition of a large promoter metal oxide

    DOEpatents

    Poston, James A.

    1997-01-01

    Mixed metal oxide pellets for removing hydrogen sulfide from fuel gas mixes derived from coal are stabilized for operation over repeated cycles of desulfurization and regeneration reactions by addition of a large promoter metal oxide such as lanthanum trioxide. The pellets, which may be principally made up of a mixed metal oxide such as zinc titanate, exhibit physical stability and lack of spalling or decrepitation over repeated cycles without loss of reactivity. The lanthanum oxide is mixed with pellet-forming components in an amount of 1 to 10 weight percent.

  2. Reduction of spalling in mixed metal oxide desulfurization sorbents by addition of a large promoter metal oxide

    DOEpatents

    Poston, J.A.

    1997-12-02

    Mixed metal oxide pellets for removing hydrogen sulfide from fuel gas mixes derived from coal are stabilized for operation over repeated cycles of desulfurization and regeneration reactions by addition of a large promoter metal oxide such as lanthanum trioxide. The pellets, which may be principally made up of a mixed metal oxide such as zinc titanate, exhibit physical stability and lack of spalling or decrepitation over repeated cycles without loss of reactivity. The lanthanum oxide is mixed with pellet-forming components in an amount of 1 to 10 weight percent.

  3. Chemical metallization of KMPR photoresist polymer in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Zeb, Gul; Duong, Xuan Truong; Vu, Ngoc Pi; Phan, Quang The; Nguyen, Duc Tuong; Ly, Viet Anh; Salimy, Siamak; Le, Xuan Tuan

    2017-06-01

    While conventional methods for preparing thin films of metals and metallic alloys on insulating substrates in the field of microelectromechanical systems (MEMS) include vapor deposition techniques, we demonstrate here that electroless deposition can be considered as an alternate efficient approach to metallize the surface of insulating substrates, such as KMPR epoxy photoresist polymer. In comparison with the physical and chemical vapor deposition methods, which are well-established for metallization of photoresist polymers, our electroless nickel plating requires only immersing the substrates into aqueous solutions in open air at low temperatures. Thin films of nickel alloy have been deposited electrolessly on KMPR surface, through a cost-effective and environmental chromium-free process, mediated through direct grafting of amine palladium complexes in aqueous medium. This covalent organic coating provides excellent adhesion between KMPR and the nickel film and allows better control of the palladium catalyst content. Covalent grafting and characterization of the deposited nickel film have been carried out by means of Fourier-transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy techniques.

  4. Residual metallic contamination of transferred chemical vapor deposited graphene.

    PubMed

    Lupina, Grzegorz; Kitzmann, Julia; Costina, Ioan; Lukosius, Mindaugas; Wenger, Christian; Wolff, Andre; Vaziri, Sam; Östling, Mikael; Pasternak, Iwona; Krajewska, Aleksandra; Strupinski, Wlodek; Kataria, Satender; Gahoi, Amit; Lemme, Max C; Ruhl, Guenther; Zoth, Guenther; Luxenhofer, Oliver; Mehr, Wolfgang

    2015-05-26

    Integration of graphene with Si microelectronics is very appealing by offering a potentially broad range of new functionalities. New materials to be integrated with the Si platform must conform to stringent purity standards. Here, we investigate graphene layers grown on copper foils by chemical vapor deposition and transferred to silicon wafers by wet etching and electrochemical delamination methods with respect to residual submonolayer metallic contaminations. Regardless of the transfer method and associated cleaning scheme, time-of-flight secondary ion mass spectrometry and total reflection X-ray fluorescence measurements indicate that the graphene sheets are contaminated with residual metals (copper, iron) with a concentration exceeding 10(13) atoms/cm(2). These metal impurities appear to be partially mobile upon thermal treatment, as shown by depth profiling and reduction of the minority charge carrier diffusion length in the silicon substrate. As residual metallic impurities can significantly alter electronic and electrochemical properties of graphene and can severely impede the process of integration with silicon microelectronics, these results reveal that further progress in synthesis, handling, and cleaning of graphene is required to advance electronic and optoelectronic applications.

  5. 3D Metal Printing - Additive Manufacturing Technologies for Frameworks of Implant-Borne Fixed Dental Prosthesis.

    PubMed

    Revilla León, M; Klemm, I M; García-Arranz, J; Özcan, M

    2017-09-01

    An edentulous patient was rehabilitated with maxillary metal-ceramic and mandibular metal-resin implant-supported fixed dental prosthesis (FDP). Metal frameworks of the FDPs were fabricated using 3D additive manufacturing technologies utilizing selective laser melting (SLM) and electron beam melting (EBM) processes. Both SLM and EBM technologies were employed in combination with computer numerical control (CNC) post-machining at the implant interface. This report highlights the technical and clinical protocol for fabrication of FDPs using SLM and EBM additive technologies. Copyright© 2017 Dennis Barber Ltd.

  6. Chemical and spectroscopic studies of metal oxide surfaces

    SciTech Connect

    Goodman, D.W.

    1996-05-01

    Thin oxide films (e.g., 5{endash}10 nm of SiO{sub 2}, Al{sub 2}O{sub 3}, NiO, MgO) supported on a refractory metal substrate (e.g., Mo, W, Ta, Re) have been prepared by deposition of the oxide metal precursor in a background of oxygen. The thin-film nature of these samples facilitates investigation by an array of surface techniques, many of which cannot be effectively utilized on the corresponding bulk oxide. The structural, electronic, and chemical properties of these films have been studied with temperature programmed desorption, Auger electron spectroscopy, X-ray photoelectron spectroscopy, ion scattering spectroscopy, high resolution electron energy loss spectroscopy, and infrared reflection absorption spectroscopy. The results of these studies demonstrate the viability of using thin oxide films as models for the corresponding bulk oxide. {copyright} {ital 1996 American Vacuum Society}

  7. Chemical and electrochemical interactions on corroding metal surfaces

    SciTech Connect

    Isaacs, H.S.; Aldykiewicz, A.J. Jr.

    1994-10-01

    The corrosion resistance of many metals and alloys depend on their ability to repassivate after breakdown of the passive film. Following breakdown localized corrosion takes place. The consequences of initiation events depends on many factors leading to a dissolution rate of the metal which may be continuous, intermittent or transitory. Major changes in the solution chemistry at the breakdown site must take place to enable active dissolution to take place and prevent repassivation. However, mass transfer of the dissolution products to the bulk environment often plays a decisive role. The composition of the environment is important. Some species inhibit while others stimulate the anodic dissolution. In the presence of particular cations, deposition slowly takes place on cathodic sites. Current density mapping measurements have been used to study pitting processes on iron and aluminum alloys. The effects of phosphate as an anodic inhibitor for steel and cerium as a cathodic inhibitor for aluminum are discussed in conjunction with related chemical processes.

  8. Chemical vapor deposition of ceramic coatings on metals and ceramic fibers

    NASA Astrophysics Data System (ADS)

    Nable, Jun Co

    2005-07-01

    The research presented in this study consists of two major parts. The first part is about the development of ceramic coatings on metals by chemical vapor deposition (CVD) and metal-organic chemical vapor deposition (MOCVD). Ceramics such as Al2O3 and Cr2O3, are used as protective coatings for materials used at elevated temperatures (>700°C). These metal oxides either exhibit oxidation resistance or have been used as environmental bond coats. Conventional methods of coating by chemical vapor deposition requires deposition temperatures of >950°C which could damage the substrate material during the coating process. Lower deposition temperatures (400 to 600°C) by MOCVD of these metal oxides were successful on Ni metal substrates. Surface modification such as pre-oxidation and etching were also investigated. In addition, a novel approach for the CVD of TiN on metals was developed. This new approach utilizes ambient pressure conditions which lead to deposition temperatures of 800°C or lower compared to conventional CVD of TiN at 1000°C. Titanium nitride can be used as an abrasive and wear coating on cutting and grinding tools. This nitride can also serve as a diffusion coating in metals. The second major part of this research involves the synthesis of interfacial coatings on ceramic reinforcing fibers for ceramic matrix composites. Aluminum and chromium oxides were deposited onto SiC, and Al2O3-SiO 2 fibers by MOCVD. The effects of the interface coatings on the tensile strength of ceramic fibers are also discussed. New duplex interface coatings consisting of BN or TiN together with Al2O3 or ZrO 2 were also successfully deposited and evaluated on SiC fibers.

  9. On the chemical state and distribution of Zr- and V-based additives in reactive hydride composites

    NASA Astrophysics Data System (ADS)

    Bösenberg, U.; Vainio, U.; Pranzas, P. K.; Bellosta von Colbe, J. M.; Goerigk, G.; Welter, E.; Dornheim, M.; Schreyer, A.; Bormann, R.

    2009-05-01

    Reactive hydride composites (RHCs) are very promising hydrogen storage materials for future applications due to their reduced reaction enthalpies and high gravimetric capacities. At present, the materials' functionality is limited by the reaction kinetics. A significant positive influence can be observed with addition of transition-metal-based additives. To understand the effect of these additives, the chemical state and changes during the reaction as well as the microstructural distribution were investigated using x-ray absorption near-edge structure (XANES) spectroscopy and anomalous small-angle x-ray scattering (ASAXS). In this work, zirconium- and vanadium-based additives were added to 2LiBH4-MgH2 composites and 2LiH-MgB2 composites and measured in the vicinity of the corresponding absorption edge. The measurements reveal the formation of finely distributed zirconium diboride and vanadium-based nanoparticles. The potential mechanisms for the observed influence on the reaction kinetics are discussed.

  10. On the chemical state and distribution of Zr- and V-based additives in reactive hydride composites.

    PubMed

    Bösenberg, U; Vainio, U; Pranzas, P K; von Colbe, J M Bellosta; Goerigk, G; Welter, E; Dornheim, M; Schreyer, A; Bormann, R

    2009-05-20

    Reactive hydride composites (RHCs) are very promising hydrogen storage materials for future applications due to their reduced reaction enthalpies and high gravimetric capacities. At present, the materials' functionality is limited by the reaction kinetics. A significant positive influence can be observed with addition of transition-metal-based additives. To understand the effect of these additives, the chemical state and changes during the reaction as well as the microstructural distribution were investigated using x-ray absorption near-edge structure (XANES) spectroscopy and anomalous small-angle x-ray scattering (ASAXS). In this work, zirconium- and vanadium-based additives were added to 2LiBH4-MgH2 composites and 2LiH-MgB2 composites and measured in the vicinity of the corresponding absorption edge. The measurements reveal the formation of finely distributed zirconium diboride and vanadium-based nanoparticles. The potential mechanisms for the observed influence on the reaction kinetics are discussed.

  11. Aerosol chemical vapor deposition of metal oxide films

    DOEpatents

    Ott, K.C.; Kodas, T.T.

    1994-01-11

    A process of preparing a film of a multicomponent metal oxide including: forming an aerosol from a solution comprised of a suitable solvent and at least two precursor compounds capable of volatilizing at temperatures lower than the decomposition temperature of said precursor compounds; passing said aerosol in combination with a suitable oxygen-containing carrier gas into a heated zone, said heated zone having a temperature sufficient to evaporate the solvent and volatilize said precursor compounds; and passing said volatilized precursor compounds against the surface of a substrate, said substrate having a sufficient temperature to decompose said volatilized precursor compounds whereby metal atoms contained within said volatilized precursor compounds are deposited as a metal oxide film upon the substrate is disclosed. In addition, a coated article comprising a multicomponent metal oxide film conforming to the surface of a substrate selected from the group consisting of silicon, magnesium oxide, yttrium-stabilized zirconium oxide, sapphire, or lanthanum gallate, said multicomponent metal oxide film characterized as having a substantially uniform thickness upon said substrate.

  12. 9 CFR 381.120 - Antioxidants; chemical preservatives; and other additives.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 9 Animals and Animal Products 2 2011-01-01 2011-01-01 false Antioxidants; chemical preservatives... Labeling and Containers § 381.120 Antioxidants; chemical preservatives; and other additives. When an antioxidant is added to a poultry product, there shall appear on the label in prominent letters and...

  13. 9 CFR 381.120 - Antioxidants; chemical preservatives; and other additives.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 9 Animals and Animal Products 2 2010-01-01 2010-01-01 false Antioxidants; chemical preservatives... Labeling and Containers § 381.120 Antioxidants; chemical preservatives; and other additives. When an antioxidant is added to a poultry product, there shall appear on the label in prominent letters and...

  14. 9 CFR 381.120 - Antioxidants; chemical preservatives; and other additives.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 9 Animals and Animal Products 2 2013-01-01 2013-01-01 false Antioxidants; chemical preservatives... Labeling and Containers § 381.120 Antioxidants; chemical preservatives; and other additives. When an antioxidant is added to a poultry product, there shall appear on the label in prominent letters and...

  15. 9 CFR 381.120 - Antioxidants; chemical preservatives; and other additives.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 9 Animals and Animal Products 2 2014-01-01 2014-01-01 false Antioxidants; chemical preservatives... Labeling and Containers § 381.120 Antioxidants; chemical preservatives; and other additives. When an antioxidant is added to a poultry product, there shall appear on the label in prominent letters and...

  16. 9 CFR 381.120 - Antioxidants; chemical preservatives; and other additives.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 9 Animals and Animal Products 2 2012-01-01 2012-01-01 false Antioxidants; chemical preservatives... Labeling and Containers § 381.120 Antioxidants; chemical preservatives; and other additives. When an antioxidant is added to a poultry product, there shall appear on the label in prominent letters and contiguous...

  17. Effect of vermicomposting on concentration and speciation of heavy metals in sewage sludge with additive materials.

    PubMed

    He, Xin; Zhang, Yaxin; Shen, Maocai; Zeng, Guangming; Zhou, Mucen; Li, Meirong

    2016-10-01

    The aim of this work was to evaluate the total content and speciation of heavy metals (As, Cr, Cd, Cu, Fe, Mn, Ni, Pb and Zn) during vermicomposting of sewage sludge by Eisenia fetida earthworm with different additive materials (soil, straw, fly ash and sawdust). Results showed that the pH, total organic carbon were reduced, while the electric conductivity and germination index increased after a combined composting - vermicomposting process. The addition of bulking agents accelerated the stabilization of sludge and eliminated its toxicity. The total heavy metals after vermicomposting in 10 scenarios were lowered as compared with the initial values and the control without amendment. BCR sequential extraction indicated that vermicomposting significantly decreased the mobility of all heavy metals by increasing the residual fractions. The activity of earthworms and appropriate addition of amendment materials played a positive role in sequestering heavy metals during the treatment of sewage sludge. Copyright © 2016 Elsevier Ltd. All rights reserved.

  18. Effect of water treatment additives on lime softening residual trace chemical composition--implications for disposal and reuse.

    PubMed

    Cheng, Weizhi; Roessler, Justin; Blaisi, Nawaf I; Townsend, Timothy G

    2014-12-01

    Drinking water treatment residues (WTR) offer potential benefits when recycled through land application. The current guidance in Florida, US allows for unrestricted land application of lime softening WTR; alum and ferric WTR require additional evaluation of total and leachable concentrations of select trace metals prior to land application. In some cases a mixed WTR is produced when lime softening is accompanied by the addition of a coagulant or other treatment chemical; applicability of the current guidance is unclear. The objective of this research was to characterize the total and leachable chemical content of WTR from Florida facilities that utilize multiple treatment chemicals. Lime and mixed lime WTR samples were collected from 18 water treatment facilities in Florida. Total and leachable concentrations of the WTR were measured. To assess the potential for disposal of mixed WTR as clean fill below the water table, leaching tests were conducted at multiple liquid to solid ratios and under reducing conditions. The results were compared to risk-based soil and groundwater contamination thresholds. Total metal concentrations of WTR were found to be below Florida soil contaminant thresholds with Fe found in the highest abundance at a concentration of 3600 mg/kg-dry. Aluminum was the only element that exceeded the Florida groundwater contaminant thresholds using SPLP (95% UCL = 0.23 mg/L; risk threshold = 0.2 mg/L). Tests under reducing conditions showed elevated concentrations of Fe and Mn, ranging from 1 to 3 orders of magnitude higher than SPLP leachates. Mixed lime WTR concentrations (total and leachable) were lower than the ferric and alum WTR concentrations, supporting that mixed WTR are appropriately represented as lime WTR. Testing of WTR under reducing conditions demonstrated the potential for release of certain trace metals (Fe, Al, Mn) above applicable regulatory thresholds; additional evaluation is needed to assess management options where

  19. MIXTURES OF THYROID DISRUPTING CHEMICALS: TESTING ADDITIVITY OF HEPATIC INDUCERS AND THYROID PEROXIDASE INHIBITORS.

    EPA Science Inventory

    Humans are exposed to chemical mixtures via diet, occupation, and the environment. Previous data demonstrated that low doses of polycyclic halogenated aromatic hydrocarbons (PHAHs) acting through similar mechanisms result in an additive reduction of thyroxine (T4). If xenobioti...

  20. MIXTURES OF THYROID DISRUPTING CHEMICALS: TESTING ADDITIVITY OF HEPATIC INDUCERS AND THYROID PEROXIDASE INHIBITORS.

    EPA Science Inventory

    Humans are exposed to chemical mixtures via diet, occupation, and the environment. Previous data demonstrated that low doses of polycyclic halogenated aromatic hydrocarbons (PHAHs) acting through similar mechanisms result in an additive reduction of thyroxine (T4). If xenobioti...

  1. A new approach to NMR chemical shift additivity parameters using simultaneous linear equation method.

    PubMed

    Shahab, Yosif A; Khalil, Rabah A

    2006-10-01

    A new approach to NMR chemical shift additivity parameters using simultaneous linear equation method has been introduced. Three general nitrogen-15 NMR chemical shift additivity parameters with physical significance for aliphatic amines in methanol and cyclohexane and their hydrochlorides in methanol have been derived. A characteristic feature of these additivity parameters is the individual equation can be applied to both open-chain and rigid systems. The factors that influence the (15)N chemical shift of these substances have been determined. A new method for evaluating conformational equilibria at nitrogen in these compounds using the derived additivity parameters has been developed. Conformational analyses of these substances have been worked out. In general, the results indicate that there are four factors affecting the (15)N chemical shift of aliphatic amines; paramagnetic term (p-character), lone pair-proton interactions, proton-proton interactions, symmetry of alkyl substituents and molecular association.

  2. Chemical and biological properties of toxic metals and use of chelating agents for the pharmacological treatment of metal poisoning.

    PubMed

    Sinicropi, Maria Stefania; Amantea, Diana; Caruso, Anna; Saturnino, Carmela

    2010-07-01

    Exposure to toxic metals is a well-known problem in industrialized countries. Metals interfere with a number of physiological processes, including central nervous system (CNS), haematopoietic, hepatic and renal functions. In the evaluation of the toxicity of a particular metal it is crucial to consider many parameters: chemical forms (elemental, organic or inorganic), binding capability, presence of specific proteins that selectively bind metals, etc. Medical treatment of acute and chronic metal toxicity is provided by chelating agents, namely organic compounds capable of interacting with metal ions to form structures called chelates. The present review attempts to provide updated information about the mechanisms, the cellular targets and the effects of toxic metals.

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

    SciTech Connect

    LICHTENBERGER, DENNIS L.

    2002-03-26

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

  4. Chemical control of the sea lamprey: the addition of a chemical to the environment.

    PubMed

    Menzie, C M; Hunn, J B

    1976-01-01

    Construction of the Welland Canal enabled shipping to by-pass Niagara Falls and enter the upper Great Lakes and also eliminated the barrier to the entry to the lakes by the sea lamprey (Petromyzon marinus Linnaeus). Within forty years the commercial fisheries of the Great Lakes was almost eliminated by this parasitic cyclostome. A search for selective chemical control of the sea lamprey was undertaken in the 1950's and culminated with the discovery of TFM (3-Trifluoromethyl-4-nitrophenol). At the request of the International Great Lakes Fishery Commission, the Bureau of Sport Fisheries and Wildlife undertook to assess the hazard of TFM to the aquatic ecosystem, to humans as well as to fish and wildlife. Studies were undertaken in Bureau laboratories as well as by contracts with university and private laboratories. Results of these studies to-date indicate that this material is not subject to biomagnification and does not pose a hazard to man or the the environment.

  5. Chemical methods and phytoremediation of soil contaminated with heavy metals.

    PubMed

    Chen, H M; Zheng, C R; Tu, C; Shen, Z G

    2000-07-01

    The effects of chemical amendments (calcium carbonate (CC), steel sludge (SS) and furnace slag (FS)) on the growth and uptake of cadmium (Cd) by wetland rice, Chinese cabbage and wheat grown in a red soil contaminated with Cd were investigated using a pot experiment. The phytoremediation of heavy metal contaminated soil with vetiver grass was also studied in a field plot experiment. Results showed that treatments with CC, SS and FS decreased Cd uptake by wetland rice, Chinese cabbage and wheat by 23-95% compared with the unamended control. Among the three amendments, FS was the most efficient at suppressing Cd uptake by the plants, probably due to its higher content of available silicon (Si). The concentrations of zinc (Zn), lead (Pb) and Cd in the shoots of vetiver grass were 42-67%, 500-1200% and 120-260% higher in contaminated plots than in control, respectively. Cadmium accumulation by vetiver shoots was 218 g Cd/ha at a soil Cd concentration of 0.33 mg Cd/kg. It is suggested that heavy metal-contaminated soil could be remediated with a combination of chemical treatments and plants.

  6. Metal organic frameworks for the catalytic detoxification of chemical warfare nerve agents

    DOEpatents

    Hupp, Joseph T.; Farha, Omar K.; Katz, Michael J.; Mondloch, Joseph E.

    2017-04-18

    A method of using a metal organic framework (MOF) comprising a metal ion and an at least bidendate organic ligand to catalytically detoxify chemical warfare nerve agents including exposing the metal-organic-framework (MOF) to the chemical warfare nerve agent and catalytically decomposing the nerve agent with the MOF.

  7. Exploring biologically relevant chemical space with metal complexes.

    PubMed

    Meggers, Eric

    2007-06-01

    Altering biological processes with small synthetic molecules is a general approach for the design of drugs and molecular probes. Medicinal chemistry and chemical biology are focused predominately on the design of organic molecules, whereas inorganic compounds find applications mainly for their reactivity (e.g. cisplatin as a DNA-reactive therapeutic) or imaging properties (e.g. gadolinium complexes as MRI diagnostics). In such inorganic pharmaceuticals or probes, coordination chemistry in the biological environment or at the target site lies at the heart of their modes of action. However, past and very recent results suggest that it is also worth exploring a different aspect of metal complexes: their ability to form structures with unique and defined shapes for the design of 'organic-like' small-molecule probes and drugs. In such metal-organic compounds, the metal has the main purpose to organize the organic ligands in three-dimensional space. It is likely that such an approach will complement the molecular diversity of organic chemistry in the quest for the discovery of compounds with superior biological activities.

  8. The chemical evolution of globular clusters - II. Metals and fluorine

    NASA Astrophysics Data System (ADS)

    Sánchez-Blázquez, P.; Marcolini, A.; Gibson, B. K.; Karakas, A. I.; Pilkington, K.; Calura, F.

    2012-01-01

    In the first paper of this series, we proposed a new framework in which to model the chemical evolution of globular clusters. This model is predicated upon the assumption that clusters form within an interstellar medium enriched locally by the ejecta of a single Type Ia supernova and varying numbers of asymptotic giant branch stars, superimposed on an ambient medium pre-enriched by low-metallicity Type II supernovae. Paper I was concerned with the application of this model to the observed abundances of several reactive elements and so-called non-metals for three classical intermediate-metallicity clusters, with the hallmark of the work being the successful recovery of many of their well-known elemental and isotopic abundance anomalies. Here, we expand upon our initial analysis by (i) applying the model to a much broader range of metallicities (from the factor of 3 explored in Paper I, to now a factor of ˜50; i.e. essentially, the full range of Galactic globular cluster abundances; and (ii) incorporating a broader suite of chemical species, including a number of iron-peak isotopes, heavier α-elements and fluorine. While allowing for an appropriate fine-tuning of the model input parameters, most empirical globular cluster abundance trends are reproduced; our model would suggest the need for a higher production of calcium, silicon and copper in low-metallicity (or so-called 'prompt') Type Ia supernovae than predicted in current stellar models in order to reproduce the observed trends in NGC 6752, and a factor of 2 reduction in carbon production from asymptotic giant branch stars to explain the observed trends between carbon and nitrogen. Observations of heavy-element isotopes produced primarily by Type Ia supernovae, including those of titanium, iron and nickel, could support/refute unequivocally our proposed framework, although currently the feasibility of the proposed observations is well beyond current instrumental capabilities. Hydrodynamical simulations would

  9. Baade's window and APOGEE. Metallicities, ages, and chemical abundances

    NASA Astrophysics Data System (ADS)

    Schultheis, M.; Rojas-Arriagada, A.; García Pérez, A. E.; Jönsson, H.; Hayden, M.; Nandakumar, G.; Cunha, K.; Allende Prieto, C.; Holtzman, J. A.; Beers, T. C.; Bizyaev, D.; Brinkmann, J.; Carrera, R.; Cohen, R. E.; Geisler, D.; Hearty, F. R.; Fernandez-Tricado, J. G.; Maraston, C.; Minnitti, D.; Nitschelm, C.; Roman-Lopes, A.; Schneider, D. P.; Tang, B.; Villanova, S.; Zasowski, G.; Majewski, S. R.

    2017-03-01

    Context. Baade's window (BW) is one of the most observed Galactic bulge fields in terms of chemical abundances. Owing to its low and homogeneous interstellar absorption it is considered the perfect calibration field for Galactic bulge studies. Aims: In the era of large spectroscopic surveys, calibration fields such as BW are necessary for cross calibrating the stellar parameters and individual abundances of the APOGEE survey. Methods: We use the APOGEE BW stars to derive the metallicity distribution function (MDF) and individual abundances for α- and iron-peak elements of the APOGEE ASPCAP pipeline (DR13), as well as the age distribution for stars in BW. Results: We determine the MDF of APOGEE stars in BW and find a remarkable agreement with that of the Gaia-ESO survey (GES). Both exhibit a clear bimodal distribution. We also find that the Mg-metallicity planes of the two surveys agree well, except for the metal-rich part ([Fe/H] > 0.1), where APOGEE finds systematically higher Mg abundances with respect to the GES. The ages based on the [C/N] ratio reveal a bimodal age distribution, with a major old population at 10 Gyr, with a decreasing tail towards younger stars. A comparison of stellar parameters determined by APOGEE and those determined by other sources reveals detectable systematic offsets, in particular for spectroscopic surface gravity estimates. In general, we find a good agreement between individual abundances of O, Na, Mg, Al, Si, K, Ca, Cr, Mn, Co, and Ni from APOGEE with that of literature values. Conclusions: We have shown that in general APOGEE data show a good agreement in terms of MDF and individual chemical abundances with respect to literature works. Using the [C/N] ratio we found a significant fraction of young stars in BW.

  10. Effect of transition-metal additives on hydrogen desorption kinetics of MgH2

    NASA Astrophysics Data System (ADS)

    Roy, Anindya; Janotti, Anderson; Van de Walle, Chris G.

    2013-01-01

    Using first-principles calculations, we study the effect of transition-metal additives (Ti, Fe, Co, and Ni) on the rate of hydrogen desorption in MgH2. The presence of large concentrations of transition-metal impurities causes the Fermi level to shift according to the position of the transition-metal acceptor/donor levels in the band gap. This shift can lower the formation energy of native defects and increase their concentration. The resulting higher rates of hydrogen desorption enhance the prospect of MgH2 as a solid-state hydrogen-storage material.

  11. 76 FR 20992 - Sun Chemical Corp.; Filing of Color Additive Petition

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-04-14

    ... HUMAN SERVICES Food and Drug Administration Sun Chemical Corp.; Filing of Color Additive Petition AGENCY: Food and Drug Administration, HHS. ACTION: Notice. SUMMARY: The Food and Drug Administration (FDA) is... Director, Office of Food Additive Safety, Center for Food Safety and Applied Nutrition. BILLING CODE 4160...

  12. Using alternative chemicals in the flotation of heavy metals from lead mill tailings

    SciTech Connect

    Benn, F.W.

    1995-04-01

    The U.S. Bureau of Mines (USBM) investigated alternative chemicals for the flotation of heavy metal values from southeast Missouri lead mill tailings. The objectives of the study were to lower the Pb remaining in the reprocessed tailings to <500 ppm, concentrate the metal values, and lower the overall toxicity of the flotation reagent scheme. Due to the high toxicity of classic flotation chemicals, collectorless flotation, as well as nontoxic or less-toxic chemicals, was studied for use in the flotation process. The investigation centered on the National tailings pile in Flat River, MO. Advantages to using alternative chemicals for the flotation process are presented. Novel reagent schemes are discussed for the treatment of the tailings. Various nontoxic or less-toxic oils were tested, and a substitute for sodium sulfide was investigated. Using a food additive oil, soda ash, and a frother as the reagent scheme, froth flotation recovered 89% of the Pb values. Further scavenging lowered the Pb remaining in the reprocessed tailings to <500 ppm. A less-toxic substitute for sodium cyanide was also studied for use in the cleaner flotation stages. Preliminary results indicate that the food additive oil, canola oil, to be as effective as classic sulfide flotation reagents.

  13. Chemical activation of molecules by metals: Experimental studies of electron distributions and bonding

    SciTech Connect

    Lichtenberger, D.L.

    1991-10-01

    The formal relationship between measured molecular ionization energies and thermodynamic bond dissociation energies has been developed into a single equation which unifies the treatment of covalent bonds, ionic bonds, and partially ionic bonds. This relationship has been used to clarify the fundamental thermodynamic information relating to metal-hydrogen, metal-alkyl, and metal-metal bond energies. We have been able to obtain a direct observation and measurement of the stabilization energy provided by the agostic interaction of the C-H bond with the metal. The ionization energies have also been used to correlate the rates of carbonyl substitution reactions of ({eta}{sup 5}-C{sub 5}H{sub 4}X)Rh(CO){sub 2} complexes, and to reveal the electronic factors that control the stability of the transition state. The extent that the electronic features of these bonding interactions transfer to other chemical systems is being investigated in terms of the principle of additivity of ligand electronic effects. Specific examples under study include metal- phosphines, metal-halides, and metallocenes. Especially interesting has been the recent application of these techniques to the characterization of the soccer-ball shaped C{sub 60} molecule, buckminsterfullerene, and its interaction with a metal surface. The high-resolution valence ionizations in the gas phase reveal the high symmetry of the molecule, and studies of thin films of C{sub 60} reveal weak intermolecular interactions. Scanning tunneling and atomic force microscopy reveal the arrangement of spherical molecules on gold substrates, with significant delocalization of charge from the metal surface. 21 refs.

  14. Chemical vapor deposition of metal diboride and metal oxide thin films from borohydride-bonded precursors

    NASA Astrophysics Data System (ADS)

    Yang, Yu

    Metal borohydrides denotes the type of metal complex in which the metals are connected to the surrounding ligands through boron-hydrogen bridge bonds. They are excellent CVD precursors owning to their outstanding volatility and high reactivity. Transition metal diboride and metal oxide thin films suitable for various technological applications are deposited from these novel precursors. In this dissertation, comprehensive investigations of thin film growth rate, composition, and properties as a function of precursor pressure and substrate temperature were carried out for the CVD of HfB2 and MgO. It is determined that their CVD growth kinetics can be well explained with a Langmuir surface reaction mechanism. A structure zone model is proposed to explain the microstructure-process relationship of the CVD thin films in general. In future generations of microelectronics fabrication, materials need to be deposited into recess features with smaller dimensions and higher aspect ratios. A new approach is developed to obtain super-conformal coating (bottom-up filling) of such high aspect ratio features. The super-conformal growth is demonstrated in the CVD of CrB2 and HfB2 films from the corresponding borohydride precursors with atomic and molecular growth suppressors. Computer simulation is employed to understand the mechanism of the super-conformal deposition. The high Tc superconductor MgB2 were deposited at low temperatures (T = 300°C--400°C) from a recently developed highly volatile borohydride-bonded Mg precursor, by means of catalyst-enhanced chemical vapor deposition. The films are stoichiometric and highly crystallized, however, the lattice constants shift away from the MgB2 structure to the diboride structure of the catalyst metal, suggesting that Mg is partially substituted by the corresponding metals.

  15. Explanation of non-additive effects in mixtures of similar mode of action chemicals.

    PubMed

    Kamo, Masashi; Yokomizo, Hiroyuki

    2015-09-01

    Many models have been developed to predict the combined effect of drugs and chemicals. Most models are classified into two additive models: independent action (IA) and concentration addition (CA). It is generally considered if the modes of action of chemicals are similar then the combined effect obeys CA; however, many empirical studies report nonlinear effects deviating from the predictions by CA. Such deviations are termed synergism and antagonism. Synergism, which leads to a stronger toxicity, requires more careful management, and hence it is important to understand how and which combinations of chemicals lead to synergism. In this paper, three types of chemical reactions are mathematically modeled and the cause of the nonlinear effects among chemicals with similar modes of action was investigated. Our results show that combined effects obey CA only when the modes of action are exactly the same. Contrary to existing knowledge, combined effects are generally nonlinear even if the modes of action of the chemicals are similar. Our results further show that the nonlinear effects vanish out when the chemical concentrations are low, suggesting that the current management procedure of assuming CA is rarely inappropriate because environmental concentrations of chemicals are generally low. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  16. Recycling of red muds with the extraction of metals and special additions to cement

    NASA Astrophysics Data System (ADS)

    Zinoveev, D. V.; Diubanov, V. G.; Shutova, A. V.; Ziniaeva, M. V.

    2015-01-01

    The liquid-phase reduction of iron oxides from red mud is experimentally studied. It is shown that, in addition to a metal, a slag suitable for utilization in the construction industry can be produced as a result of pyrometallurgical processing of red mud. Portland cement is shown to be produced from this slag with mineral additions and a high-aluminate expansion addition to cement.

  17. TANK 40 FINAL SB5 CHEMICAL CHARACTERIZATION RESULTS PRIOR TO NP ADDITION

    SciTech Connect

    Bannochie, C.; Click, D.

    2010-01-06

    A sample of Sludge Batch 5 (SB5) was pulled from Tank 40 in order to obtain radionuclide inventory analyses necessary for compliance with the Waste Acceptance Product Specifications (WAPS). This sample was also analyzed for chemical composition including noble metals. Prior to radionuclide inventory analyses, a final sample of the H-canyon Np stream will be added to bound the Np addition anticipated for Tank 40. These analyses along with the WAPS radionuclide analyses will help define the composition of the sludge in Tank 40 that is currently being fed to DWPF as SB5. At the Savannah River National Laboratory (SRNL) the 3-L Tank 40 SB5 sample was transferred from the shipping container into a 4-L high density polyethylene vessel and solids allowed to settle overnight. Supernate was then siphoned off and circulated through the shipping container to complete the transfer of the sample. Following thorough mixing of the 3-L sample, a 239 g sub-sample was removed. This sub-sample was then utilized for all subsequent analytical samples. Eight separate aliquots of the slurry were digested, four with HNO{sub 3}/HCl (aqua regia) in sealed Teflon{reg_sign} vessels and four in Na{sub 2}O{sub 2} (alkali or peroxide fusion) using Zr crucibles. Due to the use of Zr crucibles and Na in the peroxide fusions, Na and Zr cannot be determined from this preparation. Additionally, other alkali metals, such as Li and K that may be contaminants in the Na{sub 2}O{sub 2} are not determined from this preparation. Three Analytical Reference Glass - 14 (ARG-1) standards were digested along with a blank for each preparation. The ARG-1 glass allows for an assessment of the completeness of each digestion. Each aqua regia digestion and blank was diluted to 1:100 mL with deionized water and submitted to Analytical Development (AD) for inductively coupled plasma - atomic emission spectroscopy (ICPAES) analysis, inductively coupled plasma - mass spectrometry (ICP-MS) analysis of masses 81-209 and 230

  18. Chemical TOPAZ: Modifications to the heat transfer code TOPAZ: The addition of chemical reaction kinetics and chemical mixtures

    SciTech Connect

    Nichols, A.L. III.

    1990-06-07

    This is a report describing the modifications which have been made to the heat flow code TOPAZ to allow the inclusion of thermally controlled chemical kinetics. This report is broken into parts. The first part is an introduction to the general assumptions and theoretical underpinning that were used to develop the model. The second section describes the changes that have been implemented into the code. The third section is the users manual for the input for the code. The fourth section is a compilation of hints, common errors, and things to be aware of while you are getting started. The fifth section gives a sample problem using the new code. This manual addenda is written with the presumption that most readers are not fluent with chemical concepts. Therefore, we shall in this section endeavor to describe the requirements that must be met before chemistry can occur and how we have modeled the chemistry in the code.

  19. The effect of lactic acid bacterial starter culture and chemical additives on wilted rice straw silage.

    PubMed

    Wang, Yan-Su; Shi, Wei; Huang, Lin-Ting; Ding, Cheng-Long; Dai, Chuan-Chao

    2016-04-01

    Lactic acid bacteria (LAB) are suitable for rice straw silage fermentation, but have been studied rarely, and rice straw as raw material for ensiling is difficult because of its disadvantages, such as low nutrition for microbial activities and low abundances of natural populations of LAB. So we investigated the effect of application of LAB and chemical additives on the fermentation quality and microbial community of wilted rice straw silage. Treatment with chemical additives increased the concentrations of crude protein (CP), water soluble carbohydrate (WSC), acetic acid and lactic acid, reduced the concentrations of acid detergent fiber (ADF) and neutral detergent fiber (NDF), but did not effectively inhibit the growth of spoilage organisms. Inoculation with LABs did not improve the nutritional value of the silage because of poor growth of LABs in wilted rice straw. Inoculation with LAB and addition of chemical materials improved the quality of silage similar to the effects of addition of chemical materials alone. Growth of aerobic and facultatively anaerobic bacteria was inhibited by this mixed treatment and the LAB gradually dominated the microbial community. In summary, the fermentation quality of wilted rice straw silage had improved by addition of LAB and chemical materials.

  20. Textbook Errors: 137. Physical and Chemical Properties and Bonding of Metallic Elements.

    ERIC Educational Resources Information Center

    Myers, R. Thomas

    1979-01-01

    Focuses attention on the almost universal practice of discussing all metals as malleable. The author points out that some are brittle and then he presents the variation in chemical properties of metals. (SA)

  1. Precursors for chemical and photochemical vapor deposition of copper metal

    NASA Astrophysics Data System (ADS)

    James, Alicia Marie

    The colorless square-planar cluster [CuN(SiMe3)2] 4, which contains four Cu(I) ions with four bridging amide groups, was studied as a precursor for chemical and photochemical vapor deposition of Cu metal. The cluster phosphoresces in CH2Cl2 solution and in the solid state at room temperature. Its electronic spectrum in CH 2Cl2 consists of two intense bands which are assigned to symmetry-allowed 3d → 4p transitions; the phosphorescence is also likely to be metal-centered. Solid [CuN(SiMe3)2]4 luminesces with approximately the same spectrum as that of the CH2Cl2 solutions. At 77 K, the solid-state luminescence red-shifts slightly. The emission lifetime in glassy Et2O solution is 690 mus. [CuN(SiMe3) 2]4 deposits Cu metal via chemical vapor deposition under H2 carrier gas at substrate temperatures of 145--200°C. Deposition also occurs photochemically beginning at 136--138°C under near-UV irradiation. The preparation of monomeric derivatives of [CuN(SiMe3) 2]4 was attempted by using neutral donor ligands L (e.g. LnCuN(SiMe3)2; L = CO, PR3, CN-t-Bu; n = 1--3). The target compounds were expected to be more volatile than the copper cluster and still maintain photosensitivity. CuCl and [Cu(CH 3CN)4]PF6 were used as starting materials. Even in the presence of L, [CuN(SiMe3)2] 4 is a major product in reactions using CuCl and NaN(SiCH3) 2- [Cu(CH3CN)4]PF6 was a promising route for the monomeric Cu(I) complexes because of ready dissociation of its acetonitrile ligands. However, the characterization of these complexes was unsuccessful. Other Cu(I) amide clusters have been prepared; they may also be suitable for chemical and photochemical vapor deposition of Cu. [CuNEt2] 4, [CuN(i-Pr)2]4, and [CuN(t-Bu)(SiMe 3)]4 are phosphorescent though they are very air sensitive. They should be more volatile and produce Cu metal films more readily than [CuN(SiMe3)2]4 Cu(hfac)2 is a versatile Lewis acid, forming adducts with a variety of bases. The bases that were used were ethylene

  2. Topological design and additive manufacturing of porous metals for bone scaffolds and orthopaedic implants: A review.

    PubMed

    Wang, Xiaojian; Xu, Shanqing; Zhou, Shiwei; Xu, Wei; Leary, Martin; Choong, Peter; Qian, M; Brandt, Milan; Xie, Yi Min

    2016-03-01

    One of the critical issues in orthopaedic regenerative medicine is the design of bone scaffolds and implants that replicate the biomechanical properties of the host bones. Porous metals have found themselves to be suitable candidates for repairing or replacing the damaged bones since their stiffness and porosity can be adjusted on demands. Another advantage of porous metals lies in their open space for the in-growth of bone tissue, hence accelerating the osseointegration process. The fabrication of porous metals has been extensively explored over decades, however only limited controls over the internal architecture can be achieved by the conventional processes. Recent advances in additive manufacturing have provided unprecedented opportunities for producing complex structures to meet the increasing demands for implants with customized mechanical performance. At the same time, topology optimization techniques have been developed to enable the internal architecture of porous metals to be designed to achieve specified mechanical properties at will. Thus implants designed via the topology optimization approach and produced by additive manufacturing are of great interest. This paper reviews the state-of-the-art of topological design and manufacturing processes of various types of porous metals, in particular for titanium alloys, biodegradable metals and shape memory alloys. This review also identifies the limitations of current techniques and addresses the directions for future investigations. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Chemical vapour deposition: Transition metal carbides go 2D

    DOE PAGES

    Gogotsi, Yury

    2015-08-17

    Here, the research community has been steadily expanding the family of few-atom-thick crystals beyond graphene, discovering new materials or producing known materials in a 2D state and demonstrating their unique properties1, 2. Recently, nanometre-thin 2D transition metal carbides have also joined this family3. Writing in Nature Materials, Chuan Xu and colleagues now report a significant advance in the field, showing the synthesis of large-area, high-quality, nanometre-thin crystals of molybdenum carbide that demonstrate low-temperature 2D superconductivity4. Moreover, they also show that other ultrathin carbide crystals, such as tungsten and tantalum carbides, can be grown by chemical vapour deposition with a highmore » crystallinity and very low defect concentration.« less

  4. The Development of Metal Oxide Chemical Sensing Nanostructures

    NASA Technical Reports Server (NTRS)

    Hunter, G. W.; VanderWal,R. L.; Xu, J. C.; Evans, L. J.; Berger, G. M.; Kulis, M. J.

    2008-01-01

    This paper discusses sensor development based on metal oxide nanostructures and microsystems technology. While nanostructures such as nanowires show significant potential as enabling materials for chemical sensors, a number of significant technical challenges remain. This paper discusses development to address each of these technical barriers: 1) Improved contact and integration of the nanostructured materials with microsystems in a sensor structure; 2) Control of nanostructure crystallinity to allow control of the detection mechanism; and 3) Widening the range of gases that can be detected by fabricating multiple nanostructured materials. A sensor structure composed of three nanostructured oxides aligned on a single microsensor has been fabricated and tested. Results of this testing are discussed and future development approaches are suggested. It is concluded that while this work lays the foundation for further development, these are the beginning steps towards realization of repeatable, controlled sensor systems using oxide based nanostructures.

  5. Chemical vapour deposition: Transition metal carbides go 2D

    SciTech Connect

    Gogotsi, Yury

    2015-08-17

    Here, the research community has been steadily expanding the family of few-atom-thick crystals beyond graphene, discovering new materials or producing known materials in a 2D state and demonstrating their unique properties1, 2. Recently, nanometre-thin 2D transition metal carbides have also joined this family3. Writing in Nature Materials, Chuan Xu and colleagues now report a significant advance in the field, showing the synthesis of large-area, high-quality, nanometre-thin crystals of molybdenum carbide that demonstrate low-temperature 2D superconductivity4. Moreover, they also show that other ultrathin carbide crystals, such as tungsten and tantalum carbides, can be grown by chemical vapour deposition with a high crystallinity and very low defect concentration.

  6. Ligand field effect at oxide-metal interface on the chemical reactivity of ultrathin oxide film surface.

    PubMed

    Jung, Jaehoon; Shin, Hyung-Joon; Kim, Yousoo; Kawai, Maki

    2012-06-27

    Ultrathin oxide film is currently one of the paramount candidates for a heterogeneous catalyst because it provides an additional dimension, i.e., film thickness, to control chemical reactivity. Here, we demonstrate that the chemical reactivity of ultrathin MgO film grown on Ag(100) substrate for the dissociation of individual water molecules can be systematically controlled by interface dopants over the film thickness. Density functional theory calculations revealed that adhesion at the oxide-metal interface can be addressed by the ligand field effect and is linearly correlated with the chemical reactivity of the oxide film. In addition, our results indicate that the concentration of dopant at the interface can be controlled by tuning the drawing effect of oxide film. Our study provides not only profound insight into chemical reactivity control of ultrathin oxide film supported by a metal substrate but also an impetus for investigating ultrathin oxide films for a wider range of applications.

  7. Effect of metal Additions on the Hydrogen Uptake of Microporous Carbon at Near-Ambient Temperature

    SciTech Connect

    Contescu, Cristian I; Gallego, Nidia C; Bhat, Vinay V

    2010-01-01

    Enhancing the hydrogen sorption capacity of microporous carbon materials at near-ambient temperature continue to be a challenge and the subject of intense research. Physisorption alone on microporous carbons is not strong enough to provide the desired levels of hydrogen uptake. Modifying carbons with small amounts of metals has been proven effective to increase the amounts adsorbed. However, very different mechanisms may be involved when the promoters are transition metals or alkali metals. In this presentation we compare the effect of additions of palladium and/or alkali metals on the hydrogen uptake of microporous carbons, in an attempt to differentiate between the possible mechanisms leading to enhanced hydrogen capacity and fast kinetics.

  8. Cumulative effects of bamboo sawdust addition on pyrolysis of sewage sludge: Biochar properties and environmental risk from metals.

    PubMed

    Jin, Junwei; Wang, Minyan; Cao, Yucheng; Wu, Shengchun; Liang, Peng; Li, Yanan; Zhang, Jianyun; Zhang, Jin; Wong, Ming Hung; Shan, Shengdao; Christie, Peter

    2017-03-01

    A novel type of biochar was produced by mixing bamboo sawdust with sewage sludge (1:1, w/w) via a co-pyrolysis process at 400-600°C. Changes in physico-chemical properties and the intrinsic speciation of metals were investigated before and after pyrolysis. Co-pyrolysis resulted in a lower biochar yield but a higher C content in the end product compared with use of sludge alone as the raw material. FT-IR analysis indicates that phosphine derivatives containing PH bonds were formed in the co-pyrolyzed biochars. In addition, co-pyrolysis of sludge with bamboo sawdust transformed the potentially toxic metals in the sludge into more stable fractions, leading to a considerable decrease in their direct toxicity and bioavailability in the co-pyrolyzed biochar. In conclusion, the co-pyrolysis technology provides a feasible method for the safe disposal of metal-contaminated sewage sludge in an attempt to minimize the environmental risk from potentially toxic metals after land application.

  9. Influence of the aspect ratio of magnetic metallic additives on the microwave absorbing performance

    NASA Astrophysics Data System (ADS)

    de Souza Pinto, Simone; Barros Machado, João Paulo; Gomes, Newton A. S.; Cerqueira Rezende, Mirabel

    2017-09-01

    This work aims to show the behavior of radar absorbing materials (RAM) based on magnetic metallic additives with different aspect ratios. For this, two materials, carbonyl iron, constituted of spherical iron particles, and carbon-steel filaments were used. These additives were characterized considering their morphological and structural features. X-ray diffraction analysis shows that the two additives have the same crystallographic structure, but their morphologies are quite different in micrometer scale. Epoxy resin/metallic additive composites using the neat additives and their mixtures were prepared. The electromagnetic characterization of the composites evaluated the permittivity, permeability and reflectivity behaviors in the frequency range of 8.2–12.4 GHz. The results show that the samples obtained with the mixture of the two additives resulted in composites with high complex parameters of permittivity and permeability. Better RAM performance is observed for samples based on metallic filaments and for more concentrated mixtures containing the two additives (values up to  ‑14 dB or ~96% of attenuation). The influence of specimen-thickness on the RAM performance is also observed.

  10. Addition of cerium and yttrium to ferritic steel weld metal to improve hydrogen trapping efficiency

    NASA Astrophysics Data System (ADS)

    Kim, Sung Jin; Ryu, Kang Mook; Oh, Min-suk

    2017-04-01

    The applicability of Ce and Y as promising candidate elements to form irreversible traps in weld metal was investigated by thermal desorption spectroscopy (TDS) with gas chromatography (GC). The precise nature of the precipitate particles newly formed in the weld metal by the addition of Ce and Y to a certain alloy system was characterized. Moreover, the hydrogen trapping efficiency expressed as the reduction of the diffusible hydrogen in the weld metal was analyzed. The results showed that the addition of Ce and/or Y to this alloy system led to the formation of a mixed type of (Ce,Ti)-based oxide, (Y,Ni)-based carbide, or (Ce,Y,Ti)-based oxide particles. Because of the high activation energy of the mixed type of particles (≥ 150 kJ/mol), the trapping efficiency for hydrogen was considered to be sufficiently high to effectively reduce the diffusible hydrogen content.

  11. Slip casting and extruding shapes of rhenium with metal oxide additives. 1: Feasibility demonstration

    NASA Technical Reports Server (NTRS)

    Barr, F. A.; Page, R. J.

    1986-01-01

    The feasibility of fabricating small rhenium parts with metal oxide additives by means of slip casting and extrusion techniques is described. The metal oxides, ZrO2 and HfO2 were stabilized into the cubic phase with Y2O3. Additions of metal oxide to the rhenium of up to 15 weight percent were used. Tubes of 17 mm diameter with 0.5 mm walls were slip cast by adapting current ceramic oxide techniques. A complete cast double conical nozzle demonstrated the ability to meet shapes and tolerances. Extrusion of meter long tubing lengths of 3.9 mm o.d. x 2.3 mm i.d. final dimension is documented. Sintering schedules are presented to produce better than 95% of theoretical density parts. Finished machining was found possible were requried by electric discharge machining and diamond grinding.

  12. Role of Alloying Additions in Glass Formation and Properties of Bulk Metallic Glasses

    PubMed Central

    Chen, Na; Martin, Laura; Luzguine-Luzgin, Dmitri V.; Inoue, Akihisa

    2010-01-01

    Alloying addition, as a means of improving mechanical properties and saving on costs of materials, has been applied to a broad range of uses and products in the metallurgical fields. In the field of bulk metallic glasses (BMGs), alloying additions have also proven to play effective and important roles in promoting glass formation, enhancing thermal stability and improving plasticity of the materials. Here, we review the work on the role of alloying additions in glass formation and performance improvement of BMGs, with focus on our recent results of alloying additions in Pd-based BMGs. PMID:28883386

  13. Metal-mediated aminocatalysis provides mild conditions: Enantioselective Michael addition mediated by primary amino catalysts and alkali-metal ions.

    PubMed

    Leven, Matthias; Neudörfl, Jörg M; Goldfuss, Bernd

    2013-01-01

    Four catalysts based on new amides of chiral 1,2-diamines and 2-sulfobenzoic acid have been developed. The alkali-metal salts of these betaine-like amides are able to form imines with enones, which are activated by Lewis acid interaction for nucleophilic attack by 4-hydroxycoumarin. The addition of 4-hydroxycoumarin to enones gives ee's up to 83% and almost quantitative yields in many cases. This novel type of catalysis provides an effective alternative to conventional primary amino catalysis were strong acid additives are essential components.

  14. Metal-mediated aminocatalysis provides mild conditions: Enantioselective Michael addition mediated by primary amino catalysts and alkali-metal ions

    PubMed Central

    Leven, Matthias; Neudörfl, Jörg M

    2013-01-01

    Summary Four catalysts based on new amides of chiral 1,2-diamines and 2-sulfobenzoic acid have been developed. The alkali-metal salts of these betaine-like amides are able to form imines with enones, which are activated by Lewis acid interaction for nucleophilic attack by 4-hydroxycoumarin. The addition of 4-hydroxycoumarin to enones gives ee’s up to 83% and almost quantitative yields in many cases. This novel type of catalysis provides an effective alternative to conventional primary amino catalysis were strong acid additives are essential components. PMID:23400419

  15. 78 FR 68461 - Guidance for Industry: Studies To Evaluate the Utility of Anti-Salmonella Chemical Food Additives...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-11-14

    ... Anti- Salmonella Chemical Food Additives in Feeds; Request for Comments AGENCY: Food and Drug... Chemical Food Additives in Feeds,'' and is seeking comments on this guidance before revisions are made... Guidance for Industry: Studies to Evaluate the Utility of Anti-Salmonella Chemical Food Additives in Feeds...

  16. Reducing the matrix effects in chemical analysis: fusion of isotope dilution and standard addition methods

    NASA Astrophysics Data System (ADS)

    Pagliano, Enea; Meija, Juris

    2016-04-01

    The combination of isotope dilution and mass spectrometry has become an ubiquitous tool of chemical analysis. Often perceived as one of the most accurate methods of chemical analysis, it is not without shortcomings. Current isotope dilution equations are not capable of fully addressing one of the key problems encountered in chemical analysis: the possible effect of sample matrix on measured isotope ratios. The method of standard addition does compensate for the effect of sample matrix by making sure that all measured solutions have identical composition. While it is impossible to attain such condition in traditional isotope dilution, we present equations which allow for matrix-matching between all measured solutions by fusion of isotope dilution and standard addition methods.

  17. Water and a protic ionic liquid acted as refolding additives for chemically denatured enzymes.

    PubMed

    Attri, Pankaj; Venkatesu, P; Kumar, Anil

    2012-10-07

    In this communication, we present the ability of water and a protic ionic liquid, triethyl ammonium phosphate (TEAP) to act as refolding additives for the urea-induced chemical denaturated state of the two enzymes, α-chymotrypsin and succinylated Con A. We show that the enzymatic activity is regained and in certain circumstances enhanced.

  18. Kinetic effect of Pd additions on the hydrogen uptake of chemically activated, ultramicroporous carbon

    SciTech Connect

    Bhat, Vinay V; Contescu, Cristian I; Gallego, Nidia C

    2010-01-01

    The effect of mixing chemically-activated ultramicroporous carbon (UMC) with Pd nanopowder is investigated. Results show that Pd addition doubles the rate of hydrogen uptake, but does not enhance the hydrogen capacity or improve desorption kinetics. The effect of Pd on the rate of hydrogen adsorption supports the occurrence of the hydrogen spillover mechanism in the Pd - UMC system.

  19. A chemical additive to limit transfer of salmonella and campylobacter during immersion chill

    USDA-ARS?s Scientific Manuscript database

    Broiler carcasses with different types and numbers of bacteria are commonly chilled together in an ice water bath which may lead to transfer of bacteria from carcass to carcass. Historically, chill tanks have been chlorinated to help prevent cross contamination. Recently other chemical additive op...

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

    PubMed

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

    2016-03-14

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

  1. Fluid mechanics of additive manufacturing of metal objects by accretion of droplets - a survey

    NASA Astrophysics Data System (ADS)

    Tesař, Václav

    2016-03-01

    Paper presents a survey of principles of additive manufacturing of metal objects by accretion of molten metal droplets, focusing on fluid-mechanical problems that deserve being investigated. The main problem is slowness of manufacturing due to necessarily small size of added droplets. Increase of droplet repetition rate calls for basic research of the phenomena that take place inside and around the droplets: ballistics of their flight, internal flowfield with heat and mass transfer, oscillation of surfaces, and the ways to elimination of satellite droplets.

  2. Generation of reactive oxygen species by interaction between antioxidants used as food additive and metal ions.

    PubMed

    Iwasaki, Yusuke; Oda, Momoko; Tsukuda, Yuri; Nagamori, Yuki; Nakazawa, Hiroyuki; Ito, Rie; Saito, Koichi

    2014-01-01

    Food additives, such as preservatives, sweeteners, coloring agents, and flavoring agents, are widely used in food manufacturing. However, their combined effects on the human body are not known. The purpose of this study was to examine whether combinations of antioxidants and metal ions generate reactive oxygen species (ROS) under in vitro conditions using electron spin resonance (ESR). Among the metal ions examined, only iron and copper generated ROS in the presence of antioxidants. Moreover, certain phenolic antioxidants having pro-oxidant activity induced DNA oxidation and degradation via the generation of high levels of ROS in the presence of copper ion, resulting in complete degradation of DNA in vitro.

  3. Chemically synthesized metal-oxide-metal segmented nanowires with high ferroelectric response

    NASA Astrophysics Data System (ADS)

    Herderick, Edward D.; Polomoff, Nicholas A.; Huey, Bryan D.; Padture, Nitin P.

    2010-08-01

    A chemical synthesis method is presented for the fabrication of high-definition segmented metal-oxide-metal (MOM) nanowires in two different ferroelectric oxide systems: Au-BaTiO3-Au and Au-PbTiO3-Au. This method entails electrodeposition of segmented nanowires of Au-TiO2-Au inside anodic aluminum oxide (AAO) templates, followed by topotactic hydrothermal conversion of the TiO2 segments into BaTiO3 or PbTiO3 segments. Two-terminal devices from individual MOM nanowires are fabricated, and their ferroelectric properties are measured directly, without the aid of scanning probe microscopy (SPM) methods. The MOM nanowire architecture provides high-quality end-on electrical contacts to the oxide segments, and allows direct measurement of properties of nanoscale volume, strain-free oxide segments. Unusually high ferroelectric responses, for chemically synthesized oxides, in these MOM nanowires are reported, and are attributed to the lack of residual strain in the oxides. The ability to measure directly the active properties of nanoscale volume, strain-free oxides afforded by the MOM nanowire architecture has important implications for fundamental studies of not only ferroelectric nanostructures but also nanostructures in the emerging field of multiferroics.

  4. Electrochemical and Chemical Complications Resulting from Yeast Extract Addition to Stimulate Microbial Growth

    DTIC Science & Technology

    2016-09-22

    Standard dry air.12 (1) UNS numbers are listed in Metals and Alloys in the Unified Num- bering System, published by the Society of Automotive Engineers...Ecorr values of 316L in aerobic and deoxygenated seawaters with YE addition were nearly identical, with standard deviations overlapping at all times ... Standard Form 298 (Rev. 8/98) REPORT DOCUMENTATION PAGE Prescribed by ANSI Std. Z39.18 Form Approved OMB No. 0704-0188 The public reporting

  5. Tracing the migration history of metal catalysts in metal-assisted chemically etched silicon.

    PubMed

    Güder, Firat; Yang, Yang; Küçükbayrak, Umut M; Zacharias, Margit

    2013-02-26

    Three-dimensional (3D) visualization of complex embedded nanopore networks in silicon requires expensive machinery and tedious sample preparation procedures such as electron tomography, also known as 3D transmission electron microscopy. In this article, we report a new, fast, powerful, and low-cost three-dimensional imaging technique with sub-5 nm resolution. This new imaging method is applied to metal-assisted chemically etched monocrystalline Si to demonstrate its capabilities. The AFEI (atomic layer deposition-fill-etch-imaging) technique consists of three simple process steps that are available in most material research settings. First the porous substrate is conformally coated with an atomic layer deposition (ALD) metal oxide layer. ALD is able to penetrate deep into complex, high aspect ratio pores, as it is a sequential gas-phase deposition process. Next, the cross-section of the ALD-filled porous Si substrate is etched with high-density fluorine-based plasma processing, which yields very high selectivity toward Si (e.g., >400:1 for Si:ZnO). This step removes the bulk Si and exposes the metal oxide structures grown inside the pores. In the last step, the sample cross-section is examined using a standard scanning electron microscope at various angles, which allows precise imaging of hidden features and reconstruction of a 3D model of the embedded pore network.

  6. Chemical Control of Plasmons in Metal Chalcogenide and Metal Oxide Nanostructures.

    PubMed

    Mattox, Tracy M; Ye, Xingchen; Manthiram, Karthish; Schuck, P James; Alivisatos, A Paul; Urban, Jeffrey J

    2015-10-14

    The field of plasmonics has grown to impact a diverse set of scientific disciplines ranging from quantum optics and photovoltaics to metamaterials and medicine. Plasmonics research has traditionally focused on noble metals; however, any material with a sufficiently high carrier density can support surface plasmon modes. Recently, researchers have made great gains in the synthetic (both intrinsic and extrinsic) control over the morphology and doping of nanoscale oxides, pnictides, sulfides, and selenides. These synthetic advances have, collectively, blossomed into a new, emerging class of plasmonic metal chalcogenides that complement traditional metallic materials. Chalcogenide and oxide nanostructures expand plasmonic properties into new spectral domains and also provide a rich suite of chemical controls available to manipulate plasmons, such as particle doping, shape, and composition. New opportunities in plasmonic chalcogenide nanomaterials are highlighted in this article, showing how they may be used to fundamentally tune the interaction and localization of electromagnetic fields on semiconductor surfaces in a way that enables new horizons in basic research and energy-relevant applications.

  7. Recent Developments in Metal-Catalyzed Additions of Oxygen Nucleophiles to Alkenes and Alkynes

    NASA Astrophysics Data System (ADS)

    Hintermann, Lukas

    Progress in the field of metal-catalyzed redox-neutral additions of oxygen nucleophiles (water, alcohols, carboxylic acids, and others) to alkenes, alkynes, and allenes between 2001 and 2009 is critically reviewed. Major advances in reaction chemistry include development of chiral Lewis acid catalyzed asymmetric oxa-Michael additions and Lewis-acid catalyzed hydro-alkoxylations of nonactivated olefins, as well as further development of Markovnikov-selective cationic gold complex-catalyzed additions of alcohols or water to alkynes and allenes.

  8. Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O2 activation by non-adiabatic oxidative addition to a single metal center

    DOE PAGES

    Akturk, Eser S.; Yap, Glenn P. A.; Theopold, Klaus H.

    2015-10-16

    A chromium(I) dinitrogen complex reacts rapidly with O2 to form the mononuclear dioxo complex [TptBu,MeCrV(O)2] (TptBu,Me=hydrotris(3-tert-butyl-5-methylpyrazolyl)borate), whereas the analogous reaction with sulfur stops at the persulfido complex [TptBu,MeCrIII(S2)]. The transformation of the putative peroxo intermediate [TptBu,MeCrIII(O2)] (S=3/2) into [TptBu,MeCrV(O)2] (S=1/2) is spin-forbidden. The minimum-energy crossing point for the two potential energy surfaces has been identified. Finally, although the dinuclear complex [(TptBu,MeCr)2(μ-O)2] exists, mechanistic experiments suggest that O2 activation occurs on a single metal center, by an oxidative addition on the quartet surface followed by crossover to the doublet surface.

  9. Diagnosis of Chemical Reactivity and Pollution Sources from Particulate Trace Metal Distributions in Estuaries

    NASA Astrophysics Data System (ADS)

    Turner, A.

    1999-02-01

    A simple approach is outlined for the diagnosis of chemical reactivity and pollution sources from distributions of suspended particulate constituents in estuaries of low turbidity and limited bed-water column particle exchange. The approach is demonstrated using acetic acid-extractable particulate trace metal data for the Clyde Estuary, where water and particle mixing in the vertical is restricted by a strong pycnocline, resuspension is limited by slow subsurface currents and internal sediment cycling is inhibited by the topography of the outer estuary. The salinity distributions of particulate Fe and Mn result from end-member particle mixing, modified by the geochemical mechanisms controlling their particle-water exchange (salt-induced flocculation of riverine, Fe-bearing colloidal material and autocatalytic oxidation-sorption of dissolved Mn). The axial distributions of particulate Cu, Cr, Pb and Zn are, additionally, affected by external inputs to the tidal estuary. The magnitudes of internal (e.g. particle-water exchange) or external (e.g. pollution) sources are calculated from the deviation of metal concentrations from a theoretical dilution line adjoining estuarine end-members, via chemical mass balances and empirical equations defining particle-water partitioning as a function of salinity. Calculated particle-water exchanges of Fe and Mn are compatible with independent dissolved metal measurements in the Clyde Estuary. Calculated external sources of Cu and Pb are in reasonable agreement with monitored trace metal input data to the estuary, but discrepancies exist between calculated and monitored external sources of Cr and Zn because of the significance of unmonitored inputs and chemical reactivity for these metals. Although suspended particulate trace metal concentrations in the Clyde are among the highest of industrialized estuaries in the U.K., it is argued that this, in part, reflects the inability of the Clyde to buffer pollution inputs because of the

  10. Effects of chemical additives on filtration and rheological characteristics of MBR sludge.

    PubMed

    Koseoglu, H; Yigit, N O; Civelekoglu, G; Harman, B I; Kitis, M

    2012-08-01

    The main goal of this study was to control the fouling phenomena in MBR using chemical additives. In the first phase of the study, SMP removal and bound EPS formation capacity of chemical additives were determined. Highest SMP removal (72%) was achieved by the Poly-2 additive. In the second phase of the study, short term filtration tests were conducted. Poly-1 exhibited highest performance based on membrane resistance, permeability and average TMP. According to the results obtained from constant shear rate tests in fourth phase, no significant change in viscosity with time was observed. Studies for the adaptation of rheograms to common flow models showed that chitosan and starch was not able to fit to Ostwald de Waele and Bingham models. At a shear rate of 73.4 s(-1) viscosities of all samples were close to each other. Chitosan and starch achieved highest viscosity values at the shear rate of 0.6 s(-1).

  11. Metal vapor micro-jet controls material redistribution in laser powder bed fusion additive manufacturing.

    PubMed

    Ly, Sonny; Rubenchik, Alexander M; Khairallah, Saad A; Guss, Gabe; Matthews, Manyalibo J

    2017-06-22

    The results of detailed experiments and finite element modeling of metal micro-droplet motion associated with metal additive manufacturing (AM) processes are presented. Ultra high speed imaging of melt pool dynamics reveals that the dominant mechanism leading to micro-droplet ejection in a laser powder bed fusion AM is not from laser induced recoil pressure as is widely believed and found in laser welding processes, but rather from vapor driven entrainment of micro-particles by an ambient gas flow. The physics of droplet ejection under strong evaporative flow is described using simulations of the laser powder bed interactions to elucidate the experimental results. Hydrodynamic drag analysis is used to augment the single phase flow model and explain the entrainment phenomenon for 316 L stainless steel and Ti-6Al-4V powder layers. The relevance of vapor driven entrainment of metal micro-particles to similar fluid dynamic studies in other fields of science will be discussed.

  12. Transition metal-catalyzed process for addition of amines to carbon-carbon double bonds

    DOEpatents

    Hartwig, John F.; Kawatsura, Motoi; Loeber, Oliver

    2002-01-01

    The present invention is directed to a process for addition of amines to carbon-carbon double bonds in a substrate, comprising: reacting an amine with a compound containing at least one carbon-carbon double bond in the presence a transition metal catalyst under reaction conditions effective to form a product having a covalent bond between the amine and a carbon atom of the former carbon-carbon double bond. The transition metal catalyst comprises a Group 8 metal and a ligand containing one or more 2-electron donor atoms. The present invention is also directed to enantioselective reactions of amine compounds with compounds containing carbon-carbon double bonds, and a calorimetric assay to evaluate potential catalysts in these reactions.

  13. Life cycle cost study for coated conductor manufacture by metal organic chemical vapor deposition

    SciTech Connect

    Chapman, J.N.

    1999-07-13

    The purpose of this report is to calculate the cost of producing high temperature superconducting wire by the Metal Organic Chemical Vapor Deposition (MOCVD) process. The technology status is reviewed from the literature and a plant conceptual design is assumed for the cost calculation. The critical issues discussed are the high cost of the metal organic precursors, the material utilization efficiency and the capability of the final product as measured by the critical current density achieved. Capital, operating and material costs are estimated and summed as the basis for calculating the cost per unit length of wire. Sensitivity analyses of key assumptions are examined to determine their effects on the final wire cost. Additionally, the cost of wire on the basis of cost per kiloampere per meter is calculated for operation at lower temperatures than the liquid nitrogen boiling temperature. It is concluded that this process should not be ruled out on the basis of high cost of precursors alone.

  14. Pulsed supersonic molecular beam for characterization of chemically active metal-organic complexes at surfaces

    NASA Astrophysics Data System (ADS)

    Lear, Amanda M.

    Metal-organic coordination networks (MOCNs) at surfaces consist of a complex of organic ligands bound to an atomic metal center. The MOCNs, when chosen appropriately, can form highly-ordered arrays at surfaces. Ultra-high vacuum surface studies allow control of surface composition and provide 2D growth restrictions, which lead to under-coordinated metal centers. These systems provide an opportunity to tailor the chemical function of the metal centers due to the steric restrictions imposed by the surface. Tuning the adsorption/desorption energy at a metal center and developing a cooperative environment for catalysis are the key scientific questions that motivate the construction of a molecular beam surface analysis system. Characterization of the created systems can be performed utilizing a pulsed supersonic molecular beam (PSMB) in unison with a quadrupole mass spectrometer. A PSMB allows for the highly controlled delivery of reactants with well-defined energy to a given platform making it possible to elucidate detailed chemical tuning information. In this thesis, a summary of prior theoretical molecular beam derivations is provided. Design considerations and an overview of the construction procedure for the current molecular beam apparatus, including initial characterization experiments, are presented. By impinging an Ar beam on a Ag(111) surface, the location of the specular angle (˜65°) and rough sample perimeter coordinates were determined. Additionally, surface analysis experiments, mainly Auger Electron Spectroscopy (AES), were performed to investigate the oxidation of epitaxial graphene on the SiC(0001) surface utilizing an oxygen cracking method. The AES experiments are described in detail and highlight the challenges that were faced when several different graphene samples were used for the oxygen adsorption/desorption experiments.

  15. A Fully Non-Metallic Gas Turbine Engine Enabled by Additive Manufacturing

    NASA Technical Reports Server (NTRS)

    Grady, Joseph E.; Halbig, Michael C.; Singh, Mrityunjay

    2015-01-01

    In a NASA Aeronautics Research Institute (NARI) sponsored program entitled "A Fully Non-Metallic Gas Turbine Engine Enabled by Additive Manufacturing", evaluation of emerging materials and additive manufacturing technologies was carried out. These technologies may enable fully non-metallic gas turbine engines in the future. This paper highlights the results of engine system trade studies which were carried out to estimate reduction in engine emissions and fuel burn enabled due to advanced materials and manufacturing processes. A number of key engine components were identified in which advanced materials and additive manufacturing processes would provide the most significant benefits to engine operation. In addition, feasibility of using additive manufacturing technologies to fabricate gas turbine engine components from polymer and ceramic matrix composite were demonstrated. A wide variety of prototype components (inlet guide vanes (IGV), acoustic liners, engine access door) were additively manufactured using high temperature polymer materials. Ceramic matrix composite components included first stage nozzle segments and high pressure turbine nozzle segments for a cooled doublet vane. In addition, IGVs and acoustic liners were tested in simulated engine conditions in test rigs. The test results are reported and discussed in detail.

  16. A Fully Non-Metallic Gas Turbine Engine Enabled by Additive Manufacturing

    NASA Technical Reports Server (NTRS)

    Grady, Joseph E.; Halbig, Michael C.; Singh, Mrityunjay

    2015-01-01

    In a NASA Aeronautics Research Institute (NARI) sponsored program entitled "A Fully Non-Metallic Gas Turbine Engine Enabled by Additive Manufacturing," evaluation of emerging materials and additive manufacturing technologies was carried out. These technologies may enable fully non-metallic gas turbine engines in the future. This paper highlights the results of engine system trade studies which were carried out to estimate reduction in engine emissions and fuel burn enabled due to advanced materials and manufacturing processes. A number of key engine components were identified in which advanced materials and additive manufacturing processes would provide the most significant benefits to engine operation. In addition, feasibility of using additive manufacturing technologies to fabricate gas turbine engine components from polymer and ceramic matrix composite were demonstrated. A wide variety of prototype components (inlet guide vanes (IGV), acoustic liners, engine access door, were additively manufactured using high temperature polymer materials. Ceramic matrix composite components included first stage nozzle segments and high pressure turbine nozzle segments for a cooled doublet vane. In addition, IGVs and acoustic liners were tested in simulated engine conditions in test rigs. The test results are reported and discussed in detail.

  17. Computational Investigations of Potential Energy Function Development for Metal--Organic Framework Simulations, Metal Carbenes, and Chemical Warfare Agents

    NASA Astrophysics Data System (ADS)

    Cioce, Christian R.

    Metal-Organic Frameworks (MOFs) are three-dimensional porous nanomaterials with a variety of applications, including catalysis, gas storage and separation, and sustainable energy. Their potential as air filtration systems is of interest for designer carbon capture materials. The chemical constituents (i.e. organic ligands) can be functionalized to create rationally designed CO2 sequestration platforms, for example. Hardware and software alike at the bleeding edge of supercomputing are utilized for designing first principles-based molecular models for the simulation of gas sorption in these frameworks. The classical potentials developed herein are named PHAST --- Potentials with High Accuracy, Speed, and Transferability, and thus are designed via a "bottom-up" approach. Specifically, models for N2 and CH4 are constructed and presented. Extensive verification and validation leads to insights and range of applicability. Through this experience, the PHAST models are improved upon further to be more applicable in heterogeneous environments. Given this, the models are applied to reproducing high level ab initio energies for gas sorption trajectories of helium atoms in a variety of rare-gas clusters, the geometries of which being representative of sorption-like environments commonly encountered in a porous nanomaterial. This work seeks to push forward the state of classical and first principles materials modeling. Additionally, the characterization of a new type of tunable radical metal---carbene is presented. Here, a cobalt(II)---porphyrin complex, [Co(Por)], was investigated to understand its role as an effective catalyst in stereoselective cyclopropanation of a diazoacetate reagent. Density functional theory along with natural bond order analysis and charge decomposition analysis gave insight into the electronics of the catalytic intermediate. The bonding pattern unveiled a new class of radical metal---carbene complex, with a doublet cobalt into which a triplet carbene

  18. Presence of chemical additives and microbial inhibition capacity in grapefruit seed extracts used in apiculture.

    PubMed

    Spinosi, Valerio; Semprini, Primula; Langella, Vincenzo; Scortichini, Giampiero; Calvarese, Silvano

    2007-01-01

    American foulbrood, caused by Paenibacillus larvae subsp. larvae (White 1906) is one of the most serious diseases of honey bees, causing beekeepers and health workers to make difficult, complex decisions and leading to the development of 'organic' treatments, such as grapefruit seed extract, with minor residue problems in the end product. This study evaluates the chemical composition of grapefruit seed extracts using gas chromatography/mass spectrometry for the detection of benzethonium chloride, cetrimonium bromide and decyltrimethylammonium chloride. The results obtained suggest a close correlation between the microbial effect and the presence of chemical additives in the samples analysed.

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

    SciTech Connect

    Fox, K. M.; Johnson, F. C.

    2015-11-01

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

  20. Comparison of InGaAs(100) Grown by Chemical Beam Epitaxy and Metal Organic Chemical Vapor Deposition

    NASA Technical Reports Server (NTRS)

    Williams, M. D.; Greene, A. L.; Daniels-Race, T.; Lum, R. M.

    2000-01-01

    Secondary ion mass spectrometry is used to study the effects of substrate temperature on the composition and growth rate of InGaAs/InP(100) multilayers grown by chemical beam epitaxy, metal-organic chemical vapor deposition and solid source molecular beam epitaxy. The growth kinetics of the material grown by the different techniques are analyzed and compared.

  1. Comparison of InGaAs(100) Grown by Chemical Beam Epitaxy and Metal Organic Chemical Vapor Deposition

    NASA Technical Reports Server (NTRS)

    Williams, M. D.; Greene, A. L.; Daniels-Race, T.; Lum, R. M.

    2000-01-01

    Secondary ion mass spectrometry is used to study the effects of substrate temperature on the composition and growth rate of InGaAs/InP(100) multilayers grown by chemical beam epitaxy, metal-organic chemical vapor deposition and solid source molecular beam epitaxy. The growth kinetics of the material grown by the different techniques are analyzed and compared.

  2. Chemical preparation of graphene materials results in extensive unintentional doping with heteroatoms and metals.

    PubMed

    Chua, Chun Kiang; Ambrosi, Adriano; Sofer, Zdeněk; Macková, Anna; Havránek, Vladimír; Tomandl, Ivo; Pumera, Martin

    2014-11-24

    Chemical synthesis of graphene relies on the usage of various chemical reagents. The initial synthesis step, in which graphite is oxidized to graphite oxide, is achieved by a combination of chemical oxidants and acids. A subsequent chemical reduction step eliminates/reduces most oxygen functionalities to yield graphene. We demonstrate here that these chemical treatments significantly contaminate graphene with heteroatoms/metals, depending on the procedures followed. Contaminations with heteroatoms (N, B, Cl, S) or metals (Mn, Al) were present at relatively high concentrations (up to 3 at%), with their chemical states dependent on the procedures. Such unintentional contaminations (unwanted doping) during chemical synthesis are rarely anticipated and reported, although the heteroatoms/metals may alter the electronic and catalytic properties of graphene. In fact, the levels of unintentionally introduced contaminants on graphene are often higher than typical levels found on intentionally doped graphene. Our findings are important for scientists applying chemical methods to prepare graphene.

  3. Measurement of electromagnetic properties of powder and solid metal materials for additive manufacturing

    NASA Astrophysics Data System (ADS)

    Todorov, Evgueni Iordanov

    2017-04-01

    The lack of validated nondestructive evaluation (NDE) techniques for examination during and after additive manufacturing (AM) component fabrication is one of the obstacles in the way of broadening use of AM for critical applications. Knowledge of electromagnetic properties of powder (e.g. feedstock) and solid AM metal components is necessary to evaluate and deploy electromagnetic NDE modalities for examination of AM components. The objective of this research study was to develop and implement techniques for measurement of powder and solid metal electromagnetic properties. Three materials were selected - Inconel 625, duplex stainless steel 2205, and carbon steel 4140. The powder properties were measured with alternate current (AC) model based eddy current technique and direct current (DC) resistivity measurements. The solid metal properties were measured with DC resistivity measurements, DC magnetic techniques, and AC model based eddy current technique. Initial magnetic permeability and electrical conductivity were acquired for both powder and solid metal. Additional magnetic properties such as maximum permeability, coercivity, retentivity, and others were acquired for 2205 and 4140. Two groups of specimens were tested along the build length and width respectively to investigate for possible anisotropy. There was no significant difference or anisotropy when comparing measurements acquired along build length to those along the width. A trend in AC measurements might be associated with build geometry. Powder electrical conductivity was very low and difficult to estimate reliably with techniques used in the study. The agreement between various techniques was very good where adequate comparison was possible.

  4. Natural and active chemical remediation of toxic metals, organics, and radionuclides in the aquatic environment

    SciTech Connect

    McPherson, G.; Pintauro, P.; O`Connor, S.

    1996-05-02

    This project focuses on the chemical aspects of remediation, with the underlying theme that chemical remediation does occur naturally. Included are studies on the fate of heavy metal and organic contaminants discharged into aquatic environments; accurate assay metal contaminants partitioned into soils, water and tissue; development of novel polymeric membranes and microporous solids for the entrapment of heavy metals; and the development of hybrid chemo-enzymatic oxidative schemes for aromatics decontamination. 49 refs.

  5. Metal hydride/chemical heat pump development project

    NASA Astrophysics Data System (ADS)

    Madariaga, H. A.; Rohy, D. A.

    1982-02-01

    A mental hydride heat pump (MHHP) is a chemical heat pump containing two different hydrides and using hydrogen as a working fluid for the storage and/or recovery of thermal energy. It utilizes the heat of reaction of hydrogen with specific metal alloys. The MHHP design can be tailored to provide heating and cooling or temperature upgrading over a wide range of input and ambient temperatures. This system can be used with a variety of heat sources including industrial waste heat, solar energy or a fossil fuel. Temperature as low as 130 F can drive the MHHP when a suitable sink is provided. A project is currently underway to develop this unique heat pump for a specific application. The goals of the project include the development of cost effective hydride containers with high heat transfer and low mass; design and fabrication of a laboratory evaluation model; and design and fabrication of a demonstration unit. Extensive component and system test will provide the data for the design processes.

  6. Size-controlled synthesis of transition metal nanoparticles through chemical and photo-chemical routes

    NASA Astrophysics Data System (ADS)

    Tangeysh, Behzad

    The central objective of this work is developing convenient general procedures for controlling the formation and stabilization of nanoscale transition metal particles. Contemporary interest in developing alternative synthetic approaches for producing nanoparticles arises in large part from expanding applications of the nanomaterials in areas such as catalysis, electronics and medicine. This research focuses on advancing the existing nanoparticle synthetic routes by using a new class of polymer colloid materials as a chemical approach, and the laser irradiation of metal salt solution as a photo-chemical method to attain size and shape selectivity. Controlled synthesis of small metal nanoparticles with sizes ranging from 1 to 5nm is still a continuing challenge in nanomaterial synthesis. This research utilizes a new class of polymer colloid materials as nano-reactors and protective agents for controlling the formation of small transition metal nanoparticles. The polymer colloid particles were formed from cross-linking of dinegatively charged metal precursors with partially protonated poly dimethylaminoethylmethacrylate (PDMAEMA). Incorporation of [PtCl6]2- species into the colloidal particles prior to the chemical reduction was effectively employed as a new strategy for synthesis of unusually small platinum nanoparticles with narrow size distributions (1.12 +/-0.25nm). To explore the generality of this approach, in a series of proof-of-concept studies, this method was successfully employed for the synthesis of small palladium (1.4 +/-0.2nm) and copper nanoparticles (1.5 +/-0.6nm). The polymer colloid materials developed in this research are pH responsive, and are designed to self-assemble and/or disassemble by varying the levels of protonation of the polymer chains. This unique feature was used to tune the size of palladium nanoparticles in a small range from 1nm to 5nm. The procedure presented in this work is a new convenient room temperature route for synthesis of

  7. Aerosol based direct-write micro-additive fabrication method for sub-mm 3D metal-dielectric structures

    NASA Astrophysics Data System (ADS)

    Rahman, Taibur; Renaud, Luke; Heo, Deuk; Renn, Michael; Panat, Rahul

    2015-10-01

    The fabrication of 3D metal-dielectric structures at sub-mm length scale is highly important in order to realize low-loss passives and GHz wavelength antennas with applications in wearable and Internet-of-Things (IoT) devices. The inherent 2D nature of lithographic processes severely limits the available manufacturing routes to fabricate 3D structures. Further, the lithographic processes are subtractive and require the use of environmentally harmful chemicals. In this letter, we demonstrate an additive manufacturing method to fabricate 3D metal-dielectric structures at sub-mm length scale. A UV curable dielectric is dispensed from an Aerosol Jet system at 10-100 µm length scale and instantaneously cured to build complex 3D shapes at a length scale  <1 mm. A metal nanoparticle ink is then dispensed over the 3D dielectric using a combination of jetting action and tilted dispense head, also using the Aerosol Jet technique and at a length scale 10-100 µm, followed by the nanoparticle sintering. Simulation studies are carried out to demonstrate the feasibility of using such structures as mm-wave antennas. The manufacturing method described in this letter opens up the possibility of fabricating an entirely new class of custom-shaped 3D structures at a sub-mm length scale with potential applications in 3D antennas and passives.

  8. On the occurrence of metallic character in the periodic table of the chemical elements.

    PubMed

    Hensel, Friedrich; Slocombe, Daniel R; Edwards, Peter P

    2015-03-13

    The classification of a chemical element as either 'metal' or 'non-metal' continues to form the basis of an instantly recognizable, universal representation of the periodic table (Mendeleeff D. 1905 The principles of chemistry, vol. II, p. 23; Poliakoff M. & Tang S. 2015 Phil. Trans. R. Soc. A 373: , 20140211). Here, we review major, pre-quantum-mechanical innovations (Goldhammer DA. 1913 Dispersion und Absorption des Lichtes; Herzfeld KF. 1927 Phys. Rev. 29: , 701-705) that allow an understanding of the metallic or non-metallic status of the chemical elements under both ambient and extreme conditions. A special emphasis will be placed on recent experimental advances that investigate how the electronic properties of chemical elements vary with temperature and density, and how this invariably relates to a changing status of the chemical elements. Thus, the prototypical non-metals, hydrogen and helium, becomes metallic at high densities; and the acknowledged metals, mercury, rubidium and caesium, transform into their non-metallic forms at low elemental densities. This reflects the fundamental fact that, at temperatures above the absolute zero of temperature, there is therefore no clear dividing line between metals and non-metals. Our conventional demarcation of chemical elements as metals or non-metals within the periodic table is of course governed by our experience of the nature of the elements under ambient conditions. Examination of these other situations helps us to examine the exact divisions of the chemical elements into metals and non-metals (Mendeleeff D. 1905 The principles of chemistry, vol. II, p. 23). © 2015 The Author(s) Published by the Royal Society. All rights reserved.

  9. Remediation of metal polluted soils by phytorremediation combined with biochar addition

    NASA Astrophysics Data System (ADS)

    Méndez, Ana; Paz-Ferreiro, Jorge; Gómez-Limón, Dulce; César Arranz, Julio; Saa, Antonio; Gascó, Gabriel

    2016-04-01

    The main objective of this work is to optimize and quantify the treatment of metal polluted soils through phytoremediation techniques combined with the addition of biochar. Biochar is a carbon rich material obtained by thermal treatment of biomass in inert atmosphere. In recent years, it has been attracted considerable interest due to their positive effect after soil addition. The use of biochar also seems appropriate for the treatment of metal-contaminated soils decreasing their mobility. Biochar properties highly depend on the raw material composition and manufacturing conditions. This paper is based on the use of manure wastes, rich in nutrients and therefore interesting raw materials for biochar production, especially when combined with phytoremediation techniques since the biochar act as conditioner and slow release fertilizer. We are very grateful to Ministerio de Economia y Competitividad (Spain) for financial support under Project CGL2014-58322-R.

  10. A Novel Method for Fabricating Additive Manufactured Lightweight, Optical Quality Metallic Mirrors

    DTIC Science & Technology

    2016-01-04

    lighter  mirrors  can  lead to great reductions of mass in full systems [3,4].    The state of the art in this industry is ULE™,  Zerodur ™, or beryllium...1    A Novel Method for Fabricating Additive Manufactured  Lightweight, Optical Quality Metallic  Mirrors   Michael Stern, Joseph Bari  Distribution A...metallic  mirrors  fabricated by growing an additive manufactured blank, post  processing the faces, coating with electroless nickel, and diamond turning

  11. Metal-Catalyzed β-Functionalization of Michael Acceptors through Reductive Radical Addition Reactions.

    PubMed

    Streuff, Jan; Gansäuer, Andreas

    2015-11-23

    Transition-metal-catalyzed radical reactions are becoming increasingly important in modern organic chemistry. They offer fascinating and unconventional ways for connecting molecular fragments that are often complementary to traditional methods. In particular, reductive radical additions to α,β-unsaturated compounds have recently gained substantial attention as a result of their broad applicability in organic synthesis. This Minireview critically discusses the recent landmark achievements in this field in context with earlier reports that laid the foundation for today's developments.

  12. Recovery of valuable metals from electroplating sludge with reducing additives via vitrification.

    PubMed

    Huang, Ruth; Huang, Kuo-Lin; Lin, Zih-Yi; Wang, Jian-Wen; Lin, Chitsan; Kuo, Yi-Ming

    2013-11-15

    In this study, vitrification was applied to treat Ni-Cu electroplating sludge. The sludge was mixed with additives (limestone:cullet = 4:6) and then heated to 1450 °C. The cooled product could be separated into slag and ingot. An atomic absorption spectrometer was used to determine the metal levels of specimens and toxicity characteristic leaching procedure (TCLP) tests, whereas the crystalline and surface characteristics were examined using quantitative X-ray diffraction (XRD) analysis and scanning electron microscopy, respectively. With a glassy structure, the slag was mainly composed of Ca, Si, and Mg. The TCLP results of slags met the Taiwan regulated standards, suggesting that slag can be used for recycling purposes. With the aid of additives, the crystalline phase of slag was transformed form CaMgSiO4 into CsSiO3. The ingots were mainly composed of Ni (563,000-693,800 mg/kg), Cu (79,900-87,400 mg/kg), and Fe (35,000-43,600 mg/kg) (target metals) due the gravity separation during vitrification. At appropriate additives/sludge ratios (>0.2), >95% of target metals gathered in the ingot as a recoverable form (Ni-Fe alloy). The high Ni level of slag suggests that the ingot can be used as the raw materials for smelters or the additives for steel making. Therefore, the vitrification approach of this study is a promising technology to recover valuable metals from Ni-Cu electroplating sludge.

  13. Effect of transition metal salts on the initiated chemical vapor deposition of polymer thin films

    SciTech Connect

    Kwong, Philip; Seidel, Scott; Gupta, Malancha

    2015-05-15

    In this work, the effect of transition metal salts on the initiated chemical vapor deposition of polymer thin films was studied using x-ray photoelectron spectroscopy. The polymerizations of 4-vinyl pyridine and 1H,1H,2H,2H-perfluorodecyl acrylate were studied using copper(II) chloride (CuCl{sub 2}) and iron(III) chloride (FeCl{sub 3}) as the transition metal salts. It was found that the surface coverages of both poly(4-vinyl pyridine) (P4VP) and poly(1H,1H,2H,2H-perfluorodecyl acrylate) were decreased on CuCl{sub 2}, while the surface coverage of only P4VP was decreased on FeCl{sub 3}. The decreased polymer surface coverage was found to be due to quenching of the propagating radicals by the salt, which led to a reduction of the oxidation state of the metal. The identification of this reaction mechanism allowed for tuning of the effectiveness of the salts to decrease the polymer surface coverage through the adjustment of processing parameters such as the filament temperature. Additionally, it was demonstrated that the ability of transition metal salts to decrease the polymer surface coverage could be extended to the fabrication of patterned cross-linked coatings, which is important for many practical applications such as sensors and microelectronics.

  14. Use of chemical additives with steam injection to increase oil recovery. Final report

    SciTech Connect

    Handy, L.L.

    1984-09-01

    Surfactants and certain inorganic bases have been evaluated as possible chemical additives to improve performance of steamfloods. Special emphasis was given to chemicals which would reduce the residual oil saturation in regions flooded by hot water below the steam zone. Problems considered were the effect of prolonged exposure to steam temperature on the stability of petroleum sulfonates, the effect of temperature on surfactant adsorption and the effect of temperature on interfacial tensions. Methods were developed for measuring quantitatively the thermal stability of the aryl sulfonate class of surfactant. This class includes the petroleum sulfonates. The best of the surfactants evaluated in this study had marginal stability for use with steamfloods. The surfactants in combination with elevated temperatures do reduce residual oil saturations. Data are presented on the temperature effects on interfacial tensions and on adsorption. Certain inorganic chemicals which give high pH are effective and inexpensive but hydroxyl ions react with silica in the reservoir. This reaction is accentuated at higher temperatures. Data show that the pH of the injected hot water with caustic decreases with contact time. The experiments did not permit determining if an equilibrium pH would be obtained which would be high enough to be effective in recovering oil. Core floods showed that pH's in excess of 12 would be required to reduce residual oil saturations if sodium hydroxide was the injected chemical. The addition of surfactants with caustic or the use of sodium carbonate may permit recovery of oil at lower pH's. A reservoir simulator is being developed to predict performance of steamfloods with chemical additives. This has been completed for simple linear floods but is being extended to three dimensions and to more complicated flooding operations. 31 references, 43 figures, 2 tables.

  15. New chemical additive to enhance reduction of oil carryover in gas

    SciTech Connect

    Khatib, Z.I.

    1998-12-31

    Foaming and fouling in glycol contactors and/or in amine treating systems are frequent problems in gas treatment processes due to the entrainment of liquid and solid aerosols in the gas stream. Entrainment of these aerosols leads also to mechanical damage of turbines and/or unscheduled shutdown of compressor units. A new chemical additive was developed and applied in the gas stream. The additive was successful in preventing the dissemination of the oil and/or condensate carryover into aerosol sizes, thereby enhancing the performance of coalescer filters and scrubbers.

  16. ELECTRONIC AND CHEMICAL PROPERTIES OF PD IN BIMETALLIC SYSTEMS: HOW MUCH DO WE KNOW ABOUT HETERONUCLEAR METAL-METAL BONDING?

    SciTech Connect

    RODRIGUEZ,J.A.

    2001-09-27

    The experimental and theoretical studies described above illustrate the complex nature of the heteronuclear metal-metal bond. In many cases, bimetallic bonding induces a significant redistribution of charge around the bonded metals. This redistribution of charge is usually linked to the strength of the bimetallic bond, affects the position of the core and valence levels of the metals, and can determine the chemical reactivity of the system under study. New concepts are emerging [22,23,34,36] and eventually the coupling of experiment and theory can be useful for designing more efficient bimetallic catalysts [98,106,107].

  17. Bhasmas: unique ayurvedic metallic-herbal preparations, chemical characterization.

    PubMed

    Kumar, A; Nair, A G C; Reddy, A V R; Garg, A N

    2006-03-01

    Bhasmas are unique Ayurvedic metallic preparations with herbal juices/fruits, known in the Indian subcontinent since the seventh century BC and widely recommended for treatment of a variety of chronic ailments. Twenty bhasmas based on calcium, iron, zinc, mercury, silver, potassium, arsenic, copper, tin, and gemstones were analyzed for up to 18 elements by instrumental neutron activation analysis, including their C, H, N, and S contents. In addition to the major constituent element found at % level, several other essential elements such as Na, K, Ca, Mg, V, Mn, Fe, Cu, and Zn have also been found in microg/g amounts and ultratrace (ng/g) amounts of Au and Co. These seem to remain chelated with organic ligands derived from medicinal herbs. The bhasmas are biologically produced nanoparticles and are taken along with milk, butter, honey, or ghee (a preparation from milk); thus, this makes these elements easily assimilable, eliminating their harmful effects and enhancing their biocompatibility. Siddha Makaradhwaja, a mercury preparation is found to be stoichiometrically HgS without any traces of any other element. Similarly, Swet Parpati is stoichiometrically KNO3 but is found to have Mn, Cu, Zn, Na, P, and Cl as well. An attempt has been made to correlate the metallic contents with their medicinal importance. Na and K, the two electrolytic elements, seem to be well correlated, although K/Na varies in a wide range from 0.06 to 95, with specifically low values for Ca-, Fe-, and Zn-based bhasmas. K/P also varies in a wide range from 0.23 to 12, although for most bhasmas (n = 12), it is 2.3 +/- 1.2. Further, Fe/Mn is linearly correlated (r = 0.96) with Fe in nine noniron bhasmas.

  18. Fundamentals of the knowledge about chemical additives present in rubber gloves.

    PubMed

    Oliveira, Hegles Rosa de; Alchorne, Alice de Oliveira de Avelar

    2011-01-01

    One of the most frequent causes of allergic contact dermatitis of occupational origin are rubber additives, which are present in Personal Protective Equipment (PPE). The most allergenic additives of natural and synthetic gloves are thiurams, carbamates and mercapto group. To investigate the state of knowledge about the chemical additives used in the manufacture of synthetic rubber gloves. This was a qualitative research study in which professionals working in the manufacture, research, prescription and commercialization of gloves answered an open questionnaire. 30 individuals were interviewed: 4 researchers in occupational medicine, 5 occupational physicians, 2 occupational safety technicians, a rubber workers' union physician, an occupational safety engineer, a pro duction engineer of rubber gloves, 4 importers of gloves, a manufacturer of gloves, 3 businessmen who sell PPE, 3 salesclerks working in stores that sell PPE, 2 businessmen who own stores that sell products for allergic individuals, and 3 dermatologists. Knowledge of the chemical composition of rubber gloves is scant. The labeling of gloves, with the description of their chemical composition, would facilitate choosing the best type of glove for each person. This low-cost action to businesses would be a gain from the standpoint of public health, with huge repercussions for users of rubber gloves.

  19. CMB topography and electrical conductivity as additional constraints for the lowermost mantle thermo-chemical structure

    NASA Astrophysics Data System (ADS)

    Deschamps, F.; Yin, Y.; Tackley, P. J.

    2013-12-01

    A variety of seismic observations, including tomographic models, indicate that the lowermost mantle is strongly heterogeneous. Seismic observations further support a thermo-chemical origin for the large scale heterogeneities. In particular, the large low-shear wave velocity provinces (LLSVP) observed by global tomographic images are better explained by a combination of thermal and chemical anomalies. Despite the accuracy of seismic information, uncertainties and trade-off still prevent the determination of a detailed lower mantle thermo-chemical structure. For instance, the nature of chemical heterogeneities and the exact role played by the post-perovskite phase transition are still debated. Additional constraints are needed to discriminate between the possible models of structure and dynamics of the lower mantle. Here, we consider two potential additional constraints, the electrical conductivity and the dynamic topography at the core-mantle boundary (CMB). Unlike density and seismic velocities, electrical conductivity increases with temperature. In addition, it strongly varies with the iron and silicate content. Using appropriate mineral physics data, we calculated a 3D distribution of electrical conductivity in lower mantle from the thermo-chemical structure inferred by probabilistic tomography, which maps iron and silicate excess in the LLSVP. In the lowermost mantle, we observe a belt of high conductivity, with maximum values around 20 S/m located in the LLSVP. Such a belt may trigger electric currents in the lowermost mantle and induce magnetic field variations with period of one year or more. It may thus be seen by global models of electrical conductivity. Unfortunately, such models do not sample yet regions deeper than 2000 km. A second, independent constraint we explored is the dynamic topography at the CMB. We used stagYY to calculate the dynamic topography associated with several models of thermo-chemical convection, and observe strong differences

  20. Adsorption characteristics of metal ions on chitosan chemically modified by D-galactose

    SciTech Connect

    Kondo, Kazuo; Sumi, Hisaharu; Matsumoto, Michiaki

    1996-07-01

    The adsorption characteristics of metal ions on chitosan chemically modified by D-galactose were examined. The pH dependency on the distribution ratio was found to be affected by the valency of the metal ion, and the apparent adsorption equilibrium constants of the metal ions were determined. The order of adsorption of the metal ions is Ga > In > Nd > Eu for the trivalent metal ions and Cu > Ni > Co for the divalent metal ions. It is believed that amino and hydroxyl groups in the chitosan act as a chelating ligand.

  1. Selective Chemical Response of Transition Metal Dichalcogenides and Metal Dichalcogenides in Ambient Conditions.

    PubMed

    Park, Jun Hong; Vishwanath, Suresh; Wolf, Steven; Zhang, Kehao; Kwak, Iljo; Edmonds, Mary; Breeden, Michael; Liu, Xinyu; Dobrowolska, Margaret; Furdyna, Jacek; Robinson, Joshua A; Xing, Huili Grace; Kummel, Andrew C

    2017-08-30

    To fabricate practical devices based on semiconducting two-dimensional (2D) materials, the source, channel, and drain materials are exposed to ambient air. However, the response of layered 2D materials to air has not been fully elucidated at the molecular level. In the present report, the effects of air exposure on transition metal dichalcogenides (TMD) and metal dichalcogenides (MD) are studied using ultrahigh-vacuum scanning tunneling microscopy (STM). The effects of a 1-day ambient air exposure on MBE-grown WSe2, chemical vapor deposition (CVD)-grown MoS2, and MBE SnSe2 are compared. Both MBE-grown WSe2 and CVD-grown MoS2 display a selective air exposure response at the step edges, consistent with oxidation on WSe2 and adsorption of hydrocarbon on MoS2, while the terraces and domain/grain boundaries of both TMDs are nearly inert to ambient air. Conversely, MBE-grown SnSe2, an MD, is not stable in ambient air. After exposure in ambient air for 1 day, the entire surface of SnSe2 is decomposed to SnOx and SeOx, as seen with X-ray photoelectron spectroscopy. Since the oxidation enthalpy of all three materials is similar, the data is consistent with greater oxidation of SnSe2 being driven by the weak bonding of SnSe2.

  2. Additive Manufacturing and Characterization of Polylactic Acid (PLA) Composites Containing Metal Reinforcements

    NASA Technical Reports Server (NTRS)

    Kuentz, Lily; Salem, Anton; Singh, M.; Halbig, M. C.; Salem, J. A.

    2016-01-01

    Additive manufacturing of polymeric systems using 3D printing has become quite popular recently due to rapid growth and availability of low cost and open source 3D printers. Two widely used 3D printing filaments are based on polylactic acid (PLA) and acrylonitrile butadiene styrene (ABS) systems. PLA is much more environmentally friendly in comparison to ABS since it is made from renewable resources such as corn, sugarcane, and other starches as precursors. Recently, polylactic acid-based metal powder containing composite filaments have emerged which could be utilized for multifunctional applications. The composite filaments have higher density than pure PLA, and the majority of the materials volume is made up of polylactic acid. In order to utilize functionalities of composite filaments, printing behavior and properties of 3-D printed composites need to be characterized and compared with the pure PLA materials. In this study, pure PLA and composite specimens with different metallic reinforcements (Copper, Bronze, Tungsten, Iron, etc) were 3D printed at various layer heights and resulting microstructures and properties were characterized. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) behavior of filaments with different reinforcements were studied. The microscopy results show an increase in porosity between 3-D printed regular PLA and the metal composite PLA samples, which could produce weaker mechanical properties in the metal composite materials. Tensile strength and fracture toughness behavior of specimens as a function of print layer height will be presented.

  3. Progress Towards Metal Additive Manufacturing Standardization to Support Qualification and Certification

    NASA Astrophysics Data System (ADS)

    Seifi, Mohsen; Gorelik, Michael; Waller, Jess; Hrabe, Nik; Shamsaei, Nima; Daniewicz, Steve; Lewandowski, John J.

    2017-03-01

    As the metal additive manufacturing (AM) industry moves towards industrial production, the need for qualification standards covering all aspects of the technology becomes ever more prevalent. While some standards and specifications for documenting the various aspects of AM processes and materials exist and continue to evolve, many such standards still need to be matured or are under consideration/development within standards development organizations. An important subset of this evolving the standardization domain has to do with critical property measurements for AM materials. While such measurement procedures are well documented, with various legacy standards for conventional metallic material forms such as cast or wrought structural alloys, many fewer standards are currently available to enable systematic evaluation of those properties in AM-processed metallic materials. This is due in part to the current lack of AM-specific standards and specifications for AM materials and processes, which are a logical precursor to the material characterization standards for any material system. This paper summarizes some of the important standardization activities, as well as limitations associated with using currently available standards for metal AM with a focus on measuring mission-critical properties. Technical considerations in support of future standards development, as well as a pathway for qualification/certification of AM parts enabled by the appropriate standardization landscape, are discussed.

  4. Electrolyte additive enabled fast charging and stable cycling lithium metal batteries

    NASA Astrophysics Data System (ADS)

    Zheng, Jianming; Engelhard, Mark H.; Mei, Donghai; Jiao, Shuhong; Polzin, Bryant J.; Zhang, Ji-Guang; Xu, Wu

    2017-03-01

    Batteries using lithium (Li) metal as anodes are considered promising energy storage systems because of their high energy densities. However, safety concerns associated with dendrite growth along with limited cycle life, especially at high charge current densities, hinder their practical uses. Here we report that an optimal amount (0.05 M) of LiPF6 as an additive in LiTFSI-LiBOB dual-salt/carbonate-solvent-based electrolytes significantly enhances the charging capability and cycling stability of Li metal batteries. In a Li metal battery using a 4-V Li-ion cathode at a moderately high loading of 1.75 mAh cm‑2, a cyclability of 97.1% capacity retention after 500 cycles along with very limited increase in electrode overpotential is accomplished at a charge/discharge current density up to 1.75 mA cm‑2. The fast charging and stable cycling performances are ascribed to the generation of a robust and conductive solid electrolyte interphase at the Li metal surface and stabilization of the Al cathode current collector.

  5. Solidification/stabilization of fly ash from city refuse incinerator facility and heavy metal sludge with cement additives.

    PubMed

    Cerbo, Atlas Adonis V; Ballesteros, Florencio; Chen, Teng Chien; Lu, Ming-Chun

    2017-01-01

    Solidification and stabilization are well-known technologies used for treating hazardous waste. These technologies that use cementitious binder have been applied for decades as a final treatment procedure prior to the hazardous waste disposal. In the present work, hazardous waste like fly ash containing high concentrations of heavy metals such Zn (4715.56 mg/kg), Pb (1300.56 mg/kg), and Cu (534.72 mg/kg) and amounts of Ag, Cd, Co, Cr, Mn, and Ni was sampled from a city refuse incinerator facility. This fly ash was utilized in the solidification/stabilization of heavy metal sludge since fly ash has cement-like characteristics. Cement additives such as sodium sulfate, sodium carbonate, and ethylenediaminetetraacetic acid (EDTA) was incorporated to the solidified matrix in order to determine its effect on the solidification/stabilization performance. The solidified matrix was cured for 7, 14, 21, and 28 days prior for its physical and chemical characterizations. The results show that the solidified matrix containing 40% fly ash and 60% cement with heavy metal sludge was the formulation that has the highest fly ash content with a satisfactory strength. The solidified matrix was also able to immobilize the heavy metals both found in the fly ash and sludge based on the toxicity characteristic leaching procedure (TCLP) test. It also shows that the incorporation of sodium carbonate into the solidified matrix not only further improved the compressive strength from 0.36 MPa (without Na2CO3) to 0.54 MPa (with Na2CO3) but also increased its leaching resistance.

  6. Nitrite addition to acidified sludge significantly improves digestibility, toxic metal removal, dewaterability and pathogen reduction

    PubMed Central

    Du, Fangzhou; Keller, Jürg; Yuan, Zhiguo; Batstone, Damien J.; Freguia, Stefano; Pikaar, Ilje

    2016-01-01

    Sludge management is a major issue for water utilities globally. Poor digestibility and dewaterability are the main factors determining the cost for sludge management, whereas pathogen and toxic metal concentrations limit beneficial reuse. In this study, the effects of low level nitrite addition to acidified sludge to simultaneously enhance digestibility, toxic metal removal, dewaterability and pathogen reduction were investigated. Waste activated sludge (WAS) from a full-scale waste water treatment plant was treated at pH 2 with 10 mg NO2−-N/L for 5 h. Biochemical methane potential tests showed an increase in the methane production of 28%, corresponding to an improvement from 247 ± 8 L CH4/kg VS to 317 ± 1 L CH4/kg VS. The enhanced removal of toxic metals further increased the methane production by another 18% to 360 ± 6 L CH4/kg VS (a total increase of 46%). The solids content of dewatered sludge increased from 14.6 ± 1.4% in the control to 18.2 ± 0.8%. A 4-log reduction for both total coliforms and E. coli was achieved. Overall, this study highlights the potential of acidification with low level nitrite addition as an effective and simple method achieving multiple improvements in terms of sludge management. PMID:28004811

  7. A Fully Non-Metallic Gas Turbine Engine Enabled by Additive Manufacturing

    NASA Technical Reports Server (NTRS)

    Grady, Joseph E.

    2015-01-01

    The Non-Metallic Gas Turbine Engine project, funded by NASA Aeronautics Research Institute, represents the first comprehensive evaluation of emerging materials and manufacturing technologies that will enable fully nonmetallic gas turbine engines. This will be achieved by assessing the feasibility of using additive manufacturing technologies to fabricate polymer matrix composite and ceramic matrix composite turbine engine components. The benefits include: 50 weight reduction compared to metallic parts, reduced manufacturing costs, reduced part count and rapid design iterations. Two high payoff metallic components have been identified for replacement with PMCs and will be fabricated using fused deposition modeling (FDM) with high temperature polymer filaments. The CMC effort uses a binder jet process to fabricate silicon carbide test coupons and demonstration articles. Microstructural analysis and mechanical testing will be conducted on the PMC and CMC materials. System studies will assess the benefits of fully nonmetallic gas turbine engine in terms of fuel burn, emissions, reduction of part count, and cost. The research project includes a multidisciplinary, multiorganization NASA - industry team that includes experts in ceramic materials and CMCs, polymers and PMCs, structural engineering, additive manufacturing, engine design and analysis, and system analysis.

  8. Nitrite addition to acidified sludge significantly improves digestibility, toxic metal removal, dewaterability and pathogen reduction

    NASA Astrophysics Data System (ADS)

    Du, Fangzhou; Keller, Jürg; Yuan, Zhiguo; Batstone, Damien J.; Freguia, Stefano; Pikaar, Ilje

    2016-12-01

    Sludge management is a major issue for water utilities globally. Poor digestibility and dewaterability are the main factors determining the cost for sludge management, whereas pathogen and toxic metal concentrations limit beneficial reuse. In this study, the effects of low level nitrite addition to acidified sludge to simultaneously enhance digestibility, toxic metal removal, dewaterability and pathogen reduction were investigated. Waste activated sludge (WAS) from a full-scale waste water treatment plant was treated at pH 2 with 10 mg NO2‑-N/L for 5 h. Biochemical methane potential tests showed an increase in the methane production of 28%, corresponding to an improvement from 247 ± 8 L CH4/kg VS to 317 ± 1 L CH4/kg VS. The enhanced removal of toxic metals further increased the methane production by another 18% to 360 ± 6 L CH4/kg VS (a total increase of 46%). The solids content of dewatered sludge increased from 14.6 ± 1.4% in the control to 18.2 ± 0.8%. A 4-log reduction for both total coliforms and E. coli was achieved. Overall, this study highlights the potential of acidification with low level nitrite addition as an effective and simple method achieving multiple improvements in terms of sludge management.

  9. Force-induced chemical reactions on the metal centre in a single metalloprotein molecule.

    PubMed

    Zheng, Peng; Arantes, Guilherme M; Field, Martin J; Li, Hongbin

    2015-06-25

    Metalloproteins play indispensable roles in biology owing to the versatile chemical reactivity of metal centres. However, studying their reactivity in many metalloproteins is challenging, as protein three-dimensional structure encloses labile metal centres, thus limiting their access to reactants and impeding direct measurements. Here we demonstrate the use of single-molecule atomic force microscopy to induce partial unfolding to expose metal centres in metalloproteins to aqueous solution, thus allowing for studying their chemical reactivity in aqueous solution for the first time. As a proof-of-principle, we demonstrate two chemical reactions for the FeS4 centre in rubredoxin: electrophilic protonation and nucleophilic ligand substitution. Our results show that protonation and ligand substitution result in mechanical destabilization of the FeS4 centre. Quantum chemical calculations corroborated experimental results and revealed detailed reaction mechanisms. We anticipate that this novel approach will provide insights into chemical reactivity of metal centres in metalloproteins under biologically more relevant conditions.

  10. Chemical reactions at metallic and metal/semiconductor interfaces stimulated by pulsed laser annealing

    NASA Astrophysics Data System (ADS)

    Petit, E. J.; Caudano, R.

    1992-01-01

    Multilayer Al/Sb thin films have been evaporated on GaSb single crystals in ultra-high vacuum and pulsed-laser irradiated in-situ above the energy density threshold for surface melting. Superficial and interfacial chemical reactions have been characterized in-situ by Auger electron spectroscopy; and later, by X-ray photoelectron spectroscopy profiling, Rutherford backscattering spectrometry and scanning electron microscopy. The chemical reaction between the Al and Sb films is considered as a model reaction for laser-assisted synthesis of high-purity intermetallic compounds. The observation of a strong interfacial reaction between the melted film and the substrate is also a subject of great concern for optical data recording and laser alloying of ohmic contacts on semiconductors. We show that a suitable choice of the substrate and adding a low surface tension element into the metallic film can improve its stability during melting, and prevent inhomogeneous reaction and formation of holes, cracks and particles. Finally, other solutions are suggested to improve the control of these reactions.

  11. Reduction of Surface Roughness by Means of Laser Processing over Additive Manufacturing Metal Parts.

    PubMed

    Alfieri, Vittorio; Argenio, Paolo; Caiazzo, Fabrizia; Sergi, Vincenzo

    2016-12-31

    Optimization of processing parameters and exposure strategies is usually performed in additive manufacturing to set up the process; nevertheless, standards for roughness may not be evenly matched on a single complex part, since surface features depend on the building direction of the part. This paper aims to evaluate post processing treating via laser surface modification by means of scanning optics and beam wobbling to process metal parts resulting from selective laser melting of stainless steel in order to improve surface topography. The results are discussed in terms of roughness, geometry of the fusion zone in the cross-section, microstructural modification, and microhardness so as to assess the effects of laser post processing. The benefits of beam wobbling over linear scanning processing are shown, as heat effects in the base metal are proven to be lower.

  12. [Survey of toxic heavy metals and arsenic in existing food additives (natural colors)].

    PubMed

    Ogimoto, Mami; Uematsu, Yoko; Suzuki, Kumi; Kabashima, Junichiro; Nakazato, Mitsuo

    2009-10-01

    Pollution levels of toxic heavy metals (Pb, Cd, Hg) and arsenic in existing food additives used as food colors (40 samples of 15 kinds) were investigated. Heavy metals were detected in 8 samples; Pb in 1 sample (2.8 microg/g), Hg in 8 samples (0.1-3.4 microg/g) and arsenic in 2 samples (1.7, 2.6 microg/g). The Pb level in 1 sample of lac color (2.8 microg/g) exceeded the limit of 2 microg/g proposed by JECFA and Hg levels in 3 samples of cacao color (1.2-3.4 microg/g) exceeded the limit of 1 microg/g in the EU specification.

  13. Reduction of Surface Roughness by Means of Laser Processing over Additive Manufacturing Metal Parts

    PubMed Central

    Alfieri, Vittorio; Argenio, Paolo; Caiazzo, Fabrizia; Sergi, Vincenzo

    2016-01-01

    Optimization of processing parameters and exposure strategies is usually performed in additive manufacturing to set up the process; nevertheless, standards for roughness may not be evenly matched on a single complex part, since surface features depend on the building direction of the part. This paper aims to evaluate post processing treating via laser surface modification by means of scanning optics and beam wobbling to process metal parts resulting from selective laser melting of stainless steel in order to improve surface topography. The results are discussed in terms of roughness, geometry of the fusion zone in the cross-section, microstructural modification, and microhardness so as to assess the effects of laser post processing. The benefits of beam wobbling over linear scanning processing are shown, as heat effects in the base metal are proven to be lower. PMID:28772380

  14. How the toughness in metallic glasses depends on topological and chemical heterogeneity

    PubMed Central

    An, Qi; Samwer, Konrad; Demetriou, Marios D.; Floyd, Michael C.; Duggins, Danielle O.; Johnson, William L.; Goddard, William A.

    2016-01-01

    To gain insight into the large toughness variability observed between metallic glasses (MGs), we examine the origin of fracture toughness through bending experiments and molecular dynamics (MD) simulations for two binary MGs: Pd82Si18 and Cu46Zr54. The bending experiments show that Pd82Si18 is considerably tougher than Cu46Zr54, and the higher toughness of Pd82Si18 is attributed to an ability to deform plastically in the absence of crack nucleation through cavitation. The MD simulations study the initial stages of cavitation in both materials and extract the critical factors controlling cavitation. We find that for the tougher Pd82Si18, cavitation is governed by chemical inhomogeneity in addition to topological structures. In contrast, no such chemical correlations are observed in the more brittle Cu46Zr54, where topological low coordination number polyhedra are still observed around the critical cavity. As such, chemical inhomogeneity leads to more difficult cavitation initiation in Pd82Si18 than in Cu46Zr54, leading to a higher toughness. The absence of chemical separation during cavitation initiation in Cu46Zr54 decreases the energy barrier for a cavitation event, leading to lower toughness. PMID:27307438

  15. How the toughness in metallic glasses depends on topological and chemical heterogeneity.

    PubMed

    An, Qi; Samwer, Konrad; Demetriou, Marios D; Floyd, Michael C; Duggins, Danielle O; Johnson, William L; Goddard, William A

    2016-06-28

    To gain insight into the large toughness variability observed between metallic glasses (MGs), we examine the origin of fracture toughness through bending experiments and molecular dynamics (MD) simulations for two binary MGs: Pd82Si18 and Cu46Zr54 The bending experiments show that Pd82Si18 is considerably tougher than Cu46Zr54, and the higher toughness of Pd82Si18 is attributed to an ability to deform plastically in the absence of crack nucleation through cavitation. The MD simulations study the initial stages of cavitation in both materials and extract the critical factors controlling cavitation. We find that for the tougher Pd82Si18, cavitation is governed by chemical inhomogeneity in addition to topological structures. In contrast, no such chemical correlations are observed in the more brittle Cu46Zr54, where topological low coordination number polyhedra are still observed around the critical cavity. As such, chemical inhomogeneity leads to more difficult cavitation initiation in Pd82Si18 than in Cu46Zr54, leading to a higher toughness. The absence of chemical separation during cavitation initiation in Cu46Zr54 decreases the energy barrier for a cavitation event, leading to lower toughness.

  16. Arsenic Remediation Enhancement Through Chemical Additions to Pump and Treat Operations

    NASA Astrophysics Data System (ADS)

    Wovkulich, K.; Mailloux, B. J.; Stute, M.; Simpson, H. J.; Keimowitz, A. R.; Powell, A.; Lacko, A.; Chillrud, S. N.

    2008-12-01

    Arsenic is a contaminant found at more than 500 US Superfund sites. Since pump and treat technologies are widely used for remediation of contaminated groundwater, increasing the efficiency of contaminant removal at such sites should allow limited financial resources to clean up more sites. The Vineland Chemical Company Superfund site is extensively contaminated with arsenic after waste arsenic salts were stored and disposed of improperly for much of the company's 44 year manufacturing lifetime. Despite approximately eight years of pump and treat remediation, arsenic concentrations in the recovery wells can still be greater than 1000 ppb. The arsenic concentrations in the groundwater remain high because of slow desorption of arsenic from contaminated aquifer solids. Extrapolation of laboratory column experiments suggest that continuing the current groundwater remediation practice based on flushing ambient groundwater through the system may require on the order of hundreds of years to clean the site. However, chemical additions of phosphate or oxalic acid into the aquifer could decrease the remediation time scale substantially. Laboratory results from a soil column experiment using input of 10 mM oxalic acid suggest that site clean up of groundwater could be decreased to as little as four years. Pilot scale forced gradient field experiments will help establish whether chemical additions can be effective for increasing arsenic mobilization from aquifer solids and thus substantially decrease pump and treat clean up time.

  17. [Effects of nitrogen addition on soil physico-chemical properties and enzyme activities in desertified steppe].

    PubMed

    Su, Jie-Qiong; Li, Xin-Rong; Bao, Jing-Ting

    2014-03-01

    To investigate the impacts of nitrogen (N) enrichment on soil physico-chemical property and soil enzyme activities in desert ecosystems, a field experiment by adding N at 0, 1.75, 3.5, 7, or 14 g N x m(-2) a(-1) was conducted in a temperate desert steppe in the southeastern fringe of the Tengger Desert. The results showed that N addition led to accumulations of total N, NO(3-)-N, NH(4+)-N, and available N in the upper soil (0-10 cm) and subsoil (10-20 cm), however, reductions in soil pH were observed, causing soil acidification to some extent. N addition pronouncedly inhibited soil enzyme activities, which were different among N addition levels, soil depths, and years, respectively. Soil enzyme activities were significantly correlated with the soil N level, soil pH, and soil moisture content, respectively.

  18. Radiative properties of ceramic metal-halide high intensity discharge lamps containing additives in argon plasma

    NASA Astrophysics Data System (ADS)

    Cressault, Yann; Teulet, Philippe; Zissis, Georges

    2016-07-01

    The lighting represents a consumption of about 19% of the world electricity production. We are thus searching new effective and environment-friendlier light sources. The ceramic metal-halide high intensity lamps (C-MHL) are one of the options for illuminating very high area. The new C-MHL lamps contain additives species that reduce mercury inside and lead to a richer spectrum in specific spectral intervals, a better colour temperature or colour rendering index. This work is particularly focused on the power radiated by these lamps, estimated using the net emission coefficient, and depending on several additives (calcium, sodium, tungsten, dysprosium, and thallium or strontium iodides). The results show the strong influence of the additives on the power radiated despite of their small quantity in the mixtures and the increase of visible radiation portion in presence of dysprosium.

  19. Analysis of additive metals in fuel and emission aerosols of diesel vehicles with and without particle traps.

    PubMed

    Ulrich, Andrea; Wichser, Adrian

    2003-09-01

    Fuel additives used in particle traps have to comply with environmental directives and should not support the formation of additional toxic substances. The emission of metal additives from diesel engines with downstream particle traps has been studied. Aspects of the optimisation of sampling procedure, sample preparation and analysis are described. Exemplary results in form of a mass balance calculation are presented. The results demonstrate the high retention rate of the studied filter system but also possible deposition of additive metals in the engine.

  20. Thermotropic Behavior of Membranes Containing DMPC and Chemically and Stereochemically Pure Sphingomyelin upon Cholesterol Addition

    NASA Astrophysics Data System (ADS)

    Shibakami, Motonari; Sonoyama, Masashi; Goto, Rie; Mori, Michiko; Suzuki, Hikokazu; Mitaku, Shigeki

    2004-12-01

    High sensitivity differential scanning calorimetry is applied to the problem of interaction between phospholipids and cholesterol in bilayers, i.e., whether or not cholesterol shows a preferential interaction with sphingomyelins over glycerophospholipids. The simplest system yet used for exploring this problem is designed—one composed of 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC), chemically and stereochemically pure N-palmitoyl-sphingomyelin (pure-C16:0-SM), and cholesterol, based on a belief that chemically and stereochemically purity excludes chain length mismatch and chiral interaction that may affect the interaction from this system. Incremental addition of cholesterol to mixtures of DMPC and pure-C16:0-SM with a ratio of 6:4 or 4:6 leads to a continuous shift in endotherm due to DMPC toward a lower temperature. Such results indicate that cholesterol favors pure-C16:0-SM.

  1. Chemical associations and mobilization of heavy metals in fly ash from municipal solid waste incineration.

    PubMed

    Weibel, Gisela; Eggenberger, Urs; Schlumberger, Stefan; Mäder, Urs K

    2016-12-19

    This study focusses on chemical and mineralogical characterization of fly ash and leached filter cake and on the determination of parameters influencing metal mobilization by leaching. Three different leaching processes of fly ash from municipal solid waste incineration (MSWI) plants in Switzerland comprise neutral, acidic and optimized acidic (+ oxidizing agent) fly ash leaching have been investigated. Fly ash is characterized by refractory particles (Al-foil, unburnt carbon, quartz, feldspar) and newly formed high-temperature phases (glass, gehlenite, wollastonite) surrounded by characteristic dust rims. Metals are carried along with the flue gas (Fe-oxides, brass) and are enriched in mineral aggregates (quartz, feldspar, wollastonite, glass) or vaporized and condensed as chlorides or sulphates. Parameters controlling the mobilization of neutral and acidic fly ash leaching are pH and redox conditions, liquid to solid ratio, extraction time and temperature. Almost no depletion for Zn, Pb, Cu and Cd is achieved by performing neutral leaching. Acidic fly ash leaching results in depletion factors of 40% for Zn, 53% for Cd, 8% for Pb and 6% for Cu. The extraction of Pb and Cu are mainly limited due to a cementation process and the formation of a PbCu(0)-alloy-phase and to a minor degree due to secondary precipitation (PbCl2). The addition of hydrogen peroxide during acidic fly ash leaching (optimized acidic leaching) prevents this reduction through oxidation of metallic components and thus significantly higher depletion factors for Pb (57%), Cu (30%) and Cd (92%) are achieved. The elevated metal depletion using acidic leaching in combination with hydrogen peroxide justifies the extra effort not only by reduced metal loads to the environment but also by reduced deposition costs.

  2. Chemicals, metals, and pesticide pits waste unit low induction number electromagnetic survey

    SciTech Connect

    Cumbest, R.J.; Mohon, D.

    1995-06-01

    An electromagnetic survey was conducted at the Chemicals, Metals, and Pesticide Waste Unit to identify any buried metallic objects that may be present in the materials used to fill and cover the pits after removal of pit debris. The survey was conducted with a Geonics EM-31 Terrain Conductivity Meter along north - south oriented traverses with 5-ft station intervals to produce a 5-ft by 5-ft square grid node pattern. Both conductivity and in-phase components were measured at each station for vertical dipole orientation with the common axis of the dipoles in the north - south and east - west orientations. The conductivity data clearly show elevated conductivities (2.1 to 7.0 mS/m) associated with the material over the pits, as compared with the surrounding area that is characterized by lower conductivities (1 to 2 mS/m). This is probably the result of the higher clay content of the fill material relative to the surrounding area, which has a higher sand to clay ratio and the presence of a plastic cover beneath the fill that has probably trapped water. Many metal objects are present in the survey area including manhole covers, monitoring well heads, metal, signs, drain culverts, abandoned wells, and BP waste unit marker balls. AU of these exhibit associated conductivity and in-phase anomalies of various magnitude. In addition to these anomalies that can be definitely associated with surface sources, conductivity and in-phase anomalies are also present with no obvious surface source. These anomalies are probably indicative of subsurface buried metallic objects. A high concentration of these objects appears to be present in the southwest corner of the survey area.

  3. Transition-metal-catalyzed additions of C-H bonds to C-X (X = N, O) multiple bonds via C-H bond activation.

    PubMed

    Yan, Guobing; Wu, Xiangmei; Yang, Minghua

    2013-09-14

    Chemical transformations via catalytic C-H bond activation have been established as one of the most powerful tools in organic synthetic chemistry. Transition-metal-catalyzed addition reactions of C-H bonds to polar C-X (X = N, O) multiple bonds, such as aldehydes, ketones, imines, isocyanates, nitriles, isocyanides, carbon monoxide and carbon dioxide, have undergone a rapid development in recent years. In this review, recent advances in this active area have been highlighted and their mechanisms have been discussed.

  4. The effect of chemical additives on the synthesis of ethanol. Technical progress report 6, December 16, 1988--March 15, 1989

    SciTech Connect

    Chuang, S.S.C.

    1989-04-30

    The objective of this research is to elucidate the role of various chemical additives on ethanol synthesis over Rh- and Ni-based catalysts. Chemical additives used for this study will include S, P, Ag, Cu, Mn, and Na which have different electronegativeities. The effect of additives on the surface state of the catalysts, heat of adsorption of reactant molecules, reaction intermediates, reaction pathways, reaction kinetics, and product distributions is/will be investigated by a series of experimental studies of NO adsorption, reactive probing, steady state rate measurement, and transient kinetic study. CO insertion is known to be a key step to the formation of acetaldehyde and ethanol from CO hydrogenation. Reaction of ethylene with syngas is used as a probe to determine CO insertion capabilities of metal catalysts. During the sixth quarter of the project, the mechanism of CO insertion on Ni/SiO{sub 2} was investigated by in-situ infrared spectroscopy. Ni/SiO{sub 2}, a methanation catalyst, has been shown to exhibit CO insertion activity. In situ infrared studies of CO/H{sub 2} and C{sub 2}H{sub 4}/CO/H{sub 2} reactions show that the carbonylation of Ni/SiO{sub 2} to Ni(CO){sub 4} leads to an inhibition of methanation in CO hydrogenation but an enhancement of formation of propionaldehyde in C{sub 2}H{sub 4}/CO/H{sub 2} reaction. The results suggest that the sites for propionaldehyde formation is different from those for methanation.

  5. Thermal and Chemical Characterization of Non-Metallic Materials Using Coupled Thermogravimetric Analysis and Infrared Spectroscopy

    NASA Technical Reports Server (NTRS)

    Huff, Timothy L.

    2002-01-01

    Thermogravimetric analysis (TGA) is widely employed in the thermal characterization of non-metallic materials, yielding valuable information on decomposition characteristics of a sample over a wide temperature range. However, a potential wealth of chemical information is lost during the process, with the evolving gases generated during thermal decomposition escaping through the exhaust line. Fourier Transform-Infrared spectroscopy (FT-IR) is a powerful analytical technique for determining many chemical constituents while in any material state, in this application, the gas phase. By linking these two techniques, evolving gases generated during the TGA process are directed into an appropriately equipped infrared spectrometer for chemical speciation. Consequently, both thermal decomposition and chemical characterization of a material may be obtained in a single sample run. In practice, a heated transfer line is employed to connect the two instruments while a purge gas stream directs the evolving gases into the FT-IR. The purge gas can be either high purity air or an inert gas such as nitrogen to allow oxidative and pyrolytic processes to be examined, respectively. The FT-IR data is collected realtime, allowing continuous monitoring of chemical compositional changes over the course of thermal decomposition. Using this coupled technique, an array of diverse materials has been examined, including composites, plastics, rubber, fiberglass epoxy resins, polycarbonates, silicones, lubricants and fluorocarbon materials. The benefit of combining these two methodologies is of particular importance in the aerospace community, where newly developing materials have little available data with which to refer. By providing both thermal and chemical data simultaneously, a more definitive and comprehensive characterization of the material is possible. Additionally, this procedure has been found to be a viable screening technique for certain materials, with the generated data useful in

  6. Thermal and Chemical Characterization of Non-metallic Materials Using Coupled Thermogravimetric Analysis and Infrared Spectroscopy

    NASA Technical Reports Server (NTRS)

    Huff, Timothy L.; Griffin, Dennis E. (Technical Monitor)

    2001-01-01

    Thermogravimetric analysis (TGA) is widely employed in the thermal characterization of non-metallic materials, yielding valuable information on decomposition characteristics of a sample over a wide temperature range. However, a potential wealth of chemical information is lost during the process, with the evolving gases generated during thermal decomposition escaping through the exhaust line. Fourier Transform-Infrared spectroscopy (FT-IR) is a powerful analytical technique for determining many chemical constituents while in any material state, in this application, the gas phase. By linking these two techniques, evolving gases generated during the TGA process are directed into an appropriately equipped infrared spectrometer for chemical speciation. Consequently, both thermal decomposition and chemical characterization of a material may be obtained in a single sample run. In practice, a heated transfer line is employed to connect the two instruments while a purge gas stream directs the evolving gases into the FT-IR, The purge gas can be either high purity air or an inert gas such as nitrogen to allow oxidative and pyrolytic processes to be examined, respectively. The FT-IR data is collected real-time, allowing continuous monitoring of chemical compositional changes over the course of thermal decomposition. Using this coupled technique, an array of diverse materials has been examined, including composites, plastics, rubber, fiberglass epoxy resins, polycarbonates, silicones, lubricants and fluorocarbon materials. The benefit of combining these two methodologies is of particular importance in the aerospace community, where newly developing materials have little available data with which to refer. By providing both thermal and chemical data simultaneously, a more definitive and comprehensive characterization of the material is possible. Additionally, this procedure has been found to be a viable screening technique for certain materials, with the generated data useful in

  7. A Fully Non-metallic Gas Turbine Engine Enabled by Additive Manufacturing

    NASA Technical Reports Server (NTRS)

    Grady, Joseph E.

    2014-01-01

    The Non-Metallic Gas Turbine Engine project, funded by NASA Aeronautics Research Institute (NARI), represents the first comprehensive evaluation of emerging materials and manufacturing technologies that will enable fully nonmetallic gas turbine engines. This will be achieved by assessing the feasibility of using additive manufacturing technologies for fabricating polymer matrix composite (PMC) and ceramic matrix composite (CMC) gas turbine engine components. The benefits of the proposed effort include: 50 weight reduction compared to metallic parts, reduced manufacturing costs due to less machining and no tooling requirements, reduced part count due to net shape single component fabrication, and rapid design change and production iterations. Two high payoff metallic components have been identified for replacement with PMCs and will be fabricated using fused deposition modeling (FDM) with high temperature capable polymer filaments. The first component is an acoustic panel treatment with a honeycomb structure with an integrated back sheet and perforated front sheet. The second component is a compressor inlet guide vane. The CMC effort, which is starting at a lower technology readiness level, will use a binder jet process to fabricate silicon carbide test coupons and demonstration articles. The polymer and ceramic additive manufacturing efforts will advance from monolithic materials toward silicon carbide and carbon fiber reinforced composites for improved properties. Microstructural analysis and mechanical testing will be conducted on the PMC and CMC materials. System studies will assess the benefits of fully nonmetallic gas turbine engine in terms of fuel burn, emissions, reduction of part count, and cost. The proposed effort will be focused on a small 7000 lbf gas turbine engine. However, the concepts are equally applicable to large gas turbine engines. The proposed effort includes a multidisciplinary, multiorganization NASA - industry team that includes experts in

  8. Exploiting Diffusion Barrier and Chemical Affinity of Metal-Organic Frameworks for Efficient Hydrogen Isotope Separation.

    PubMed

    Kim, Jin Yeong; Balderas-Xicohténcatl, Rafael; Zhang, Linda; Kang, Sung Gu; Hirscher, Michael; Oh, Hyunchul; Moon, Hoi Ri

    2017-09-29

    Deuterium plays a pivotal role in industrial and scientific research, and is irreplaceable for various applications such as isotope tracing, neutron moderation, and neutron scattering. In addition, deuterium is a key energy source for fusion reactions. Thus, the isolation of deuterium from a physico-chemically almost identical isotopic mixture is a seminal challenge in modern separation technology. However, current commercial approaches suffer from extremely low separation efficiency (i.e., cryogenic distillation, selectivity of 1.5 at 24 K), requiring a cost-effective and large-scale separation technique. Herein, we report a highly effective hydrogen isotope separation system based on metal-organic frameworks (MOFs) having the highest reported separation factor as high as ∼26 at 77 K by maximizing synergistic effects of the chemical affinity quantum sieving (CAQS) and kinetic quantum sieving (KQS). For this purpose, the MOF-74 system having high hydrogen adsorption enthalpies due to strong open metal sites is chosen for CAQS functionality, and imidazole molecules (IM) are employed to the system for enhancing the KQS effect. To the best of our knowledge, this work is not only the first attempt to implement two quantum sieving effects, KQS and CAQS, in one system, but also provides experimental validation of the utility of this system for practical industrial usage by isolating high-purity D2 through direct selective separation studies using 1:1 D2/H2 mixtures.

  9. Physical defect formation in few layer graphene-like carbon on metals: influence of temperature, acidity, and chemical functionalization.

    PubMed

    Schumacher, Christoph M; Grass, Robert N; Rossier, Michael; Athanassiou, Evagelos K; Stark, Wendelin J

    2012-03-06

    A systematical examination of the chemical stability of cobalt metal nanomagnets with a graphene-like carbon coating is used to study the otherwise rather elusive formation of nanometer-sized physical defects in few layer graphene as a result of acid treatments. We therefore first exposed the core-shell nanomaterial to well-controlled solutions of altering acidity and temperature. The release of cobalt into these solutions over time offered a simple tool to monitor the progress of particle degradation. The results suggested that the oxidative damage of the graphene-like coatings was the rate-limiting step during particle degradation since only fully intact or entirely emptied carbon shells were found after the experiments. If ionic noble metal species were additionally present in the acidic solutions, the noble metal was found to reduce on the surface of specific, defective particles. The altered electrochemical gradients across the carbon shells were however not found to lead to a faster release of cobalt from the particles. The suggested mechanistic insight was further confirmed by the covalent chemical functionalization of the particle surface with chemically inert aryl species, which leads to an additional thickening of the shells. This leads to reduced cobalt release rates as well as slower noble metal reduction rates depending on the augmentation of the shell thickness.

  10. Metal vapor micro-jet controls material redistribution in laser powder bed fusion additive manufacturing

    DOE PAGES

    Ly, Sonny; Rubenchik, Alexander M.; Khairallah, Saad A.; ...

    2017-06-22

    The results of detailed experiments and finite element modeling of metal micro-droplet motion associated with metal additive manufacturing (AM) processes are presented. Ultra high speed imaging of melt pool dynamics reveals that the dominant mechanism leading to micro-droplet ejection in a laser powder bed fusion AM is not from laser induced recoil pressure as is widely believed and found in laser welding processes, but rather from vapor driven entrainment of micro-particles by an ambient gas flow. The physics of droplet ejection under strong evaporative flow is described using simulations of the laser powder bed interactions to elucidate the experimental results.more » Hydrodynamic drag analysis is used to augment the single phase flow model and explain the entrainment phenomenon for 316 L stainless steel and Ti-6Al-4V powder layers. The relevance of vapor driven entrainment of metal micro-particles to similar fluid dynamic studies in other fields of science will be discussed.« less

  11. Effect of Polyaniline additions on structural and gas sensing behaviour of metal oxides thin films

    NASA Astrophysics Data System (ADS)

    Hj. Jumali, Mohammad H.; Izzuddin, Izura; Ramli, Norhashimah; Mat Salleh, Muhamad; Yahaya, Muhammad

    2009-07-01

    The structural and gas sensing behaviour of metal oxides namely TiO2 and ZnO thin films were investigated. In this paper, commercial Polyaniline (PANi) powder were added into two different metal oxides sol gel solutions with PANi : metal oxides weight ratios of 1wt.%, 2wt.% and 3wt.%. The thin films were fabricated using spin coating technique. Structural investigation using XRD presented that all films exhibited amorphous structure. Typical films surface morphology consists of agglomerated round shaped particles with the particles size varies between 57nm to 200nm. Addition of PANi formed network chains between the particles. Ethanol vapor detection test conducted at room temperature showed that both TiO2 and ZnO based films were capable to sense the vapor. The optimum ratio in sensing ethanol vapour for both PANi-TiO2 and PANi-ZnO films was 3:1. However, other issues such as reliability, selectability and repeatability remain as the major problems.

  12. Characterisation of the topography of metal additive surface features with different measurement technologies

    NASA Astrophysics Data System (ADS)

    Senin, Nicola; Thompson, Adam; Leach, Richard K.

    2017-09-01

    The challenges of measuring the surface topography of metallic surfaces produced by additive manufacturing are investigated. The differences between measurements made using various optical and non-optical technologies, including confocal and focus-variation microscopy, coherence scanning interferometry and x-ray computed tomography, are examined. As opposed to concentrating on differences which may arise through computing surface texture parameters from measured topography datasets, a comparative analysis is performed focussing on investigation of the quality of the topographic reconstruction of a series of surface features. The investigation is carried out by considering the typical surface features of a metal powder-bed fusion process: weld tracks, weld ripples, attached particles and surface recesses. Results show that no single measurement technology provides a completely reliable rendition of the topographic features that characterise the metal powder-bed fusion process. However, through analysis of measurement discrepancies, light can be shed on where instruments are more susceptible to error, and why differences between measurements occur. The results presented in this work increase the understanding of the behaviour and performance of areal topography measurement, and thus promote the development of improved surface characterisation pipelines.

  13. A brief survey of sensing for metal-based powder bed fusion additive manufacturing

    NASA Astrophysics Data System (ADS)

    Foster, Bryant K.; Reutzel, Edward W.; Nassar, Abdalla R.; Dickman, Corey J.; Hall, Benjamin T.

    2015-05-01

    Purpose - Powder bed fusion additive manufacturing (PBFAM) of metal components has attracted much attention, but the inability to quickly and easily ensure quality has limited its industrial use. Since the technology is currently being investigated for critical engineered components and is largely considered unsuitable for high volume production, traditional statistical quality control methods cannot be readily applied. An alternative strategy for quality control is to monitor the build in real time with a variety of sensing methods and, when possible, to correct any defects as they occur. This article reviews the cause of common defects in powder bed additive manufacturing, briefly surveys process monitoring strategies in the literature, and summarizes recently-developed strategies to monitor part quality during the build process. Design/methodology/approach - Factors that affect part quality in powder bed additive manufacturing are categorized as those influenced by machine variables and those affected by other build attributes. Within each category, multiple process monitoring methods are presented. Findings - A multitude of factors contribute to the overall quality of a part built using PBFAM. Rather than limiting processing to a pre-defined build recipe and assuming complete repeatability, part quality will be ensured by monitoring the process as it occurs and, when possible, altering the process conditions or build plan in real-time. Recent work shows promise in this area and brings us closer to the goal of wide-spread adoption of additive manufacturing technology. Originality/value - This work serves to introduce and define the possible sources of defects and errors in metal-based PBFAM, and surveys sensing and control methods which have recently been investigated to increase overall part quality. Emphasis has been placed on novel developments in the field and their contribution to the understanding of the additive manufacturing process.

  14. Elucidating triplet-sensitized photolysis mechanisms of sulfadiazine and metal ions effects by quantum chemical calculations.

    PubMed

    Wang, Se; Song, Xuedan; Hao, Ce; Gao, Zhanxian; Chen, Jingwen; Qiu, Jieshan

    2015-03-01

    Sulfadiazine (SDZ) mainly proceeds triplet-sensitized photolysis with dissolved organic matter (DOM) in the aquatic environment. However, the mechanisms underlying the triplet-sensitized photolysis of SDZ with DOM have not been fully worked out. In this study, we investigated the mechanisms of triplet-sensitized photolysis of SDZ(0) (neutral form) and SDZ(-) (anionic form) with four DOM analogues, i.e., fluorenone (FL), thioxanthone (TX), 2-acetonaphthone (2-AN), and 4-benzoylbenzoic acid (CBBP), and three metal ions (i.e., Mg(2+), Ca(2+), and Zn(2+)) effects using quantum chemical calculations. Results indicated that the triplet-sensitized photolysis mechanism of SDZ(0) with FL, TX, and 2-AN was hydrogen transfer, and with CBBP was electron transfer along with proton transfer (for complex SDZ(0)-CBBP2) and hydrogen transfer (for complex SDZ(0)-CBBP1). The triplet-sensitized photolysis mechanisms of SDZ(-) with FL, TX, and CBBP was electron transfer along with proton transfer, and with 2-AN was hydrogen transfer. The triplet-sensitized photolysis product of both SDZ(0) and SDZ(-) was a sulfur dioxide extrusion product (4-(2-iminopyrimidine-1(2H)-yl)aniline), but the formation routs of the products for SDZ(0) and SDZ(-) were different. In addition, effects of the metal ions on the triplet-sensitized photolysis of SDZ(0) and SDZ(-) were different. The metal ions promoted the triplet-sensitized photolysis of SDZ(0), but inhibited the triplet-sensitized photolysis of SDZ(-).

  15. Manipulating thermal conductance at metal-graphene contacts via chemical functionalization.

    PubMed

    Hopkins, Patrick E; Baraket, Mira; Barnat, Edward V; Beechem, Thomas E; Kearney, Sean P; Duda, John C; Robinson, Jeremy T; Walton, Scott G

    2012-02-08

    Graphene-based devices have garnered tremendous attention due to the unique physical properties arising from this purely two-dimensional carbon sheet leading to tremendous efficiency in the transport of thermal carriers (i.e., phonons). However, it is necessary for this two-dimensional material to be able to efficiently transport heat into the surrounding 3D device architecture in order to fully capitalize on its intrinsic transport capabilities. Therefore, the thermal boundary conductance at graphene interfaces is a critical parameter in the realization of graphene electronics and thermal solutions. In this work, we examine the role of chemical functionalization on the thermal boundary conductance across metal/graphene interfaces. Specifically, we metalize graphene that has been plasma functionalized and then measure the thermal boundary conductance at Al/graphene/SiO(2) contacts with time domain thermoreflectance. The addition of adsorbates to the graphene surfaces are shown to influence the cross plane thermal conductance; this behavior is attributed to changes in the bonding between the metal and the graphene, as both the phonon flux and the vibrational mismatch between the materials are each subject to the interfacial bond strength. These results demonstrate plasma-based functionalization of graphene surfaces is a viable approach to manipulate the thermal boundary conductance.

  16. Chemical and biological extraction of metals present in E waste: A hybrid technology.

    PubMed

    Pant, Deepak; Joshi, Deepika; Upreti, Manoj K; Kotnala, Ravindra K

    2012-05-01

    Management of metal pollution associated with E-waste is widespread across the globe. Currently used techniques for the extraction of metals from E-waste by using either chemical or biological leaching have their own limitations. Chemical leaching is much rapid and efficient but has its own environmental consequences, even the future prospects of associated nanoremediation are also uncertain. Biological leaching on the other hand is comparatively a cost effective technique but at the same moment it is time consuming and the complete recovery of the metal, alone by biological leaching is not possible in most of the cases. The current review addresses the individual issues related to chemical and biological extraction techniques and proposes a hybrid-methodology which incorporates both, along with safer chemicals and compatible microbes for better and efficient extraction of metals from the E-waste.

  17. Webinar Presentation: Metals, Endocrine Disrupting Chemicals and Biomarkers of Metabolic Syndrome Risk in Adolescence

    EPA Pesticide Factsheets

    This presentation, Metals, Endocrine Disrupting Chemicals and Biomarkers of Metabolic Syndrome Risk in Adolescence, was given at the NIEHS/EPA Children's Centers 2015 Webinar Series held on Feb. 11, 2015.

  18. 78 FR 74218 - Imposition of Additional Sanctions on Syria Under the Chemical and Biological Weapons Control and...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-12-10

    ... Imposition of Additional Sanctions on Syria Under the Chemical and Biological Weapons Control and Warfare... the Chemical and Biological Weapons Control and Warfare Elimination Act of 1991, 22 U.S.C. 5604(a) and...(b) of the Chemical and Biological Weapons Control and Warfare Elimination Act of 1991, as...

  19. Quasi-chemical approach for adsorption of mixtures with non-additive lateral interactions

    NASA Astrophysics Data System (ADS)

    Pinto, O. A.; Pasinetti, P. M.; Ramirez-Pastor, A. J.

    2017-01-01

    The statistical thermodynamics of binary mixtures with non-additive lateral interactions was developed on a generalization in the spirit of the lattice-gas model and the classical quasi-chemical approximation (QCA). The traditional assumption of a strictly pairwise additive nearest-neighbors interaction is replaced by a more general one, namely that the bond linking a certain atom with any of its neighbors depends considerably on how many of them are actually present (or absent) on the sites in the first coordination shell of the atom. The total and partial adsorption isotherms are given for both attractive and repulsive lateral interactions between the adsorbed species. Interesting behaviors are observed and discussed in terms of the low-temperature phases formed in the system. Comparisons with Monte Carlo simulations are performed in order to test the validity of the theoretical model.

  20. Biosensor and chemical sensor probes for calcium and other metal ions

    DOEpatents

    Vo-Dinh, Tuan; Viallet, Pierre

    1996-01-01

    The present invention relates to chemical sensor and biosensor probes for measuring low concentration of metals and metal ions in complex samples such as biological fluids, living cells, and environmental samples. More particularly the present invention relates to a gel-based Indo-1 and Fura-2 chemical sensor probes for the measurement of low concentrations of calcium, cadmium, magnesium and the like. Also disclosed is a detector device using the sensors of the present invention.

  1. ProPhenol-Catalyzed Asymmetric Additions by Spontaneously Assembled Dinuclear Main Group Metal Complexes

    PubMed Central

    2016-01-01

    Conspectus The development of catalytic enantioselective transformations has been the focus of many research groups over the past half century and is of paramount importance to the pharmaceutical and agrochemical industries. Since the award of the Nobel Prize in 2001, the field of enantioselective transition metal catalysis has soared to new heights, with the development of more efficient catalysts and new catalytic transformations at increasing frequency. Furthermore, catalytic reactions that allow higher levels of redox- and step-economy are being developed. Thus, alternatives to asymmetric alkene dihydroxylation and the enantioselective reduction of α,β-unsaturated ketones can invoke more strategic C–C bond forming reactions, such as asymmetric aldol reactions of an aldehyde with α-hydroxyketone donors or enantioselective alkynylation of an aldehyde, respectively. To facilitate catalytic enantioselective addition reactions, including the aforementioned aldol and alkynylation reactions, our lab has developed the ProPhenol ligand. In this Account, we describe the development and application of the ProPhenol ligand for asymmetric additions of both carbon- and heteroatom-based nucleophiles to various electrophiles. The ProPhenol ligand spontaneously forms chiral dinuclear metal complexes when treated with an alkyl metal reagent, such as Et2Zn or Bu2Mg. The resulting complex contains both a Lewis acidic site to activate an electrophile and a Brønsted basic site to deprotonate a pronucleophile. Initially, our research focused on the use of Zn-ProPhenol complexes to facilitate the direct aldol reaction. Fine tuning of the reaction through ligand modification and the use of additives enabled the direct aldol reaction to proceed in high yields and stereoselectivities with a broad range of donor substrates, including acetophenones, methyl ynones, methyl vinyl ketone, acetone, α-hydroxy carbonyl compounds, and glycine Schiff bases. Additionally, an analogous

  2. Receiving Wear-Resistance Coverings Additives of Nanoparticles of Refractory Metals at a Laser Cladding

    NASA Astrophysics Data System (ADS)

    Murzakov, M. A.; Petrovskiy, V. N.; Bykovskiy, D. P.; Andreev, A. O.; Birukov, V. P.; Markushov, Y. V.

    2016-02-01

    Laser cladding technology was used to conduct experiments on production of wear-resistant coatings with additive nanoparticles of refractory metals (WC, TaC). Mechanical testing of coating abrasion was made using Brinell-Howarth method. The obtained data was compared with wear- resistance of commercial powder containing WC. It was found that at a concentration 10-15% coating with nanopowder additives shows a dramatic increase in wear-resistance by 4-6 times as compared to carbon steel substrate. There were conducted metallurgical studies of coatings on inverse electron reflection. There was determined elemental composition of deposited coating and substrate, and microhardness measured. It was found that structure of deposited coating with nanoparticles is fine.

  3. A metal-ligand cooperative pathway for intermolecular oxa-Michael additions to unsaturated nitriles.

    PubMed

    Perdriau, Sébastien; Zijlstra, Douwe S; Heeres, Hero J; de Vries, Johannes G; Otten, Edwin

    2015-03-27

    An unprecedented catalytic pathway for oxa-Michael addition reactions of alcohols to unsaturated nitriles has been revealed using a PNN pincer ruthenium catalyst with a dearomatized pyridine backbone. The isolation of a catalytically competent Ru-dieneamido complex from the reaction between the Ru catalyst and pentenenitrile in combination with DFT calculations supports a mechanism in which activation of the nitrile through metal-ligand cooperativity is a key step. The nitrile-derived Ru-N moiety is sufficiently Brønsted basic to activate the alcohol and initiate conjugate addition of the alkoxide to the α,β-unsaturated fragment. This reaction proceeds in a concerted manner and involves a six-membered transition state. These features allow the reaction to proceed at ambient temperature in the absence of external base. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Evaluation of Additively Manufactured Metals for Use in Oxygen Systems Project

    NASA Technical Reports Server (NTRS)

    Tylka, Jonathan; Cooper, Ken; Peralta, Stephen; Wilcutt, Terrence; Hughitt, Brian; Generazio, Edward

    2016-01-01

    Space Launch System, Commercial Resupply, and Commercial Crew programs have published intent to use additively manufactured (AM) components in propulsion systems and are likely to include various life support systems in the future. Parts produced by these types of additive manufacturing techniques have not been fully evaluated for use in oxygen systems and the inherent risks have not been fully identified. Some areas of primary concern in the SLS process with respect to oxygen compatibility may be the porosity of the printed parts, fundamental differences in microstructure of an AM part as compared to traditional materials, or increased risk of shed metal particulate into an oxygen system. If an ignition were to occur the printed material could be more flammable than components manufactured from a traditional billet of raw material and/or present a significant hazards if not identified and rigorously studied in advance of implementation into an oxygen system.

  5. Nutrients removal and recovery from anaerobically digested swine wastewater by struvite crystallization without chemical additions.

    PubMed

    Song, Yong-Hui; Qiu, Guang-Lei; Yuan, Peng; Cui, Xiao-Yu; Peng, Jian-Feng; Zeng, Ping; Duan, Liang; Xiang, Lian-Cheng; Qian, Feng

    2011-06-15

    Anaerobically digested swine wastewater contains high concentrations of phosphorus (P) and nitrogen (N). A pilot-scale experiment was carried out for nutrients removal and recovery from anaerobically digested swine wastewater by struvite crystallization. In the pilot plant, a sequencing batch reactor (SBR) and a continuous-flow reactor with struvite accumulation devices were designed and employed. The wastewater pH value was increased by CO(2) stripping, and the struvite crystallization process was performed without alkali and Mg(2+) additions. Results of the long-term operation of the system showed that, both reactors provided up to 85% P removal and recovery over wide ranges of aeration times (1.0-4.0 h), hydraulic retention times (HRT) (6.0-15.0 h) and temperatures (0-29.5°C) for an extended period of 247 d, in which approximate 30% of P was recovered by the struvite accumulation devices. However, 40-90% of NH(4)(+)-N removed was through air stripping instead of being immobilized in the recovered solids. The recovered products were detected and analyzed by scanning electron microscope (SEM), X-ray diffraction (XRD) and chemical methods, which were proved to be struvite with purity of more than 90%. This work demonstrated the feasibility and effects of nutrients removal and recovery from anaerobically digested swine wastewater by struvite crystallization without chemical additions.

  6. Preliminary assessment of metal-porcelain bonding strength of CoCrW alloy after 3wt.% Cu addition.

    PubMed

    Lu, Yanjin; Zhao, Chaoqian; Ren, Ling; Guo, Sai; Gan, Yiliang; Yang, Chunguang; Wu, Songquan; Lin, Junjie; Huang, Tingting; Yang, Ke; Lin, Jinxin

    2016-06-01

    In this work, a novel Cu-bearing CoCrW alloy fabricated by selective laser melting for dental application has been studied. For its successful application, the bonding strength of metal-porcelain is essential to be systematically investigated. Therefore, the aim of this study was to evaluate the metal-porcelain bonding strength of CoCrWCu alloy by three-point bending test, meanwhile the Ni-free CoCrW alloy was used as control. The oxygen content was investigated by an elemental analyzer; X-ray photoelectron spectroscopy (XPS) was used to analyze the surface chemical composition of CoCrW based alloy after preoxidation treatment; the fracture mode was investigated by X-ray energy spectrum analysis (EDS) and scanning electron microscope (SEM). Result from the oxygen content analysis showed that the content of oxygen dramatically increased after the Cu addition. And the XPS suggested that Co-oxidation, Cr2O3, CrO2, WO3, Cu2O and CuO existed on the preoxidated surface of the CoCrWCu alloy; the three-point bending test showed that the bonding strength of the CoCrWCu alloy was 43.32 MPa, which was lower than that of the CoCrW group of 47.65 MPa. However, the average metal-porcelain bonding strength is significantly higher than the minimum value in the ISO 9693 standard. Results from the SEM images and EDS indicated that the fracture mode of CoCrWCu-porcelain was mixed between cohesive and adhesive. Based on the results obtained in this study, it can be indicated that the Cu-bearing CoCrW alloy fabricated by the selective laser melting is a promising candidate for use in dental application.

  7. Characterization of peptides in ensiled alfalfa treated with different chemical additives.

    PubMed

    Ding, Wurong; Guo, Xusheng; Ataku, Kazuo

    2013-12-01

    Effects of different chemical additives on peptide composition in ensiled alfalfa (Medicago sativa L.) were investigated by using gel filtration and determination of N characteristics. The alfalfa silages were prepared untreated (control) or with formic acid, formaldehyde or tannic acid as additives at ensiling. All additives reduced non-protein N (NPN), ammonia nitrogen (NH3 -N) and amino acid N (AA-N) in the ensiled forage, and the most effective reduction of NPN and AA-N was observed in the formaldehyde-treated silages. Peptides in the control silage were mainly dipeptides to peptides with five amino acid residues. Most peptides in the formic acid-treated silage contained 4-12 amino acid residues. Although most peptides in the formaldehyde-treated silages contained 4-6 amino acid residues, there was a considerable proportion of peptides with 7-11 amino acid residues. Tannic acid had little effect on peptide size of ensiled alfalfa extract in which most peptides contained 5-6 amino acid residues. Peptide size in formic acid-treated alfalfa silage was greater than that in the other treatments. Addition of formic acid and formaldehyde not only increased the peptide concentration in alfalfa silage, but enlarged the peptide size. © 2013 Japanese Society of Animal Science.

  8. Metal hydride and pyrophoric fuel additives for dicyclopentadiene based hybrid propellants

    NASA Astrophysics Data System (ADS)

    Shark, Steven C.

    The purpose of this study is to investigate the use of reactive energetic fuel additives that have the potential to increase the combustion performance of hybrid rocket propellants in terms of solid fuel regression rate and combustion efficiency. Additives that can augment the combustion flame zone in a hybrid rocket motor by means of increased energy feedback to the fuel grain surface are of great interest. Metal hydrides have large volumetric hydrogen densities, which gives these materials high performance potential as fuel additives in terms of specifc impulse. The excess hydrogen and corresponding base metal may also cause an increase in the hybrid rocket solid fuel regression rate. Pyrophoric additives also have potential to increase the solid fuel regression rate by reacting more readily near the burning fuel surface providing rapid energy feedback. An experimental performance evaluation of metal hydride fuel additives for hybrid rocket motor propulsion systems is examined in this study. Hypergolic ignition droplet tests and an accelerated aging study revealed the protection capabilities of Dicyclopentadiene (DCPD) as a fuel binder, and the ability for unaided ignition. Static hybrid rocket motor experiments were conducted using DCPD as the fuel. Sodium borohydride (NabH4) and aluminum hydride (AlH3) were examined as fuel additives. Ninety percent rocket grade hydrogen peroxide (RGHP) was used as the oxidizer. In this study, the sensitivity of solid fuel regression rate and characteristic velocity (C*) efficiency to total fuel grain port mass flux and particle loading is examined. These results were compared to HTPB combustion performance as a baseline. Chamber pressure histories revealed steady motor operation in most tests, with reduced ignition delays when using NabH4 as a fuel additive. The addition of NabH4 and AlH3 produced up to a 47% and 85% increase in regression rate over neat DCPD, respectively. For all test conditions examined C* efficiency ranges

  9. Controlling nucleation of monolayer WSe2 during metal-organic chemical vapor deposition growth

    NASA Astrophysics Data System (ADS)

    Eichfeld, Sarah M.; Oliveros Colon, Víctor; Nie, Yifan; Cho, Kyeongjae; Robinson, Joshua A.

    2016-06-01

    Tungsten diselenide (WSe2) is a semiconducting, two-dimensional (2D) material that has gained interest in the device community recently due to its electronic properties. The synthesis of atomically thin WSe2, however, is still in its infancy. In this work we elucidate the requirements for large selenium/tungsten precursor ratios and explain the effect of nucleation temperature on the synthesis of WSe2 via metal-organic chemical vapor deposition (MOCVD). The introduction of a nucleation-step prior to growth demonstrates that increasing nucleation temperature leads to a transition from a Volmer-Weber to Frank-van der Merwe growth mode. Additionally, the nucleation step prior to growth leads to an improvement of WSe2 layer coverage on the substrate. Finally, we note that the development of this two-step technique may allow for improved control and quality of 2D layers grown via CVD and MOCVD processes.

  10. Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition.

    PubMed

    Nguyen, Khoa D; Park, Boyoung Y; Luong, Tom; Sato, Hiroki; Garza, Victoria J; Krische, Michael J

    2016-10-21

    α-Olefins are the most abundant petrochemical feedstock beyond alkanes, yet their use in commodity chemical manufacture is largely focused on polymerization and hydroformylation. The development of byproduct-free catalytic C-C bond-forming reactions that convert olefins to value-added products remains an important objective. Here, we review catalytic intermolecular reductive couplings of unactivated and activated olefin-derived nucleophiles with carbonyl partners. These processes represent an alternative to the longstanding use of stoichiometric organometallic reagents in carbonyl addition. Copyright © 2016, American Association for the Advancement of Science.

  11. Influencing the arc and the mechanical properties of the weld metal in GMA-welding processes by additive elements on the wire electrode surface

    NASA Astrophysics Data System (ADS)

    Wesling, V.; Schram, A.; Müller, T.; Treutler, K.

    2016-03-01

    Under the premise of an increasing scarcity of raw materials and increasing demands on construction materials, the mechanical properties of steels and its joints are gaining highly important. In particular high- and highest-strength steels are getting in the focus of the research and the manufacturing industry. To the same extent, the requirements for filler metals are increasing as well. At present, these low-alloy materials are protected by a copper coating (<1μm) against corrosion. In addition, the coating realizes a good ohmic contact and good sliding properties between the welding machine and the wire during the welding process. By exchanging the copper with other elements it should be possible to change the mechanical properties of the weld metal and the arc stability during gas metal arc welding processes and keep the basic functions of the coating nearly untouched. On a laboratory scale solid wire electrodes with coatings of various elements and compounds such as titanium oxide were made and processed with a Gas Metal Arc Welding process. During the processing a different process behavior between the wire electrodes, coated and original, could be observed. The influences ranges from greater/shorter arc-length over increasing/decreasing droplets to larger/smaller arc foot point. Furthermore, the weld metal of the coated electrodes has significantly different mechanical and technological characteristics as the weld metal from the copper coated ground wire. The yield strength and tensile strength can be increased by up to 50%. In addition, the chemical composition of the weld metal was influenced by the application of coatings with layer thicknesses to 15 microns in the lower percentage range (up to about 3%). Another effect of the coating is a modified penetration. The normally occurring “argon finger” can be suppressed or enhanced by the choice of the coating. With the help of the presented studies it will be shown that Gas Metal Arc Welding processes

  12. Chemical-looping combustion of coal with metal oxide oxygen carriers

    SciTech Connect

    Ranjani Siriwardane; Hanjing Tian; George Richards; Thomas Simonyi; James Poston

    2009-08-15

    The combustion and reoxidation properties of direct coal chemical-looping combustion (CLC) over CuO, Fe{sub 2}O{sub 3}, CO{sub 3}O{sub 4}, NiO, and Mn{sub 2}O{sub 3} were investigated using thermogravimetric analysis (TGA) and bench-scale fixed-bed flow reactor studies. When coal is heated in either nitrogen or carbon dioxide (CO{sub 2}), 50% of weight loss was observed because of partial pyrolysis, consistent with the proximate analysis. Among various metal oxides evaluated, CuO showed the best reaction properties: CuO can initiate the reduction reaction as low as 500{sup o}C and complete the full combustion at 700{sup o}C. In addition, the reduced copper can be fully reoxidized by air at 700{sup o}C. The combustion products formed during the CLC reaction of the coal/metal oxide mixture are CO{sub 2} and water, while no carbon monoxide was observed. Multicycle TGA tests and bench-scale fixed-bed flow reactor tests strongly supported the feasibility of CLC of coal by using CuO as an oxygen carrier. Scanning electron microscopy (SEM) images of solid reaction products indicated some changes in the surface morphology of a CuO-coal sample after reduction/oxidation reactions at 800 {sup o}C. However, significant surface sintering was not observed. The interactions of fly ash with metal oxides were investigated by X-ray diffraction and thermodynamic analysis. Overall, the results indicated that it is feasible to develop CLC with coal by metal oxides as oxygen carriers. 22 refs., 12 figs., 2 tabs.

  13. The dynamics of molecular interactions and chemical reactions at metal surfaces: testing the foundations of theory.

    PubMed

    Golibrzuch, Kai; Bartels, Nils; Auerbach, Daniel J; Wodtke, Alec M

    2015-04-01

    We review studies of molecular interactions and chemical reactions at metal surfaces, emphasizing progress toward a predictive theory of surface chemistry and catalysis. For chemistry at metal surfaces, a small number of central approximations are typically made: (a) the Born-Oppenheimer approximation of electronic adiabaticity, (b) the use of density functional theory at the generalized gradient approximation level, (c) the classical approximation for nuclear motion, and (d) various reduced-dimensionality approximations. Together, these approximations constitute a provisional model for surface chemical reactivity. We review work on some carefully studied examples of molecules interacting at metal surfaces that probe the validity of various aspects of the provisional model.

  14. The Dynamics of Molecular Interactions and Chemical Reactions at Metal Surfaces: Testing the Foundations of Theory

    NASA Astrophysics Data System (ADS)

    Golibrzuch, Kai; Bartels, Nils; Auerbach, Daniel J.; Wodtke, Alec M.

    2015-04-01

    We review studies of molecular interactions and chemical reactions at metal surfaces, emphasizing progress toward a predictive theory of surface chemistry and catalysis. For chemistry at metal surfaces, a small number of central approximations are typically made: (a) the Born-Oppenheimer approximation of electronic adiabaticity, (b) the use of density functional theory at the generalized gradient approximation level, (c) the classical approximation for nuclear motion, and (d) various reduced-dimensionality approximations. Together, these approximations constitute a provisional model for surface chemical reactivity. We review work on some carefully studied examples of molecules interacting at metal surfaces that probe the validity of various aspects of the provisional model.

  15. Chemical intercalation of zerovalent metals into 2D layered Bi2Se3 nanoribbons.

    PubMed

    Koski, Kristie J; Wessells, Colin D; Reed, Bryan W; Cha, Judy J; Kong, Desheng; Cui, Yi

    2012-08-22

    We have developed a chemical method to intercalate a variety of zerovalent metal atoms into two-dimensional (2D) layered Bi(2)Se(3) chalcogenide nanoribbons. We use a chemical reaction, such as a disproportionation redox reaction, to generate dilute zerovalent metal atoms in a refluxing solution, which intercalate into the layered Bi(2)Se(3) structure. The zerovalent nature of the intercalant allows superstoichiometric intercalation of metal atoms such as Ag, Au, Co, Cu, Fe, In, Ni, and Sn. We foresee the impact of this methodology in establishing novel fundamental physical behaviors and in possible energy applications.

  16. Increasing the reliability and quality of important cast products made of chemically active metals and alloys

    NASA Astrophysics Data System (ADS)

    Varfolomeev, M. S.; Moiseev, V. S.; Shcherbakova, G. I.

    2017-01-01

    A technology is developed to produce highly thermoresistant ceramic monoxide corundum molds using investment casting and an aluminum-organic binder. This technology is a promising trend in creating ceramic molds for precision complex-shape casting of important ingots made of high-alloy steels, high-temperature and titanium alloys, and refractory metals. The use of the casting molds that have a high thermal and chemical resistance to chemically active metals and alloys under high-temperature casting minimizes the physicochemical interaction and substantially decreases the depth of the hard-to-remove metal oxide layer on important products, which increases their service properties.

  17. Metal ion-mobilizing additives for comprehensive detection of femtomole amounts of phosphopeptides by reversed phase LC-MS.

    PubMed

    Seidler, Joerg; Zinn, Nico; Haaf, Erik; Boehm, Martin E; Winter, Dominic; Schlosser, Andreas; Lehmann, Wolf D

    2011-07-01

    It is hypothesized that metal ion-mediated adsorption of phosphorylated peptides on stationary phases of LC-columns is the major cause for their frequently observed poor detection efficiency in LC-MS. To study this phenomenon in more detail, sample solutions spiked with metal ion-mobilizing additives were analyzed by reversed phase μLC-ICP-MS or nanoLC-ESI-MS. Using μLC-ICP-MS, metal ions were analyzed directly as atomic ions. Using electrospray ionization, either metal ion chelates or phosphopeptide standard mixtures injected in subpicomole amounts were analyzed. Deferoxamine, imidazole, ascorbate, citrate, EDTA, and the tetrapeptide pSpSpSpS were tested as sample additives for the interlinked purposes of metal ion-mobilization and improvement of phosphopeptide recovery. Iron probably represents the major metal ion contamination of reversed phase columns. Based on the certified iron level in LC-grade solvents, a daily metal ion load of >10 pmol was estimated for typical nanoLC flow rates. In addition, phosphopeptide fractions from IMAC columns were identified as source for metal ion contamination of the LC column, as demonstrated for Ga(3+)-IMAC. The three metal ion-chelating additives, EDTA, citrate and pSpSpSpS, were found to perform best for improving the LC recovery of multiply phosphorylated peptides injected at subpicomole amounts. The benefits of metal ion-mobilizing LC (mimLC) characterized by metal ion complexing sample additives is demonstrated for three different instrumental setups comprising (a) a nanoUPLC-system with direct injection on the analytical column, (b) a nanoLC system with inclusion of a trapping column, and (c) the use of a HPLC-Chip system with integrated trapping and analytical column.

  18. Study of metal whiskers growth and mitigation technique using additive manufacturing

    NASA Astrophysics Data System (ADS)

    Gullapalli, Vikranth

    For years, the alloy of choice for electroplating electronic components has been tin-lead (Sn-Pb) alloy. However, the legislation established in Europe on July 1, 2006, required significant lead (Pb) content reductions from electronic hardware due to its toxic nature. A popular alternative for coating electronic components is pure tin (Sn). However, pure tin has the tendency to spontaneously grow electrically conductive Sn whisker during storage. Sn whisker is usually a pure single crystal tin with filament or hair-like structures grown directly from the electroplated surfaces. Sn whisker is highly conductive, and can cause short circuits in electronic components, which is a very significant reliability problem. The damages caused by Sn whisker growth are reported in very critical applications such as aircraft, spacecraft, satellites, and military weapons systems. They are also naturally very strong and are believed to grow from compressive stresses developed in the Sn coating during deposition or over time. The new directive, even though environmentally friendly, has placed all lead-free electronic devices at risk because of whisker growth in pure tin. Additionally, interest has occurred about studying the nature of other metal whiskers such as zinc (Zn) whiskers and comparing their behavior to that of Sn whiskers. Zn whiskers can be found in flooring of data centers which can get inside electronic systems during equipment reorganization and movement and can also cause systems failure. Even though the topic of metal whiskers as reliability failure has been around for several decades to date, there is no successful method that can eliminate their growth. This thesis will give further insights towards the nature and behavior of Sn and Zn whiskers growth, and recommend a novel manufacturing technique that has potential to mitigate metal whiskers growth and extend life of many electronic devices.

  19. Heavy metals and its chemical speciation in sewage sludge at different stages of processing.

    PubMed

    Tytła, Malwina; Widziewicz, Kamila; Zielewicz, Ewa

    2016-01-01

    The analysis of heavy metal concentrations and forms in sewage sludge constitutes an important issue in terms of both health and environmental hazards the metals pose. The total heavy metals concentration enables only the assessment of its contamination. Hence the knowledge of chemical forms is required to determine their environmental mobility and sludge final disposal. Heavy metals speciation was studied by using four-stage sequential extraction BCR (Community Bureau of Reference). This study was aimed at determining the total concentration of selected heavy metals (Zn, Cu, Ni, Pb, Cd, Cr and Hg) and their chemical forms (except for Hg) in sludge collected at different stages of its processing at two municipal Wastewater Treatment Plants in southern Poland. Metals contents in sludge samples were determined by using flame atomic absorption spectrometry (FAAS) and electrothermal atomic absorption spectrometry (ETAAS). This study shows that Zn and Cu appeared to be the most abundant in sludge, while Cd and Hg were in the lowest concentrations. The sewage sludge revealed the domination of immobile fractions over the mobile ones. The oxidizable and residual forms were dominant for all the heavy metals. There was also a significant difference in metals speciation between sludges of different origin which was probably due to differences in wastewater composition and processes occurring in biological stage of wastewater treatment. The results indicate a negligible capability of metals to migrate from sludge into the environment. Our research revealed a significant impact of thickening, stabilization and hygienization on the distribution of heavy metals in sludge and their mobility.

  20. A Preferable Method for the Formation of Vesicles from Lamellar Liquid Crystals Using Chemical Additives.

    PubMed

    Enomoto, Yasutaka; Imai, Yoko; Tajima, Kazuo

    2017-01-01

    We present a method for vesicle formation from lamellar liquid crystals (LCs) using a cationic amphiphilic substance, namely 2-hydroxyethyl di(alkanol)oxyethyl methylammonium methylsulfate (DEAE). Vesicle formation from the DEAE lamellar dispersion occurred via a two-step chemical addition. This method required neither additional mechanical energy nor the use of special solvents. The transition was solubilized using an organic substance (e.g., limonene) in the lamellar DEAE LC, after which, a small amount of inorganic salt was added to the solubilized lamellar LC dispersion with gentle stirring. The viscosity of the DEAE dispersion following salt addition decreased sharply from 10(5) mPa·s to 10(2) mPa·s, and the DEAE dispersion was converted into a high fluidity liquid. Several organic substances were examined as potential solubilizates to initiate the lamellar-vesicle transition. Inorganic salts were also examined as transition triggers using various types of electrolytes; only neutral salts were effective as trigger additives. Dissociation of inorganic salts yielded anions, which inserted between the DEAE bilayer membranes and induced OH(-) ion exchange. In addition, a number of cations simultaneously formed ion pairs with the DEAE counter ions (CH3SO4(-) ions). However, as the amount of solubilized organic substances in the DEAE bilayer membrane decreased over time, the vesicles were transformed into lamellar LCs once again. The DEAE states in each step were measured by monitoring the zeta potential, pH, viscosity, and by examination of scanning electron microscopy and atomic force microscopy images. A possible molecular mechanism for the lamellar-vesicle transition of DEAE was proposed.

  1. Effect of GdL Addition on Physico-chemical Properties of Fermented Sausages during Ripening.

    PubMed

    Yim, Dong-Gyun; Jang, Kyoung-Hwan; Chung, Ku-Young

    2015-01-01

    This study investigated the effects of glucono-δ-lactone (GdL) addition on physicochemical and microbiological characteristics of fermented sausages during ripening and drying. Five batches of sausages were produced under ripening conditions: without GdL and with 0, 0.1, 0.25, 0.5 and 0.75% of GdL addition. Samples from each treatment were taken for physicochemical and microbiological analyses on the 0, 1, 3, 5, 7, 10, 15, 20 and 25th day of ripening. Chemical analysis showed a significant decrease in moisture content of sausages with increasing amounts of GdL added (p<0.05). The moisture contents decreased, whereas the fat, protein and ash contents increased throughout ripening (p<0.05). Increasing levels of GdL caused a decrease in the pH values (p<0.05), which can have an inhibitory effect against microflora. Water holding capacity content of samples decreased with increasing GdL concentration (p<0.05). The shear force values of fermented sausages showed the highest in T4 (p<0.05). During ripening, the shear force values of sausages were increased on the 25th day compared to day 0 (p<0.05). The higher GdL level produced lighter and more yellow sausages. The addition of 0.75% GdL was effective in controlling bacteria counts. Addition of GdL in sausages resulted in the physicochemical and microbiological attributes equal to or better than no addition of GdL without any harmful effect.

  2. Effect of indium addition in U-Zr metallic fuel on lanthanide migration

    NASA Astrophysics Data System (ADS)

    Kim, Yeon Soo; Wiencek, T.; O'Hare, E.; Fortner, J.; Wright, A.; Cheon, J. S.; Lee, B. O.

    2017-02-01

    Advanced fast reactor concepts to achieve ultra-high burnup (∼50%) require prevention of fuel-cladding chemical interaction (FCCI). Fission product lanthanide accumulation at high burnup is substantial and significantly contributes to FCCI upon migration to the cladding interface. Diffusion barriers are typically used to prevent interaction of the lanthanides with the cladding. A more active method has been proposed which immobilizes the lanthanides through formation of stable compounds with an additive. Theoretical analysis showed that indium, thallium, and antimony are good candidates. Indium was the strongest candidate because of its low reactivity with iron-based cladding alloys. Characterization of the as-fabricated alloys was performed to determine the effectiveness of the indium addition in forming compounds with lanthanides, represented by cerium. Tests to examine how effectively the dopant prevents lanthanide migration under a thermal gradient were also performed. The results showed that indium effectively prevented cerium migration.

  3. Effect of additives on the properties of polyaniline nanofibers prepared by high gravity chemical oxidative polymerization.

    PubMed

    Zhao, Yibo; Arowo, Moses; Wu, Wei; Chen, Jianfeng

    2015-05-12

    Polyaniline (PANI) nanofibers with improved properties were prepared by high gravity chemical oxidative polymerization in a rotating packed bed with the assistance of p-aminodiphenylamine (AD) and p-phenylenediamine (AP). The effects of reactor type, additive dosage, reaction temperature, and high-gravity level on the properties of products were investigated in detail. Three conclusions were made: (1) a small amount of additive can significantly improve some properties of the nanofibers such as uniformity, specific surface area, and specific capacitance; (2) in order to obtain high-quality nanofibers, the high-gravity level should coordinate with the reaction rate; (3) the molecular weight and conductivity of PANI decrease with the increase of additive dosage. The products have larger specific surface areas of up to 73.9 and 68.4 m(2)/g and consequently improved specific capacitance of up to 527.5 and 552 F/g for the PANI nanofibers prepared with AD and AP, respectively. However, the specific surface area and specific capacitance of pure PANI are only 49.1 m(2)/g and 333.3 F/g, respectively. This research provides a simple, reliable, and scalable method to produce PANI nanofibers of high performances.

  4. Modifications of chemical functional groups of Pandanus amaryllifolius Roxb and its effect towards biosorption of heavy metals

    SciTech Connect

    Abdullah, Mohd Zamri Ismail, Siti Salwa

    2015-07-22

    The utilization of non-living biomass as an alternative biosorbent for heavy metal removal has gain a tremendous consideration through the years. Pandanus amaryllifolius Roxb or pandan leaves, which is widely used as food additives in the South East Asia region, has been selected for its viability in the said effort due to the presence of chemical functional groups on its cellular network that enables the sorption to occur. In order to elucidate the possible mechanisms participated during the heavy metal removal process, the biosorbent undergone a series of modification techniques to alter the chemical functional groups present on its constituent. From the outcome of the chemically-modified biosorbent being subjected to the contact with metal cations, nitrogen- and oxygen-containing groups present on the biosorbent are believed to be responsible for the metal uptake to occur through complexation mechanism. Modifying amine groups causes 14% reduction of Cu(II) uptake, whereas removing protein element increases the uptake to 26% as compared to the unmodified biosorbent. Also, scanning electron micrographs further suggested that the adsorption mechanism could perform in parallel, as attributed to the evidence of porous structure throughout the biosorbent fibrous nature.

  5. Modifications of chemical functional groups of Pandanus amaryllifolius Roxb and its effect towards biosorption of heavy metals

    NASA Astrophysics Data System (ADS)

    Abdullah, Mohd. Zamri; Ismail, Siti Salwa

    2015-07-01

    The utilization of non-living biomass as an alternative biosorbent for heavy metal removal has gain a tremendous consideration through the years. Pandanus amaryllifolius Roxb or pandan leaves, which is widely used as food additives in the South East Asia region, has been selected for its viability in the said effort due to the presence of chemical functional groups on its cellular network that enables the sorption to occur. In order to elucidate the possible mechanisms participated during the heavy metal removal process, the biosorbent undergone a series of modification techniques to alter the chemical functional groups present on its constituent. From the outcome of the chemically-modified biosorbent being subjected to the contact with metal cations, nitrogen- and oxygen-containing groups present on the biosorbent are believed to be responsible for the metal uptake to occur through complexation mechanism. Modifying amine groups causes 14% reduction of Cu(II) uptake, whereas removing protein element increases the uptake to 26% as compared to the unmodified biosorbent. Also, scanning electron micrographs further suggested that the adsorption mechanism could perform in parallel, as attributed to the evidence of porous structure throughout the biosorbent fibrous nature.

  6. Laser-shocked energetic materials with metal additives: evaluation of detonation performance

    NASA Astrophysics Data System (ADS)

    Gottfried, Jennifer; Bukowski, Eric

    A focused, nanosecond-pulsed laser with sufficient energy to exceed the breakdown threshold of a material generates a laser-induced plasma with high peak temperatures, pressures, and shock velocities. Depending on the laser parameters and material properties, nanograms to micrograms of material is ablated, atomized, ionized and excited in the laser-induced plasma. The subsequent shock wave expansion into the air above the sample has been monitored using high-speed schlieren imaging in a recently developed technique, laser-induced air shock from energetic materials (LASEM). The estimated detonation velocities using LASEM agree well with published experimental values. A comparison of the measured shock velocities for various energetic materials including RDX, DNTF, and LLM-172 doped with Al or B to the detonation velocities predicted by CHEETAH for inert or active metal participation demonstrates that LASEM has potential for predicting the early time participation of metal additives in detonation events. The LASEM results show that reducing the amount of hydrogen present in B formulations increases the resulting detonation velocities

  7. Separation of alkali metals using isotachophoresis with cryptand 222 as a leading electrolyte additive.

    PubMed

    Prest, Jeff E; Fielden, Peter R; Qi, Yanhua

    2012-10-19

    This work shows how the inclusion of cryptand 222 as a leading electrolyte additive in isotachophoresis affects the electrophoretic mobilities of alkali metal cations. Using isotachophoresis the separation of alkali metals can be difficult due to the similar electrophoretic mobilities of three of the ions: caesium, rubidium and potassium. However, the presence of cryptand 222 in the leading electrolyte retards the mobilities of the caesium, rubidium and potassium to a different extent allowing separations to be made. A novel electrolyte system was formulated which consisted of a leading electrolyte of 10 mM caesium hydroxide, 0.75 mM cryptand 222 buffered to pH 9.4 with glycylglycine and a terminating electrolyte of 10 mM tetrabutylammonium hydroxide. The use of this electrolyte system allowed good separations of mixtures of rubidium, potassium, sodium and lithium to be achieved. The method was also applied to the analysis of edible salt samples. Copyright © 2012 Elsevier B.V. All rights reserved.

  8. Active metal-matrix composites with embedded smart materials by ultrasonic additive manufacturing

    NASA Astrophysics Data System (ADS)

    Hahnlen, Ryan; Dapino, Marcelo J.

    2010-04-01

    This paper presents the development of active aluminum-matrix composites manufactured by Ultrasonic Additive Manufacturing (UAM), an emerging rapid prototyping process based on ultrasonic metal welding. Composites created through this process experience temperatures as low as 25 °C during fabrication, in contrast to current metal-matrix fabrication processes which require temperatures of 500 °C and above. UAM thus provides unprecedented opportunities to develop adaptive structures with seamlessly embedded smart materials and electronic components without degrading the properties that make these materials and components attractive. This research focuses on developing UAM composites with aluminum matrices and embedded shape memory NiTi, magnetostrictive Galfenol, and electroactive PVDF phases. The research on these composites will focus on: (i) electrical insulation between NiTi and Al phases for strain sensors, investigation and modeling of NiTi-Al composites as tunable stiffness materials and thermally invariant structures based on the shape memory effect; (ii) process development and composite testing for Galfenol-Al composites; and (iii) development of PVDF-Al composites for embedded sensing applications. We demonstrate a method to electrically insulate embedded materials from the UAM matrix, the ability create composites containing up to 22.3% NiTi, and their resulting dimensional stability and thermal actuation characteristics. Also demonstrated is Galfenol-Al composite magnetic actuation of up to 54 μ(see manuscript), and creation of a PVDF-Al composite sensor.

  9. Performance and modeling of active metal-matrix composites manufactured by ultrasonic additive manufacturing

    NASA Astrophysics Data System (ADS)

    Hahnlen, Ryan; Dapino, Marcelo J.

    2011-04-01

    This paper presents the development and characterization of active aluminum-matrix composites manufactured by Ultrasonic Additive Manufacturing (UAM), an emerging rapid prototyping process based on ultrasonic metal welding. The primary benefit of UAM over other metal-matrix fabrication processes is the low process temperatures, as low as 25 °C. UAM thus provides unprecedented opportunities to develop adaptive structures with seamlessly embedded smart materials and electronic components without degrading the properties that make these materials and components attractive. The objective of this research is to develop UAM composites with aluminum matrices and embedded shape memory NiTi, magnetostrictive Galfenol (FeGa), and polyvinylidene fluoride (PVDF) phases. The paper is focused on the thermally induced strain response and stiffness behavior of NiTi-Al composites, the actuation properties of FeGa-Al composites, and the embedded sensing capabilities of PVDF-Al composites. We observe up to a 10% increase over room temperature stiffness for NiTi-Al composites and a magnetomechanical response in the FeGa-Al composite up to 52.4 μɛ. The response of the PVDF-Al composite to harmonic loads is observed over a frequency range of 10 to 1000 Hz.

  10. A mild, chemical conversion of cellulose to hexene and other liquid hydrocarbon fuels and additives

    SciTech Connect

    Robinson, J.M.

    1995-12-31

    A unique biomass fractionation is used to feed a novel chemical reduction process that converts carbohydrates with 100% carbon conversion into hydrocarbon fuels. Six strategic goals have been accomplished: (1) Lignin is cleanly removed in a single step, (2) The carbon chain of the sugar monomers remains intact, (3) Each reaction occurs at mild conditions and gives essentially quantitative yield, (4) Each reaction is catalytic, (5) Initial reactions occur in an aqueous medium, which (6) allows the use of wet feedstocks. Catalytic recycling of the chemical reducing agents thus provides the equivalent of an efficient biomass reduction. Conversion of cellulose (1) to hexenes (8) sequentially via sorbitol (4) and 2-iodohexane (6) typifies the process. Step 2 of the process is highly tunable and can directly produce about 80% hydrocarbon oligomers, C{sub 12}H{sub 22} (12) and C{sub 18}H{sub 32} (13). Oxygenate fuel additives such as 2-hexanol (14) are also available by further reactions of hexene.

  11. Influence of Alumina Additions on the Physical and Chemical Properties of Lithium-iron-phosphate Glasses

    NASA Astrophysics Data System (ADS)

    Liu, Huali; Yang, Ruijuan; Wang, Yinghui; Liu, Shiquan

    Alumina improves the properties and depresses the devitrification of soda-lime-silicate glasses. Herein, the influence of alumina on the glass transition temperature, density, chemical durability, crystallization of lithium-iron-phosphate (LIP) glass has been investigated. As alumina was added to replace the iron oxide in a base LIP glass with the molar composition of Li2O:Fe2O3:P2O5=30:20:50, the alumina-containing glasses have increased Tg, densities and chemical stabilities than the base glass. When the amount of alumina is increased from 2 to 6 mol, the Tg value slightly increases, whereas the density decreases. However, the smallest weight loss is shown for the glass containing 3.2 mol of alumina. The variations of the properties with alumina are explained based on the infrared structure analysis results. In addition, it is found the either the base or the alumina-containing glasses have surface crystallization upon heat-treatments. Under the same treatment conditions, the base glass exhibits a thin layer of crystallization with LiFeP2O7 as the main phase. In contrast, alumina-containing glasses show much higher degree of crystallization, which is further increased with the amount of alumina. This trend is opposite to that of silicate glass. Besides the LiFeP2O7 main phase, Fe7(PO4) phase is also identified in the crystallized alumina-containing glasses.

  12. Modified lignosulfonates as additives in oil recovery processes involving chemical recovery agents

    SciTech Connect

    Kalfoglou, G.

    1982-08-17

    A process for producing petroleum from subterranean formations is disclosed wherein production from the formation is obtained by driving a fluid from an injection well to a production well. The process involves injecting via the injection well into the formation an aqueous solution of modified lignosulfonate salt as a sacrificial agent to inhibit the deposition of surfactant and/or polymer on the reservoir matrix. The process may best be carried out by injecting the modified lignosulfonates into the formation through the injection well mixed with either a polymer, a surfactant solution and/or a micellar dispersion. This mixture would then be followed by a drive fluid such as water to push the chemicals to the production well. The lignosulfonates may be modified by any combination of any two or more of: reaction with chloroacetic acid, reaction with carbon dioxide, addition of the methylene sulfonate radical to the lignosulfonate molecule and oxidation with oxygen.

  13. Evaluation of Chemical Clarification Polymers and Methods for Removal of Dissolved Metals from CDF Effluent

    DTIC Science & Technology

    2006-07-01

    chemical flocculation . Clarification is intended for removal of solids from CDF effluent, and in doing so, much of the metals contamination is also...removed with the solids. Likewise, the ability of the chemical flocculation to remove dissolved phase contaminants should also be considered...since this may be an important, simultaneous benefit. As effluent discharge standards become more stringent, the benefits of new chemical flocculation

  14. Chemical etching and EDAX analysis of beryllium-free nickel-chromium ceramo-metal alloy.

    PubMed

    Atta, O M; Mosleh, I E; Shehata, M T

    1995-10-01

    A chemical etching technique is described for producing etch patterns in beryllium-free nickel chromium ceramo-metal alloy. Disc-shaped samples were chemically etched, evaluated with SEM and analysed by the EDAX technique. Scanning electron micrographs revealed, profound retentive cavities. The EDAX analysis provided a comprehensive interpretation of the etch mechanism. The obtained results show that the developed chemical etching has the potential to produce a highly retentive etched surface with less problematic and less technique sensitive than electrolytic etching.

  15. Influence of catalytic gold and silver metal nanoparticles on structural, optical, and vibrational properties of silicon nanowires synthesized by metal-assisted chemical etching

    NASA Astrophysics Data System (ADS)

    Dawood, M. K.; Tripathy, S.; Dolmanan, S. B.; Ng, T. H.; Tan, H.; Lam, J.

    2012-10-01

    We report on the structural and vibrational characterization of silicon (Si) nanowire arrays synthesized by metal-assisted chemical etching (MACE) of Si deposited with metal nanoparticles. Gold (Au) and silver (Ag) metal nanoparticles were synthesized by glancing angle deposition, and MACE was performed in a mixture of H2O2 and HF solution. We studied the structural differences between Au and Ag-etched Si nanowires. The morphology of the synthesized nanowires was characterized by scanning electron microscopy and transmission electron microscopy. The optical and vibrational properties of the Si nanostructures were studied by photoluminescence and Raman spectroscopy using three different excitation sources (UV, visible, and near-infrared) and are correlated to their microstructures. The structural differences between Au-etched and Ag-etched nanowires are due to the higher degree of hole injection by the Au nanoparticle and diffusion into the Si nanowires, causing enhanced Si etching by HF on the nanowire surface. Au-etched nanowires were observed to be mesoporous throughout the nanowire while Ag-etched nanowires consisted of a thin porous layer around the crystalline core. In addition, the surface-enhanced resonant Raman scattering observed is attributed to the presence of the sunken metal nanoparticles. Such Si nanostructures may be useful for a wide range of applications such as photovoltaic and biological and chemical sensing.

  16. Enhanced Metal Contacts to Carbon Nanotube Networks through Chemical and Physical Modification

    NASA Astrophysics Data System (ADS)

    Cox, Nathanael David

    Carbon nanotubes (CNTs) are an emerging class of nano-structured carbon materials which are currently being studied for applications which would benefit from their desirable electrical and mechanical properties. Potential benefits such as improved current density, flexure tolerance, weight savings, and even radiation tolerance have led to their implementation into numerous devices and structures, many of which are slated for use in space environments. The role of CNTs can be quite diverse, with varied CNT electronic-types and morphologies dictated by the specific application. Despite numerous CNT types and morphologies employed by these technologies, a common link between nearly all of these devices and structures is metal contact to CNTs, where the metal components often provide the link between the carbon nanotubes and the external system. In this work, a variety of CNT-metal systems were characterized in terms of metal morphology analysis and CNT-metal electrical and mechanical interactions, in response to chemical and structural modifications. A large portion of the work additionally focuses on ion irradiation environments. A diverse number of experiments related to CNT-metal interactions will be discussed. For instance, electrochemical interactions between ion-irradiated single-wall CNTs (SWCNTs) and metal salt solutions were utilized to selectively deposit Au nanoparticles (Au-NPs) onto the SWCNTs. A direct correlation was established between defect density and Au-NP areal density, resulting in a method for rapid spatial profiling of ion-irradiation induced defects in SWCNTs. The effect of ion irradiation on the CNT-metal interface was also investigated and it was found that the contact resistance of Ag-SWCNT structures increases, while the specific contact resistance decreases. The increase in overall contact resistance was attributed to increased series resistance in the system due to damage of the bulk SWCNT films, while the decrease in specific contact

  17. Laser powder bed fusion additive manufacturing of metals; physics, computational, and materials challenges

    SciTech Connect

    King, W. E.; Anderson, A. T.; Ferencz, R. M.; Hodge, N. E.; Kamath, C.; Khairallah, S. A.; Rubencik, A. M.

    2015-12-29

    The production of metal parts via laser powder bed fusion additive manufacturing is growing exponentially. However, the transition of this technology from production of prototypes to production of critical parts is hindered by a lack of confidence in the quality of the part. Confidence can be established via a fundamental understanding of the physics of the process. It is generally accepted that this understanding will be increasingly achieved through modeling and simulation. However, there are significant physics, computational, and materials challenges stemming from the broad range of length and time scales and temperature ranges associated with the process. In this study, we review the current state of the art and describe the challenges that need to be met to achieve the desired fundamental understanding of the physics of the process.

  18. Laser powder bed fusion additive manufacturing of metals; physics, computational, and materials challenges

    DOE PAGES

    King, W. E.; Anderson, A. T.; Ferencz, R. M.; ...

    2015-12-29

    The production of metal parts via laser powder bed fusion additive manufacturing is growing exponentially. However, the transition of this technology from production of prototypes to production of critical parts is hindered by a lack of confidence in the quality of the part. Confidence can be established via a fundamental understanding of the physics of the process. It is generally accepted that this understanding will be increasingly achieved through modeling and simulation. However, there are significant physics, computational, and materials challenges stemming from the broad range of length and time scales and temperature ranges associated with the process. In thismore » study, we review the current state of the art and describe the challenges that need to be met to achieve the desired fundamental understanding of the physics of the process.« less

  19. New water-soluble metal working fluids additives from phosphonic acid derivatives for aluminum alloy materials.

    PubMed

    Kohara, Ichitaro; Tomoda, Hideyuki; Watanabe, Shoji

    2007-01-01

    Water-soluble metal working fluids are used for processing of aluminum alloy materials. This short paper describes properties of new additives for water-soluble cutting fluids for aluminum alloy materials. Some alkyldiphosphonic acids were prepared with known method. Amine salts of these phosphonic acids showed anti-corrosion property for aluminum alloy materials. However, they have no hard water tolerance. Monoesters of octylphosphonic acid were prepared by the reaction of octylphosphonic acid dichloride with various alcohols in the presence of triethylamine. Amine salts of monoester of octylphosphonic acid with diethyleneglycol monomethyl ether, ethyleneglycol monomethyl ether and triethyleneglycol monomethyl ether showed both of a good anti-corrosion property for aluminum alloy materials and hard water tolerance.

  20. Laser powder bed fusion additive manufacturing of metals; physics, computational, and materials challenges

    NASA Astrophysics Data System (ADS)

    King, W. E.; Anderson, A. T.; Ferencz, R. M.; Hodge, N. E.; Kamath, C.; Khairallah, S. A.; Rubenchik, A. M.

    2015-12-01

    The production of metal parts via laser powder bed fusion additive manufacturing is growing exponentially. However, the transition of this technology from production of prototypes to production of critical parts is hindered by a lack of confidence in the quality of the part. Confidence can be established via a fundamental understanding of the physics of the process. It is generally accepted that this understanding will be increasingly achieved through modeling and simulation. However, there are significant physics, computational, and materials challenges stemming from the broad range of length and time scales and temperature ranges associated with the process. In this paper, we review the current state of the art and describe the challenges that need to be met to achieve the desired fundamental understanding of the physics of the process.

  1. Laser powder bed fusion additive manufacturing of metals; physics, computational, and materials challenges

    SciTech Connect

    King, W. E.; Anderson, A. T.; Ferencz, R. M.; Hodge, N. E.; Khairallah, S. A.; Kamath, C.; Rubenchik, A. M.

    2015-12-15

    The production of metal parts via laser powder bed fusion additive manufacturing is growing exponentially. However, the transition of this technology from production of prototypes to production of critical parts is hindered by a lack of confidence in the quality of the part. Confidence can be established via a fundamental understanding of the physics of the process. It is generally accepted that this understanding will be increasingly achieved through modeling and simulation. However, there are significant physics, computational, and materials challenges stemming from the broad range of length and time scales and temperature ranges associated with the process. In this paper, we review the current state of the art and describe the challenges that need to be met to achieve the desired fundamental understanding of the physics of the process.

  2. Defect Characterization for Material Assurance in Metal Additive Manufacturing (FY15-0664)

    SciTech Connect

    Salzbrenner, Bradley; Boyce, Brad; Jared, Bradley Howell; Rodelas, Jeffrey; Laing, John Robert

    2016-02-01

    No industry-wide standards yet exist for minimum properties in additively manufactured (AM) metals. While AM alloys such as 17-4 precipitation hardened stainless steel have been shown to have average properties that can be comparable to wrought or cast product, they suffer from inconsistent performance. Variability in the feedstock powder, feature sizes, thermal history, and laser performance can lead to unpredictable surface finish, chemistry, phase content, and defects. To address this issue, rapid, efficient, high-throughput mechanical testing and data analysis was developed, providing profound statistical insight into the stochastic variability in properties. With this new approach, 1000’s of comprehensive tensile tests can be performed for the cost of 10’s of conventional tests. This new high-throughput approach provides a material qualification pathway that is commensurate with the quick turn-around benefit of AM.

  3. Leachability of Cr(VI) and other metals from asphalt composites with addition of filter dust.

    PubMed

    Vahcic, Mitja; Milacic, Radmila; Mladenovic, Ana; Murko, Simona; Zuliani, Tea; Zupancic, Marija; Scancar, Janez

    2008-12-01

    The potential use of filter dust in asphalt composites for road construction was investigated. Filter dust contains high concentrations of metals, of which Cr(VI) and Pb are leached with water. Compact and ground asphalt composites with addition of 2% of filter dust by mass were studied. In order to evaluate their environmental impact, leachability tests were performed using water and salt water as leaching agents. The concentrations of Cr(VI) and Pb were determined in leachates over a time period of 182 days. The results indicated that Pb was not leached with leaching agents from asphalt composites. Cr(VI) was also not leached with leaching agents from compact asphalt composites. However, in ground asphalt composites, Cr(VI) was leached with water in concentrations up to 220 microg L(-1) and in salt water up to 150 microg L(-1). From the physico-mechanical and environmental aspects, filter dust can be used as a component in asphalt mixtures.

  4. Highly diastereo- and regioselective transition metal-catalyzed additions of metal hydrides and bimetallic species to cyclopropenes: easy access to multisubstituted cyclopropanes.

    PubMed

    Trofimov, Alexander; Rubina, Marina; Rubin, Michael; Gevorgyan, Vladimir

    2007-11-09

    The first highly efficient, diastereo- and regioselective transition metal-catalyzed addition of metal hydrides (stannanes, silanes, and germanes) and bimetallic species (ditins and silyltins) to cyclopropenes has been developed. It was shown that the addition across the double bond of cyclopropenes is generally controlled by steric factors and proceeds from the least hindered face. This methodology represents a powerful and atom-economic approach toward a wide variety of highly substituted stereodefined cyclopropylmetals, useful building blocks unavailable by other methods.

  5. Thin films of metal oxides grown by chemical vapor deposition from volatile transition metal and lanthanide metal complexes

    NASA Astrophysics Data System (ADS)

    Pollard, Kimberly Dona

    1998-08-01

    This thesis describes the synthesis and characterization of novel volatile metal-organic complexes for the chemical vapor deposition (CVD) of metal oxides. Monomeric tantalum complexes, lbrack Ta(OEt)sb4(beta-diketonate)) are prepared by the acid-base reaction of lbrack Tasb2(OEt)sb{10}rbrack with a beta-diketone, (RC(O)CHsb2C(O)Rsp' for R = CHsb3, Rsp' = CFsb3; R = Rsp'=C(CHsb3)sb3; R = Csb3Fsb7,\\ Rsp'=C(CHsb3)sb3;\\ R=Rsp'=CFsb3; and R = Rsp' = CHsb3). The products are characterized spectroscopically. Thermal CVD using these complexes as precursors gave good quality Tasb2Osb5 thin films which are characterized by XPS, SEM, electrical measurements, and XRD. Factors affecting the film deposition such as the type of carrier gas and the temperature of the substrate were considered. Catalyst-enhanced CVD reactions with each of the precursors and a palladium catalyst, ((2-methylallyl)Pd(acac)), were studied as a lower temperature route to good quality Tasb2Osb5 films. The decomposition mechanism at the hot substrate surface was studied. Precursors for the formation of yttria by CVD were examined. New complexes of the form (Y(hfac)sb3(glyme)), (hfac = \\{CFsb3C(O)CHC(O)CFsb3\\}sp-,\\ glyme=CHsb3O(CHsb2CHsb2O)sb{n}CHsb3 for n = 1-4) were synthesized and characterized spectroscopically. X-ray structural determinations of three new complexes were obtained. CVD reaction conditions were determined which give YOF films and, with catalyst-enhanced CVD, reaction conditions which give selective formation of Ysb2Osb3, YOF, or YFsb3. The films were studied by XPS, SEM, and XRD. Decomposition mechanisms which lead to film formation, together with a possible route for fluorine atom transfer from the ligand to the metal resulting in fluorine incorporation, were studied by analysis of exhaust products using GC-MS. Novel precursors of the form lbrack Ce(hfac)sb3(glyme)rbrack,\\ (hfac=\\{CFsb3C(O)CHC(O)CFsb3\\}sp-,\\ glyme=CHsb3O(CHsb2CHsb2O)sb{n}CHsb3, n = 1-4) for CVD of ceria were

  6. Sample-free control of the mechanical properties of aluminum-based alloys with rare-earth metal additions

    NASA Astrophysics Data System (ADS)

    Matyunin, V. M.; Agafonov, R. Yu.; Zarubin, A. L.; Danilin, V. V.; Popkova, O. G.

    2015-12-01

    A technique is developed for sample-free control of the 0.2 offset yield strength and the ultimate tensile strength of aluminum alloys with rare-earth metal additions using indentation with a spherical indenter.

  7. Y-Ba-Cu-O film deposition by metal organic chemical vapor deposition on buffered metal substrates.

    SciTech Connect

    Selvamanickam, V.; Galinski, G.; DeFrank, J.; Trautwein, C.; Haldar, P.; Balachandran, U.; Lanagan, M.; Chudzik, M.

    1999-10-12

    YBa{sub 2}Cu{sub 3}O{sub 2} (YBCO) films have been deposited on buffered metal substrates by Metal Organic Chemical Vapor Deposition (MOCVD). Cube-textured nickel substrates were fabricated by a thermomechanical process. Epitaxial CeO{sub 2}films were deposited on these substrates by thermal evaporation. Nickel alloy substrates with biaxially-textured Yttria-Stabilized Zirconia (YSZ) buffer layers deposited by Ion Beam Assisted Deposition were also prepared. Highly biaxially-textured YBCO films were deposited by MOCVD on both types of metal substrates. A critical current density greater than 10{sup 5} A/cm{sup 2} at 77 K has been achieved in YBCO films on metal substrates.

  8. Preparations and properties of anti-corrosion additives of water-soluble metal working fluids for aluminum alloy materials.

    PubMed

    Watanabe, Shoji

    2008-01-01

    This short review describes various types of anti-corrosion additives of water-soluble metal working fluids for aluminum alloy materials. It is concerned with synthetic additives classified according to their functional groups; silicone compounds, carboxylic acids and dibasic acids, esters, Diels-Alder adducts, various polymers, nitrogen compounds, phosphoric esters, phosphonic acids, and others. Testing methods for water-soluble metal working fluids for aluminum alloy materials are described for a practical application in a laboratory.

  9. Comparative evaluation of microbial and chemical leaching processes for heavy metal removal from dewatered metal plating sludge.

    PubMed

    Bayat, Belgin; Sari, Bulent

    2010-02-15

    The purpose of the study described in this paper was to evaluate the application of bioleaching technique involving Acidithiobacillus ferrooxidans to recover heavy metals (Zn, Cu, Ni, Pb, Cd and Cr) in dewatered metal plating sludge (with no sulfide or sulfate compounds). The effect of some conditional parameters (i.e. pH, oxidation-reduction potential (ORP), sulfate production) and operational parameters (i.e. pulp density of the sludge and agitation time) were investigated in a 3l completely mixed batch (CMB) reactor. The metal recovery yields in bioleaching were also compared with chemical leaching of the sludge waste using commercial inorganic acids (sulfuric acids and ferric chloride). The leaching of heavy metals increased with decreasing of pH and increasing of ORP and sulfate production during the bioleaching experiment. Optimum pulp density for bioleaching was observed at 2% (w/v), and leaching efficiency decreased with increasing pulp density in bioleaching experiments. Maximum metal solubilization (97% of Zn, 96% of Cu, 93% of Ni, 84% of Pb, 67% of Cd and 34% of Cr) was achieved at pH 2, solids contents of 2% (w/v), and a reaction temperature of 25+/-2 degrees C during the bioleaching process. The maximum removal efficiencies of 72% and 79% Zn, 70% and 75% Cu, 69% and 73% Ni, 57% and 70% Pb, 55% and 65% Cd, and 11% and 22% Cr were also attained with the chemical leaching using sulfuric acids and ferric chloride, respectively, at pH 2, solids contents of 2% (w/v), and a reaction temperature of 25+/-2 degrees C during the acid leaching processes. The rates of metal leaching for bioleaching and chemical leaching are well described by a kinetic equation related to time. Although bioleaching generally requires a longer period of operation compared to chemical leaching, it achieves higher removal efficiency for heavy metals. The efficiency of leaching processes can be arranged in descending order as follows: bioleaching>ferric chloride leaching>sulfuric acid

  10. Toxicogenomics concepts and applications to study hepatic effects of food additives and chemicals

    SciTech Connect

    Stierum, Rob . E-mail: stierum@voeding.tno.nl; Heijne, Wilbert; Kienhuis, Anne; Ommen, Ben van; Groten, John

    2005-09-01

    Transcriptomics, proteomics and metabolomics are genomics technologies with great potential in toxicological sciences. Toxicogenomics involves the integration of conventional toxicological examinations with gene, protein or metabolite expression profiles. An overview together with selected examples of the possibilities of genomics in toxicology is given. The expectations raised by toxicogenomics are earlier and more sensitive detection of toxicity. Furthermore, toxicogenomics will provide a better understanding of the mechanism of toxicity and may facilitate the prediction of toxicity of unknown compounds. Mechanism-based markers of toxicity can be discovered and improved interspecies and in vitro-in vivo extrapolations will drive model developments in toxicology. Toxicological assessment of chemical mixtures will benefit from the new molecular biological tools. In our laboratory, toxicogenomics is predominantly applied for elucidation of mechanisms of action and discovery of novel pathway-supported mechanism-based markers of liver toxicity. In addition, we aim to integrate transcriptome, proteome and metabolome data, supported by bioinformatics to develop a systems biology approach for toxicology. Transcriptomics and proteomics studies on bromobenzene-mediated hepatotoxicity in the rat are discussed. Finally, an example is shown in which gene expression profiling together with conventional biochemistry led to the discovery of novel markers for the hepatic effects of the food additives butylated hydroxytoluene, curcumin, propyl gallate and thiabendazole.

  11. Tunable Surface Structuration of Silicon by Metal Assisted Chemical Etching with Pt Nanoparticles under Electrochemical Bias.

    PubMed

    Torralba, Encarnación; Le Gall, Sylvain; Lachaume, Raphaël; Magnin, Vincent; Harari, Joseph; Halbwax, Mathieu; Vilcot, Jean-Pierre; Cachet-Vivier, Christine; Bastide, Stéphane

    2016-11-16

    An in-depth study of metal assisted chemical etching (MACE) of p-type c-Si in HF/H2O2 aqueous solutions using Pt nanoparticles as catalysts is presented. Combination of cyclic voltammetry, open circuit measurements, chronoamperometry, impedance spectroscopy, and 2D band bending modeling of the metal/semiconductor/electrolyte interfaces at the nanoscale and under different etching conditions allows gaining physical insights into this system. Additionally, in an attempt to mimic the etching conditions, the modeling has been performed with a positively biased nanoparticle buried in the Si substrate. Following these findings, the application of an external polarization during etching is introduced as a novel efficient approach for achieving straightforward control of the pore morphology by acting upon the band bending at the Si/electrolyte junction. In this way, nanostructures ranging from straight mesopores to cone-shaped macropores are obtained as the Si sample is biased from negative to positive potentials. Remarkably, macroscopic cone-shaped pores in the 1-5 μm size range with a high aspect ratio (L/W ∼ 1.6) are obtained by this method. This morphology leads to a reduction of the surface reflectance below 5% over the entire VIS-NIR domain, which outperforms macrostructures made by state of the art texturization techniques for Si solar cells.

  12. Damage-tolerant metallic composites via melt infiltration of additively manufactured preforms

    DOE PAGES

    Pawlowski, Alexander E.; Cordero, Zachary C.; French, Matthew R.; ...

    2017-04-22

    A facile two-step approach for 3D printing metal-metal composites with precisely controlled microstructures is described. Composites made with this approach exhibit tailorable thermal and mechanical properties as well as exceptional damage tolerance.

  13. Chemically stable ceramic-metal composite membrane for hydrogen separation

    DOEpatents

    Chen, Fanglin; Fang, Shumin; Brinkman, Kyle S.

    2017-06-27

    A hydrogen permeation membrane is provided that can include a metal and a ceramic material mixed together. The metal can be Ni, Zr, Nb, Ta, Y, Pd, Fe, Cr, Co, V, or combinations thereof, and the ceramic material can have the formula: BaZr.sub.1-x-yY.sub.xT.sub.yO.sub.3-.delta. where 0.ltoreq.x.ltoreq.0.5, 0.ltoreq.y.ltoreq.0.5, (x+y)>0; 0.ltoreq..delta..ltoreq.0.5, and T is Sc, Ti, Nb, Ta, Mo, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Sn, or combinations thereof. A method of forming such a membrane is also provided. A method is also provided for extracting hydrogen from a feed stream.

  14. Formation of amorphous metal alloys by chemical vapor deposition

    DOEpatents

    Mullendore, Arthur W.

    1990-01-01

    Amorphous alloys are deposited by a process of thermal dissociation of mixtures or organometallic compounds and metalloid hydrides, e.g., transition metal carbonyl such as nickel carbonyl, and diborane. Various sizes and shapes of deposits can be achieved, including near-net-shape free standing articles, multilayer deposits, and the like. Manipulation or absence of a magnetic field affects the nature and the structure of the deposit.

  15. Formation of amorphous metal alloys by chemical vapor deposition

    DOEpatents

    Mullendore, A.W.

    1988-03-18

    Amorphous alloys are deposited by a process of thermal dissociation of mixtures of organometallic compounds and metalloid hydrides,e.g., transition metal carbonyl, such as nickel carbonyl and diborane. Various sizes and shapes of deposits can be achieved, including near-net-shape free standing articles, multilayer deposits, and the like. Manipulation or absence of a magnetic field affects the nature and the structure of the deposit. 1 fig.

  16. Chemical changes in heavy metals in the leachates from Technosols.

    PubMed

    Yao, F X; Macías, F; Virgel, S; Blanco, F; Jiang, X; Camps Arbestain, M

    2009-09-01

    A 2 month long column study was conducted to evaluate the mobility of heavy metals eluting from Technosols constituted from sewage sludges (aerobic or anaerobic) (as controls) or a mixture of different types of sewage sludges with green foundry sand (FS) or/and Linz-Donowitz slag (LD). The organic and inorganic wastes were mixed at a ratio of 56:44 (w/w). The mixtures and the controls were moistened to field capacity before adding them to the polypropylene columns (4.5 cm wide and 14 cm long). During the 8-week experimental period, the columns were watered, twice a week, with 100 mL of deionised water. The concentrations of heavy metals (Cu, Zn, Ni, Pb, Cd, and Cr) in the leachates were determined periodically. The concentrations of all the heavy metals were generally higher in the leachates from the Technosols containing anaerobic sewage sludge as a component. The concentration of Cu was strongly dependent on pH and was significantly higher (P<0.05) in the most alkaline leachates (pH>10) than in the other leachates. More Zn was mobilized in the most acidic leachates (pH<6) than in other leachates. The concentration of Ni in 80% of the leachates exceeded the EU drinking water limit for Ni (0.02 mgL(-1)). The concentrations of Pb were lower in the Technosols containing FS. The concentrations of Cd in the leachates from Technosols containing the conditioners were relatively high, while concentrations of Cr were higher in the controls. As far as the potential toxicity of heavy metals is concerned, the combination of aerobic sludge, inorganic conditioners able to buffer the pH to around neutrality, and reactive aluminosilicates, can be regarded as suitable choice for formulating Technosols from wastes.

  17. Composite of liposome and metal complexes: Toward creating a new chemical reaction space

    NASA Astrophysics Data System (ADS)

    Koshiyama, Tomomi; Ohba, Masaaki

    2015-12-01

    The purpose of our research is to construct a novel functional space by fixation of various metal complexes into the liposome space. For the functionalization of liposome surface, we designed lipophilic metal complexes and succeeded in the fixation of various metal complexes such as oxidation catalysts. In addition, reactivities of metal complexes on the liposome surface were optimized by controlling their surrounding environment using various types of phospholipids. Furthermore, we succeeded in the incorporation of coordination polymers in inner water phase of liposomes using antibiotic ion channel, and the composites showed absorption of metal ions through antibiotic ion channels.

  18. Results of chemical decontamination of DOE`s uranium-enrichment scrap metal

    SciTech Connect

    Levesque, R.G.

    1997-02-01

    The CORPEX{reg_sign} Nuclear Decontamination Processes were used to decontaminate representative scrap metal specimens obtained from the existing scrap metal piles located at the Department of Energy (DOE) Portsmouth Gaseous Diffusion Plant (PORTS), Piketon, Ohio. In September 1995, under contract to Lockheed Martin Energy Systems, MELE Associates, Inc. performed the on-site decontamination demonstration. The decontamination demonstration proved that significant amounts of the existing DOE scrap metal can be decontaminated to levels where the scrap metal could be economically released by DOE for beneficial reuse. This simple and environmentally friendly process can be used as an alternative, or in addition to, smelting radiologically contaminated scrap metal.

  19. Chemical and biological extraction of metals present in E waste: A hybrid technology

    SciTech Connect

    Pant, Deepak; Joshi, Deepika; Upreti, Manoj K.; Kotnala, Ravindra K.

    2012-05-15

    Highlights: Black-Right-Pointing-Pointer Hybrid methodology for E waste management. Black-Right-Pointing-Pointer Efficient extraction of metals. Black-Right-Pointing-Pointer Trace metal extraction is possible. - Abstract: Management of metal pollution associated with E-waste is widespread across the globe. Currently used techniques for the extraction of metals from E-waste by using either chemical or biological leaching have their own limitations. Chemical leaching is much rapid and efficient but has its own environmental consequences, even the future prospects of associated nanoremediation are also uncertain. Biological leaching on the other hand is comparatively a cost effective technique but at the same moment it is time consuming and the complete recovery of the metal, alone by biological leaching is not possible in most of the cases. The current review addresses the individual issues related to chemical and biological extraction techniques and proposes a hybrid-methodology which incorporates both, along with safer chemicals and compatible microbes for better and efficient extraction of metals from the E-waste.

  20. Bonding in diborane-metal complexes: a quantum-chemical and experimental study of complexes featuring early and late transition metals.

    PubMed

    Wagner, Arne; Kaifer, Elisabeth; Himmel, Hans-Jörg

    2013-06-03

    The coordination chemistry of the doubly base-stabilised diborane(4), [HB(hpp)]2 (hpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido-[1,2-a]pyrimidinate), was extended by the synthesis of new late transition-metal complexes containing Cu(I) and Rh(I) fragments. A detailed experimental study was conducted and quantum-chemical calculations on the metal-ligand bonding interactions for [HB(hpp)]2 complexes of Group 6, 9, 11 and 12 metals revealed the dominant B-H-M interactions in the case of early transition-metal fragments, whereas the B-B-M bonding prevails in the case of the late d-block compounds. These findings support the experimental results as reflected by the IR and NMR spectroscopic parameters of the investigated compounds. DFT calculations on [MeB(hpp)]2 and model reactions between [B2H4⋅2NMe3] and [Rh(μ-Cl)(C2H4)2] showed that the bicyclic guanidinate allows in principle for an oxidative addition of the B-B bond. However, the formation of σ-complexes is thermodynamically favoured. The results point to the selective B-H or B-B bond-activation of diborane compounds by complexation, depending on the chosen transition-metal fragment.

  1. Modulating laser intensity profile ellipticity for microstructural control during metal additive manufacturing

    DOE PAGES

    Roehling, Tien T.; Wu, Sheldon S. Q.; Khairallah, Saad A.; ...

    2017-02-12

    Additively manufactured (AM) metals are often highly textured, containing large columnar grains that initiate epitaxially under steep temperature gradients and rapid solidification conditions. These unique microstructures partially account for the massive property disparity existing between AM and conventionally processed alloys. Although equiaxed grains are desirable for isotropic mechanical behavior, the columnar-to-equiaxed transition remains difficult to predict for conventional solidification processes, and much more so for AM. In this study, the effects of laser intensity profile ellipticity on melt track macrostructures and microstructures were studied in 316L stainless steel. Experimental results were supported by temperature gradients and melt velocities simulated usingmore » the ALE3D multi-physics code. As a general trend, columnar grains preferentially formed with increasing laser power and scan speed for all beam profiles. However, when conduction mode laser heating occurs, scan parameters that result in coarse columnar microstructures using Gaussian profiles produce equiaxed or mixed equiaxed-columnar microstructures using elliptical profiles. Furthermore, by modulating spatial laser intensity profiles on the fly, site-specific microstructures and properties can be directly engineered into additively manufactured parts.« less

  2. Characterization of embedded fiber optic strain sensors into metallic structures via ultrasonic additive manufacturing

    NASA Astrophysics Data System (ADS)

    Schomer, John J.; Hehr, Adam J.; Dapino, Marcelo J.

    2016-04-01

    Fiber Bragg Grating (FBG) sensors measure deviation in a reflected wavelength of light to detect in-situ strain. These sensors are immune to electromagnetic interference, and the inclusion of multiple FBGs on the same fiber allows for a seamlessly integrated sensing network. FBGs are attractive for embedded sensing in aerospace applications due to their small noninvasive size and prospect of constant, real-time nondestructive evaluation. In this study, FBG sensors are embedded in aluminum 6061 via ultrasonic additive manufacturing (UAM), a rapid prototyping process that uses high power ultrasonic vibrations to weld similar and dissimilar metal foils together. UAM was chosen due to the desire to embed FBG sensors at low temperatures, a requirement that excludes other additive processes such as selective laser sintering or fusion deposition modeling. In this paper, the embedded FBGs are characterized in terms of birefringence losses, post embedding strain shifts, consolidation quality, and strain sensing performance. Sensors embedded into an ASTM test piece are compared against an exterior surface mounted foil strain gage at both room and elevated temperatures using cyclic tensile tests.

  3. High temperature hydrogen sulfide adsorption on activated carbon - I. Effects of gas composition and metal addition

    USGS Publications Warehouse

    Cal, M.P.; Strickler, B.W.; Lizzio, A.A.

    2000-01-01

    Various types of activated carbon sorbents were evaluated for their ability to remove H2S from a simulated coal gas stream at a temperature of 550 ??C. The ability of activated carbon to remove H2S at elevated temperature was examined as a function of carbon surface chemistry (oxidation, thermal desorption, and metal addition), and gas composition. A sorbent prepared by steam activation, HNO3 oxidation and impregnated with Zn, and tested in a gas stream containing 0.5% H2S, 50% CO2 and 49.5% N2, had the greatest H2S adsorption capacity. Addition of H2, CO, and H2O to the inlet gas stream reduced H2S breakthrough time and H2S adsorption capacity. A Zn impregnated activated carbon, when tested using a simulated coal gas containing 0.5% H2S, 49.5% N2, 13% H2, 8.5% H2O, 21% CO, and 7.5% CO2, had a breakthrough time of 75 min, which was less than 25 percent of the length of breakthrough for screening experiments performed with a simplified gas mixture of 0.5% H2S, 50% CO2, and 49.5% N2.

  4. Octahedral Chiral-at-Metal Iridium Catalysts: Versatile Chiral Lewis Acids for Asymmetric Conjugate Additions.

    PubMed

    Shen, Xiaodong; Huo, Haohua; Wang, Chuanyong; Zhang, Bo; Harms, Klaus; Meggers, Eric

    2015-06-26

    Octahedral iridium(III) complexes containing two bidentate cyclometalating 5-tert-butyl-2-phenylbenzoxazole (IrO) or 5-tert-butyl-2-phenylbenzothiazole (IrS) ligands in addition to two labile acetonitrile ligands are demonstrated to constitute a highly versatile class of asymmetric Lewis acid catalysts. These complexes feature the metal center as the exclusive source of chirality and serve as effective asymmetric catalysts (0.5-5.0 mol % catalyst loading) for a variety of reactions with α,β-unsaturated carbonyl compounds, namely Friedel-Crafts alkylations (94-99% ee), Michael additions with CH-acidic compounds (81-97% ee), and a variety of cycloadditions (92-99% ee with high d.r.). Mechanistic investigations and crystal structures of an iridium-coordinated substrates and iridium-coordinated products are consistent with a mechanistic picture in which the α,β-unsaturated carbonyl compounds are activated by two-point binding (bidentate coordination) to the chiral Lewis acid.

  5. Effect of transition-metal additives on dehydrogenation kinetics of MgH2

    NASA Astrophysics Data System (ADS)

    Roy, Anindya; Janotti, Anderson; van de Walle, Chris G.

    2013-03-01

    Using first-principles calculations based on hybrid density functional theory we study the (de)hydrogenation process in MgH2, an important solid-state hydrogen storage material. This reaction proceeds through diffusion processes, mediated by native point defects such as vacancies and interstitials. Reducing the formation energy of relevant defects increases their concentrations, resulting in higher diffusion rates and an enhancement in kinetics. We investigate the formation energies of native point defects in MgH2 and determine the position of the Fermi level in the band gap using the charge neutrality condition. The presence of transition-metal (TM) impurities (Ti, Fe, Co and Ni) causes the Fermi level to shift according to the position of the TM acceptor/donor levels in the band gap. This shift can bring down the formation energy of native defects. Our calculations predict that all of the TM additives, in either interstitial or substitutional configurations, may cause such a shift in the Fermi level and thus increase the concentration of the hydrogen vacancies that govern hydrogen diffusion. Our proposed mechanism explains the experimentally observed enhancement in the rate of dehydrogenation of MgH2 upon addition of TM impurities. U.S. Department of Energy (Grant No. DE-FG02-07ER46434), National Energy Research Scientific Computing Center

  6. Effect of yttrium additions on void swelling in Liquid Metal Fast Breeder Reactor candidate cladding alloys

    SciTech Connect

    Hopson, R.D.

    1981-10-01

    Candidate Liquid Metal Fast Breeder Reactor cladding alloys AL1 (Fe-26% Ni-9% Cr) and AL2 (Fe-35% Ni-12% Cr) without and with the addition of 0.1% yttrium were bombarded by 4 MeV/sup 56/Fe/sup 2 +/ ions without and with simultaneous bombardment by 0.4 MeV /sup 4/He/sup +/ ions. These bombardments were conducted at various irradiation temperatures to determine the effect of yttrium on void swelling. The addition of yttrium decreased peak swelling for 4 MeV /sup 56/Fe/sup 2 +/ ion bombarded AL1 and AL2 by 28% and 20%, respectively. In all cases where similar sample comparisons were made (i.e., undoped with undoped and doped with doped) and where bombardment conditions were similar (i.e., single with single beam and dual with dual beam), AL1 showed less peak swelling than did AL2. Simultaneously implanting helium during heavy-ion bombardment increased peak swelling in undoped and doped AL1 by factors of 2.3 and 2.6, respectively.

  7. Room-Temperature Chemical Welding and Sintering of Metallic Nanostructures by Capillary Condensation.

    PubMed

    Yoon, Sung-Soo; Khang, Dahl-Young

    2016-06-08

    Room-temperature welding and sintering of metal nanostructures, nanoparticles and nanowires, by capillary condensation of chemical vapors have successfully been demonstrated. Nanoscale gaps or capillaries that are abundant in layers of metal nanostructures have been found to be the preferred sites for the condensation of chemically oxidizing vapor, H2O2 in this work. The partial dissolution and resolidification at such nanogaps completes the welding/sintering of metal nanostructures within ∼10 min at room-temperature, while other parts of nanostructures remain almost intact due to negligible amount of condensation on there. The welded networks of Ag nanowires have shown much improved performances, such as high electrical conductivity, mechanical flexibility, optical transparency, and chemical stability. Chemically sintered layers of metal nanoparticles, such as Ag, Cu, Fe, Ni, and Co, have also shown orders of magnitude increase in electrical conductivity and improved environmental stability, compared to nontreated ones. Pertinent mechanisms involved in the chemical welding/sintering process have been discussed. Room-temperature welding and sintering of metal nanostructures demonstrated here may find widespread application in diverse fields, such as displays, deformable electronics, wearable heaters, and so forth.

  8. Evaluation of four chemical extractants for metal determinations in wetland soils

    SciTech Connect

    Sistani, K.R.; Mays, D.A.; Taylor, R.W.; Buford, C.

    1995-12-01

    Wetland soils (hydric soils) are unique in their chemical characteristics compared to upland soils. It is known that they are capable of removing a variety of wastes from polluted water entering the wetland including metals and potentially toxic heavy metals. When these metals are determined in wetland soils, it is necessary to use the proper chemical extractant(s). Four commonly used chemical extractants (Mehlich 1, Mehlich 3, 0.1 M HC1, and DTPA) for soil fertility evaluation were selected to measure metal concentrations of three different wetland soils/spoils. Soil samples were collected from the constructed wetland cells which were lined with Abernathy silt loam topsoil and two different mine spoil materials [collected from active coal strip-mined sites in Alabama (pH 5.9) and Tennessee (pH 3.2)]. Mehlich 3 extracted the most zinc (Zn), iron (Fe), manganese (Mn), calcium (Ca), magnesium (Mg), potassium (K), sodiumm (Na), and aluminum (Al), while 0.1 M HCl extracted more cadmium (Cd), copper (Cu), and lead (Pb). Extractants followed the same trend in removing quantities of the metals from the three soil/spoil materials, with DTPA generally extracting the least amount of the metal (the trend was Mehlich 3 > 0.1N HCl > Mehlich 1 > DTPA). However, DTPA removed large quantities of metals from Tennessee spoil compared to Alabama spoil and topsoil, suggesting the higher effectiveness of DTPA under acidic conditions. Metal concentrations in plant tissue did not show a definite trend in correlation with metals extracted by four chemical extractants. 16 refs., 7 figs.

  9. LIFE Chamber Chemical Equilibrium Simulations with Additive Hydrogen, Oxygen, and Nitrogen

    SciTech Connect

    DeMuth, J A; Simon, A J

    2009-09-03

    In order to enable continuous operation of a Laser Inertial confinement Fusion Energy (LIFE) engine, the material (fill-gas and debris) in the fusion chamber must be carefully managed. The chamber chemical equilibrium compositions for post-shot mixtures are evaluated to determine what compounds will be formed at temperatures 300-5000K. It is desired to know if carbon and or lead will deposit on the walls of the chamber, and if so: at what temperature, and what elements can be added to prevent this from happening. The simulation was conducted using the chemical equilibrium solver Cantera with a Matlab front-end. Solutions were obtained by running equilibrations at constant temperature and constant specific volume over the specified range of temperatures. It was found that if nothing is done, carbon will deposit on the walls once it cools to below 2138K, and lead below 838K. Three solutions to capture the carbon were found: adding pure oxygen, hydrogen/nitrogen combo, and adding pure nitrogen. The best of these was the addition of oxygen which would readily form CO at around 4000K. To determine the temperature at which carbon would deposit on the walls, temperature solutions to evaporation rate equations needed to be found. To determine how much carbon or any species was in the chamber at a given time, chamber flushing equations needed to be developed. Major concerns are deposition of carbon and/or oxygen on the tungsten walls forming tungsten oxides or tungsten carbide which could cause embrittlement and cause failure of the first wall. Further research is needed.

  10. Comparison between electrocoagulation and chemical precipitation for metals removal from acidic soil leachate.

    PubMed

    Meunier, Nathalie; Drogui, Patrick; Montané, Camille; Hausler, Robert; Mercier, Guy; Blais, Jean-François

    2006-09-01

    This paper provides a quantitative comparison between electrocoagulation and chemical precipitation based on heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) removal from acidic soil leachate (ASL) at the laboratory pilot scale. Chemical precipitation was evaluated using either calcium hydroxide or sodium hydroxide, whereas electrocoagulation was evaluated via an electrolytic cell using mild steel electrodes. Chemical precipitation was as effective as electrocoagulation in removing metals from ASL having low contamination levels (30 mg Pbl(-1) and 18 mg Znl(-1)). For ASL enriched with different metals (each concentration of metals was initially adjusted to 100 mg l(-1)), the residual Cr, Cu, Pb and Zn concentrations at the end of the experiments were below the acceptable level recommended for discharge in sewage urban works (more than 99.8% of metal was removed) using either electrocoagulation or chemical precipitation. Cd was more effectively removed by electrochemical treatment, whereas Ni was easily removed by chemical treatment. The cost for energy, chemicals and disposal of metallic residue of electrocoagulation process ranged from USD 8.83 to 13.95 tds(-1), which was up to five times lower than that recorded using chemical precipitation. Highly effective electrocoagulation was observed as the ASL was specifically enriched with high concentration of Pb (250-2000 mg Pbl(-1)). More than 99.5% of Pb was removed regardless of the initial Pb concentration imposed in ASL and, in all cases, the residual Pb concentrations (0.0-1.44 mg l(-1)) were below the limiting value (2.0 mg l(-1)) for effluent discharge in sewage works.

  11. Effects of chemical composition of fly ash on efficiency of metal separation in ash-melting of municipal solid waste

    SciTech Connect

    Okada, Takashi; Tomikawa, Hiroki

    2013-03-15

    Highlights: ► Separation of Pb and Zn from Fe and Cu in ash-melting of municipal solid waste. ► Molar ratio of Cl to Na and K in fly ash affected the metal-separation efficiency. ► The low molar ratio and a non-oxidative atmosphere were better for the separation. - Abstract: In the process of metal separation by ash-melting, Fe and Cu in the incineration residue remain in the melting furnace as molten metal, whereas Pb and Zn in the residue are volatilized. This study investigated the effects of the chemical composition of incineration fly ash on the metal-separation efficiency of the ash-melting process. Incineration fly ash with different chemical compositions was melted with bottom ash in a lab-scale reactor, and the efficiency with which Pb and Zn were volatilized preventing the volatilization of Fe and Cu was evaluated. In addition, the behavior of these metals was simulated by thermodynamic equilibrium calculations. Depending on the exhaust gas treatment system used in the incinerator, the relationships among Na, K, and Cl concentrations in the incineration fly ash differed, which affected the efficiency of the metal separation. The amounts of Fe and Cu volatilized decreased by the decrease in the molar ratio of Cl to Na and K in the ash, promoting metal separation. The thermodynamic simulation predicted that the chlorination volatilization of Fe and Cu was prevented by the decrease in the molar ratio, as mentioned before. By melting incineration fly ash with the low molar ratio in a non-oxidative atmosphere, most of the Pb and Zn in the ash were volatilized leaving behind Fe and Cu.

  12. Effects of simulated acid rain, EDTA, or their combination, on migration and chemical fraction distribution of extraneous metals in Ferrosol.

    PubMed

    Wen, Fang; Hou, Hong; Yao, Na; Yan, Zengguang; Bai, Liping; Li, Fasheng

    2013-01-01

    A laboratory repacked soil-leaching column experiment was conducted to study the effects of simulated acid rain or EDTA by themselves or in combination, on migration and chemical speciation distribution of Pb and its alternative rare metals including Ag, Bi, In, Sb, and Sn. Experimental results demonstrate that leaching with simulated acid rain promoted the migration of Bi, In and Pb, and their migration reached down to 8 cm in the soil profile, no enhancement of Sb, Ag or Sn migration was observed. Addition of EDTA significantly enhanced the migration of all six metals, especially Bi, In and Pb. The migration of metals was in the order Pb>Bi>In>Sb>Sn>Ag. The individual and combined effects of acid rain and EDTA increased the environmental risk of metals, by increasing the soluble content of metals in soil solutions and the relative distribution of the exchangeable fraction. Leaching risks of Bi, In and Pb were higher than other three metals. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

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

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

  14. A generalized physiologically-based toxicokinetic modeling system for chemical mixtures containing metals

    PubMed Central

    2010-01-01

    Background Humans are routinely and concurrently exposed to multiple toxic chemicals, including various metals and organics, often at levels that can cause adverse and potentially synergistic effects. However, toxicokinetic modeling studies of exposures to these chemicals are typically performed on a single chemical basis. Furthermore, the attributes of available models for individual chemicals are commonly estimated specifically for the compound studied. As a result, the available models usually have parameters and even structures that are not consistent or compatible across the range of chemicals of concern. This fact precludes the systematic consideration of synergistic effects, and may also lead to inconsistencies in calculations of co-occurring exposures and corresponding risks. There is a need, therefore, for a consistent modeling framework that would allow the systematic study of cumulative risks from complex mixtures of contaminants. Methods A Generalized Toxicokinetic Modeling system for Mixtures (GTMM) was developed and evaluated with case studies. The GTMM is physiologically-based and uses a consistent, chemical-independent physiological description for integrating widely varying toxicokinetic models. It is modular and can be directly "mapped" to individual toxicokinetic models, while maintaining physiological consistency across different chemicals. Interaction effects of complex mixtures can be directly incorporated into the GTMM. Conclusions The application of GTMM to different individual metals and metal compounds showed that it explains available observational data as well as replicates the results from models that have been optimized for individual chemicals. The GTMM also made it feasible to model toxicokinetics of complex, interacting mixtures of multiple metals and nonmetals in humans, based on available literature information. The GTMM provides a central component in the development of a "source-to-dose-to-effect" framework for modeling

  15. Chemical fraction, leachability, and bioaccessibility of heavy metals in contaminated soils, Northeast China.

    PubMed

    Yutong, Zong; Qing, Xiao; Shenggao, Lu

    2016-12-01

    Heavy metals in urban soils may pose risks to both urban environment and human health. However, only a fraction of heavy metals in soil is mobile and/or bioavailable for plant uptake and human ingestion. This study evaluates the chemical fraction and potential mobility and bioaccessibility of heavy metals (Cd, Cr, Cu, Pb, and Zn) in the contaminated urban topsoils from steel-industrial city (Anshan), Northeastern China. Chemical forms of heavy metals in soils are determined using Tessier sequential extraction technique. The toxicity characteristic leaching procedure (TCLP), ethylenediaminetetraacetic acid (EDTA), and US Pharmacopeia methodology (USPM) are used to determine the operationally defined potentially mobile and bioaccessible metal fractions, respectively. Sequential extraction results show that Cd has the highest percentage of exchangeable form, whereas Cr primarily exists in residual form. The non-residual fraction of heavy metals increases in the order of Cr < Cu < Pb < Zn < Cd. The leachability of heavy metals evaluated by TCLP test indicates that Cd, Zn, Cu, and Pb have much higher mobile than Cr. The bioavailability of heavy metals determined by EDTA extraction decreases in the order of Pb > Cu ≅ Zn > Cd > Cr. The order of bioaccessibility determined by USPM extraction is Pb = Cu > Zn > Cd > Cr. The Cr exhibits the lowest leachability and bioaccessibility among the investigated metals. The Pb has the highest bioaccessibility, indicating higher potential hazard for the human health. There are significant relationships between the EDTA- and USPM-extractable metals (Cd, Cu, Pb, and Zn) and the sum of first three steps of sequential extraction. Highly significant correlation is found between amounts of EDTA-extractable Cd, Cu, Pb, and Zn and USPM-extractable metals. The result suggests that EDTA extraction can be helpful to estimate the bioaccessibility of heavy metals for human ingestion. Introduction of mobile and human bioaccessible concentrations

  16. EFFECT OF NITROGEN AND METAL ADDITIONS ON NITROGEN FIXATION ACTIVITY IN BIOLOGICAL SOIL CRUSTS

    NASA Astrophysics Data System (ADS)

    Alexander, K.; Lui, D.; Anbar, A. D.; Garcia-Pichel, F.; Hartnett, H. E.

    2009-12-01

    Biological soil crusts (BSCs) are diverse consortia of microorganisms that live in intimate association with soils in arid environments. Also called cryptogamic or microbiotic crusts, these communities can include cyanobacteria, algae, heterotrophic bacteria, fungi, lichens, and mosses. Together, these organisms provide many services to their surrounding ecosystems, including reduction of water runoff, promotion of water infiltration, and prevention of soil erosion. The cyanobacteria and algae also provide fixed carbon (C) to the soil through photosynthesis, and because atmospheric deposition of nitrogen (N) in arid environments is low, the major input of biologically available N comes from cyanobacteria capable of converting nitrogen gas (N2) to ammonium (NH4+). Biological soil crusts are easily destroyed by livestock grazing, motor vehicle travel, and many forms of recreational and agricultural land use. Loss of BSC cover can leave the soil vulnerable to intense erosion that can remove the nutrients necessary to sustain plant and animal life, thus accelerating the process of desertification. In order to preserve existing crusts and encourage the development of new crusts, it is crucial to understand the nutrient requirements of metabolism and growth in these microbial communities. This study investigated the affect of nitrogen and metal additions on N2-fixation activity in cyanobacterially-dominated crusts from the Colorado Plateau near Moab, Utah. Although N2-fixation has been studied in this system before, the affect of nutrient additions on N2-fixation activity has not been documented. The goal of this work was to understand how N and metal supplementation affects crust N metabolism. Three experiments were conducted to observe how N2-fixation activity changed with the addition of N, molybdenum (Mo), and vanadium (V). Molybdenum and vanadium were chosen because they are most commonly found at the active site of the enzyme nitrogenase, the molecule responsible

  17. Testing for Additivity in Chemical Mixtures Using a Fixed-Ratio Ray Design and Statistical Equivalence Testing Methods

    EPA Science Inventory

    Fixed-ratio ray designs have been used for detecting and characterizing interactions of large numbers of chemicals in combination. Single chemical dose-response data are used to predict an “additivity curve” along an environmentally relevant ray. A “mixture curve” is estimated fr...

  18. Testing for Additivity in Chemical Mixtures Using a Fixed-Ratio Ray Design and Statistical Equivalence Testing Methods

    EPA Science Inventory

    Fixed-ratio ray designs have been used for detecting and characterizing interactions of large numbers of chemicals in combination. Single chemical dose-response data are used to predict an “additivity curve” along an environmentally relevant ray. A “mixture curve” is estimated fr...

  19. A chemically stable europium metal-organic framework for bifunctional chemical sensor and recyclable on-off-on vapor response

    NASA Astrophysics Data System (ADS)

    Wang, Dongbo; Liu, Jingjuan; Liu, Zhiliang

    2017-07-01

    A ratiometric luminescence sensing method is developed and makes the chemically stable Eu metal-organic framework to be the first bifunctional chemical sensor for Cd2+ and F- ions with naked-eye observation in the field of sensing applications utilizing luminescent Ln-MOFs. This is the first example of luminescent colorimetric sensor caused by the direct dual emissions of a single Ln-MOF. A recyclable vapoluminescent sensor for HCl and NH3 by the naked eye has also been realized.

  20. Review and evaluation of literature on testing of chemical additives for scale control in geothermal fluids. Final report

    SciTech Connect

    Crane, C.H.; Kenkeremath, D.C.

    1981-01-01

    A selected group of reported tests of chemical additives in actual geothermal fluids are reviewed and evaluated to summarize the status of chemical scale-control testing and identify information and testing needs. The task distinguishes between scale control in the cooling system of a flash plant and elsewhere in the utilization system due to the essentially different operating environments involved. Additives for non-cooling geothermal fluids are discussed by scale type: silica, carbonate, and sulfide.

  1. Chemically enhanced ion etching on refractory metal silicides

    SciTech Connect

    O'Brien, W.L.; Rhodin, T.N.; Rathbun, L.C.

    1988-05-01

    Mechanisms of chemically enhanced ion etching on TiSi/sub 2/ and MoSi/sub 2/ were studied using high-resolution (250 ns) direct time-of-flight (TOF) spectroscopy and steady-state surface techniques (Auger electron spectroscopy and x-ray photoelectron spectroscopy). Argon ion pulses (4 ..mu..s, 0.2 mA/cm/sup 2/) were used in combination with a high-pressure chlorine gas doser (1 x 10/sup -5/ Torr) to study ion etchant product distributions. Ion product TOF distributions were interpreted in terms of the collisional cascade model with corrections for ionization probability. Surface chemical and compositional changes were measured after etching the silicide surfaces. Differences in TOF distributions of the same species from different substrates (e.g., Si from Si, TiSi/sub 2/ and MoSi/sub 2/) are discussed on the basis of these chemical and compositional changes. Etching mechanisms for the silicides are discussed by comparison to the etching of the elemental surfaces.

  2. Chemical and Sensory Quality Preservation in Coated Almonds with the Addition of Antioxidants.

    PubMed

    Larrauri, Mariana; Demaría, María Gimena; Ryan, Liliana C; Asensio, Claudia M; Grosso, Nelson R; Nepote, Valeria

    2016-01-01

    Almonds provide many benefits such as preventing heart disease due to their high content of oleic fatty acid-rich oil and other important nutrients. However, they are susceptible to oxidation reactions causing rancidity during storage. The objective of this work was to evaluate the chemical and sensory quality preservation of almonds coated with carboxymethyl cellulose and with the addition of natural and synthetic antioxidants during storage. Four samples were prepared: almonds without coating (C), almonds coated with carboxymethyl cellulose (CMC), almonds coated with CMC supplemented with peanut skins extract (E), and almonds coated with CMC and supplemented with butylhydroxytoluene (BHT). Proximate composition and fatty acid profile were determined on raw almonds. Almond samples (C, CMC, E and BHT) were stored at 40 °C for 126 d. Lipid oxidation indicators: peroxide value (PV), conjugated dienes (CD), volatile compounds (hexanal and nonanal), and sensory attributes were determined for the stored samples. Samples showed small but significant increases in PV, CD, hexanal and nonanal contents, and intensity ratings of negative sensory attributes (oxidized and cardboard). C had the highest tendency to deterioration during storage. At the end of storage (126 d), C had the highest PV (3.90 meqO2 /kg), and BHT had the lowest PV (2.00 meqO2 /kg). CMC and E samples had similar intermediate PV values (2.69 and 2.57 meqO2 /kg, respectively). CMC coating and the addition of natural (peanut skin extract) and synthetic (BHT) antioxidants provide protection to the roasted almond product. © 2015 Institute of Food Technologists®

  3. Cyclic catalytic upgrading of chemical species using metal oxide materials

    DOEpatents

    White, James H; Schutte, Erick J; Rolfe, Sara L

    2013-05-07

    Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having the following formulas: (a) Ce.sub.xB.sub.yB'.sub.zB''O.sub..delta., wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, and/or Fe; B''=Cu; 0.01metal oxides.

  4. Cyclic Catalytic Upgrading of Chemical Species Using Metal Oxide Materials

    NASA Technical Reports Server (NTRS)

    White, James H. (Inventor); Schutte, Erick J. (Inventor); Rolfe, Sara L. (Inventor)

    2013-01-01

    Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having the following formulas: (a) Ce(sub x)B(sub y)B'(sub z)B''O(sub gamma; wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, and/or Fe; B''=Cu; 0.01metal oxides.

  5. Vitrified metal finishing wastes I. Composition, density and chemical durability.

    PubMed

    Bingham, P A; Hand, R J

    2005-03-17

    Durable phosphate glasses were formed by vitrifying waste filter cakes from two metal finishing operations. Some melts formed crystalline components during cooling. Compositional analysis of dried, heat treated and vitrified samples was made using energy-dispersive X-ray spectroscopy, X-ray fluorescence spectroscopy, inductively-coupled plasma spectroscopy and Leco induction furnace combustion analysis. Hydrolytic dissolution, measured by an adapted product consistency test, was reduced by up to 3 orders of magnitude upon heat treatment or vitrification, surpassing the performance of borosilicate glass in some cases. This was attributed to the high levels of iron and zinc in the wastes, which greatly improve the durability of phosphate glasses. One of the wastes arose from a metal phosphating process and was particularly suitable for vitrification due to its high P2O5 content and favourable melting behaviour. The other waste, which arose from a number of processes, was less suitable as it had a low P2O5 content and during heating it emitted harmful corrosive gases and underwent violent reactions. Substantial volume reductions were obtained by heat treatment and vitrification of both wastes. Compositions and performances of some vitrified wastes were comparable with those of glasses which are under consideration for the immobilisation of toxic and nuclear wastes.

  6. Chemical bonding of hydrogen molecules to transition metal complexes

    SciTech Connect

    Kubas, G.J.

    1990-01-01

    The complex W(CO){sub 3}(PR{sub 3}){sub 2}(H{sub 2}) (CO = carbonyl; PR{sub 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{sub 2} exchanges easily with D{sub 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{sub 2} bonding electron pair to a vacant metal d-orbital. A series of complexes of molybdenum of the type Mo(CO)(H{sub 2})(R{sub 2}PCH{sub 2}CH{sub 2}PR{sub 2}){sub 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.

  7. A new route toward ultrasensitive, flexible chemical sensors: metal nanotubes by wet-chemical synthesis along sacrificial nanowire templates.

    PubMed

    Lim, Mi Ae; Kim, Dong Hwan; Park, Chong-Ook; Lee, Young Wook; Han, Sang Woo; Li, Zhiyong; Williams, R Stan; Park, Inkyu

    2012-01-24

    We developed a novel low-temperature, wet-chemical process for the facile synthesis of metal nanotube arrays through the reduction of metal precursors along sacrificial metal oxide nanowire templates and demonstrated its applications to the ultrasensitive, low-power, mechanically robust, and flexible chemical sensors. The in situ dissolution of ZnO nanowire templates, which were hydrothermally grown on electrode surfaces, during the reaction allows the direct formation of tubular Pd nanostructures on the sensor devices without the need of complex processes for device integration or template removal. Moreover, this simple synthesis was carried out at low-temperature with mild chemical conditions; therefore we could make Pd nanotube devices not only on silicon substrates but also on flexible polymer substrates. The H(2) sensing of such Pd nanotube devices was investigated under various mechanical loading and showed excellent reliability and robustness. The sensitivity of our devices was found to be at least 2 orders of magnitude higher than literature values for H(2) sensors, which can be attributed to the high surface area and the well-formed interconnect of Pd tubular nanostructures in our devices.

  8. Using additive modelling to quantify the effect of chemicals on phytoplankton diversity and biomass.

    PubMed

    Viaene, K P J; De Laender, F; Van den Brink, P J; Janssen, C R

    2013-04-01

    Environmental authorities require the protection of biodiversity and other ecosystem properties such as biomass production. However, the endpoints listed in available ecotoxicological datasets generally do not contain these two ecosystem descriptors. Inferring the effects of chemicals on such descriptors from micro- or mesocosm experiments is often hampered by inherent differences in the initial biodiversity levels between experimental units or by delayed community responses. Here we introduce additive modelling to establish the effects of a chronic application of the herbicide linuron on 10 biodiversity indices and phytoplankton biomass in microcosms. We found that communities with a low (high) initial biodiversity subsequently became more (less) diverse, indicating an equilibrium biodiversity status in the communities considered here. Linuron adversely affected richness and evenness while dominance increased but no biodiversity indices were different from the control treatment at linuron concentrations below 2.4 μg/L. Richness-related indices changed at lower linuron concentrations (effects noticeable from 2.4 μg/L) than other biodiversity indices (effects noticeable from 14.4 μg/L) and, in contrast to the other indices, showed no signs of recovery following chronic exposure. Phytoplankton biomass was unaffected by linuron due to functional redundancy within the phytoplankton community. Comparing thresholds for biodiversity with conventional toxicity test results showed that standard ecological risk assessments also protect biodiversity in the case of linuron.

  9. Pilot scale cooling tower fouled fill treatment: AFCATT (Anti-Fouling Chemical Additive Test Tower)

    SciTech Connect

    Newton, M.T.; Noble, R.T.; Philpot, E.F.; Eastis, J.H.

    1995-02-01

    Polyvinylchloride (PVC) film-type cellular fill is the fill of choice in replacing cement asbestor board fill in existing cooling towers and in new cooling towers because of its high thermal performance, ease of installation, and low initial cost. However, PVC fill has been found to foul quickly with biological and sediment material, significant reducing tower performance and the fill`s useful life. The Anti-Fouling Chemical Additives Test Tower (AFCATT) has been built to study accumulation rates of fouling deposits in corrugated PVC film fill and to study methods of cleaning and preventing the fouling deposits. This small mechanical draft cooling tower is located next to the Unit 4 natural draft cooling tower at Georgia Power Company`s Plant Bowen. The once-through mechanical draft tower receives hot water from the condenser and returns the cold water to the basin of the host tower. The pilot tower is divided into four chambers allowing for three different treatment programs and one control to be run simultaneously. PVC fill packs are suspended from load cells to allow the weight of the fill packs to be measured continuously. Six vendors participated in the summer 1993 test program. Each proposed different methods of cleaning the fouled fill and were given the opportunity to try their proposed method of fill cleaning. The success of each treatment program was determined by its ability to reduce fill pack weight (i.e., reduce fouling).

  10. Chemical Reactions of Metal-Metal Bonded Compounds of the Transition Elements.

    DTIC Science & Technology

    1981-05-18

    in the compounds formed by reaction 23 can be used to prepare triangulo -metal complexes with capping i3-CR ligands as is schematically shown in 24. R...8 and Rh2(G-CO)2(C 5- Me5 )2 with the alkylidene compound p-tolyl-C=W(CO) 2Cp. They obtained the alkylidine capped triangulo compounds (XIX) and (XX...are triangulo Lompounds of the type noted in Table 1.2. 2.4. By Reduction of Mononuclear Metal Halides For transition metals with odd numbers of

  11. Enhancing current-induced torques by abutting additional spin polarizer layer to nonmagnetic metal layer.

    PubMed

    Go, Gyungchoon; Lee, Kyung-Jin; Kim, Young Keun

    2017-04-04

    Recently, the switching of a perpendicularly magnetized ferromagnet (FM) by injecting an in-plane current into an attached non-magnet (NM) has become of emerging technological interest. This magnetization switching is attributed to the spin-orbit torque (SOT) originating from the strong spin-orbit coupling of the NM layer. However, the switching efficiency of the NM/FM structure itself may be insufficient for practical use, as for example, in spin transfer torque (STT)-based magnetic random access memory (MRAM) devices. Here we investigate spin torque in an NM/FM structure with an additional spin polarizer (SP) layer abutted to the NM layer. In addition to the SOT contribution, a spin-polarized current from the SP layer creates an extra spin chemical potential difference at the NM/FM interface and gives rise to a STT on the FM layer. We show that, using typical parameters including device width, thickness, spin diffusion length, and the spin Hall angle, the spin torque from the SP layer can be much larger than that from the spin Hall effect (SHE) of the NM.

  12. Enhancing current-induced torques by abutting additional spin polarizer layer to nonmagnetic metal layer

    PubMed Central

    Go, Gyungchoon; Lee, Kyung-Jin; Kim, Young Keun

    2017-01-01

    Recently, the switching of a perpendicularly magnetized ferromagnet (FM) by injecting an in-plane current into an attached non-magnet (NM) has become of emerging technological interest. This magnetization switching is attributed to the spin-orbit torque (SOT) originating from the strong spin-orbit coupling of the NM layer. However, the switching efficiency of the NM/FM structure itself may be insufficient for practical use, as for example, in spin transfer torque (STT)-based magnetic random access memory (MRAM) devices. Here we investigate spin torque in an NM/FM structure with an additional spin polarizer (SP) layer abutted to the NM layer. In addition to the SOT contribution, a spin-polarized current from the SP layer creates an extra spin chemical potential difference at the NM/FM interface and gives rise to a STT on the FM layer. We show that, using typical parameters including device width, thickness, spin diffusion length, and the spin Hall angle, the spin torque from the SP layer can be much larger than that from the spin Hall effect (SHE) of the NM. PMID:28374805

  13. Enhancing current-induced torques by abutting additional spin polarizer layer to nonmagnetic metal layer

    NASA Astrophysics Data System (ADS)

    Go, Gyungchoon; Lee, Kyung-Jin; Kim, Young Keun

    2017-04-01

    Recently, the switching of a perpendicularly magnetized ferromagnet (FM) by injecting an in-plane current into an attached non-magnet (NM) has become of emerging technological interest. This magnetization switching is attributed to the spin-orbit torque (SOT) originating from the strong spin-orbit coupling of the NM layer. However, the switching efficiency of the NM/FM structure itself may be insufficient for practical use, as for example, in spin transfer torque (STT)-based magnetic random access memory (MRAM) devices. Here we investigate spin torque in an NM/FM structure with an additional spin polarizer (SP) layer abutted to the NM layer. In addition to the SOT contribution, a spin-polarized current from the SP layer creates an extra spin chemical potential difference at the NM/FM interface and gives rise to a STT on the FM layer. We show that, using typical parameters including device width, thickness, spin diffusion length, and the spin Hall angle, the spin torque from the SP layer can be much larger than that from the spin Hall effect (SHE) of the NM.

  14. Fabrication of a single metal nanowire connected with dissimilar metal electrodes and its application to chemical sensing.

    PubMed

    Lin, Hsin-Yu; Chen, Hsiang-An; Lin, Heh-Nan

    2008-03-15

    We report a convenient method for the fabrication of a single metal nanowire connected with dissimilar metal electrodes and its application to chemical sensing. The method is based on a combination of atomic force microscopy nanomachining and conventional photolithography. The success of this integrated approach is confirmed by the linear current-voltage behavior of the created nanowires and comparable resistivities with those reported previously. The chemical sensing capability is demonstrated by the selective binding of a self-assembled monolayer onto a single Au nanowire connected with Ti electrodes and the subsequent resistance increase due to increased surface scattering effects after adsorption. It is found that the resistance increases by around 9% after the complete coverage of either octadecanethiol or dodecanethiol molecules onto a 20 nm thick Au nanowire. A theoretical explanation for the relationship between the resistance increase and the alkanethiol concentration is also given.

  15. TOPICAL REVIEW: Determination of oxygen content and metal valences in oxide superconductors by chemical methods

    NASA Astrophysics Data System (ADS)

    Karppinen, M.; Fukuoka, A.; Niinistö, L.; Yamauchi, H.

    1996-03-01

    Several methods of chemical analysis, for example various redox titrations and thermogravimetric approaches, have been adapted to establish the oxygen content in superconducting cuprates and to determine the higher oxidation states of copper and other mixed-valent metals. The present review discusses and complements the authors' own experimental results on the oxygen content and metal valence analyses, but literature data from about 150 other references are reviewed as well.

  16. High index of refraction films for dielectric mirrors prepared by metal-organic chemical vapor deposition

    SciTech Connect

    Brusasco, R.M.

    1989-01-01

    A wide variety of metal oxides with high index of refraction can be prepared by Metal-Organic Chemical Vapor Deposition. We present some recent optical and laser damage results on oxide films prepared by MOCVD which could be used in a multilayer structure for highly reflecting (HR) dielectric mirror applications. The method of preparation affects both optical properties and laser damage threshold. 10 refs., 8 figs., 4 tabs.

  17. Asymmetric Michael addition of ketones to alkylidene malonates and allylidene malonates via enamine-metal Lewis acid bifunctional catalysis.

    PubMed

    Liu, Lu; Sarkisian, Ryan; Xu, Zhenghu; Wang, Hong

    2012-09-07

    Novel enamine-metal Lewis acid bifunctional catalysts were successfully applied to the asymmetric Michael addition of ketones to alkylidene malonates, offering excellent stereoselectivity (up to >99% ee and >99:1 dr). The asymmetric Michael addition of ketones to allylidene malonates was also achieved.

  18. Transition-Metal-Catalyzed C-H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds.

    PubMed

    Hummel, Joshua R; Boerth, Jeffrey A; Ellman, Jonathan A

    2016-12-12

    The transition-metal-catalyzed addition of C-H bonds to carbonyls, imines, and related polarized π bonds has emerged as a particularly efficient and powerful approach for the construction of an incredibly diverse array of heteroatom-substituted products. Readily available and stable inputs are typically employed, and reactions often proceed with very high functional group compatibility and without the production of waste byproducts. Additionally, many transition-metal-catalyzed C-H bond additions to polarized π bonds occur within cascade reaction sequences to provide rapid access to a diverse array of different heterocyclic as well as carbocyclic products. This review highlights the diversity of transformations that have been achieved, catalysts that have been used, and types of products that have been prepared through the transition-metal-catalyzed addition of C-H bonds to carbonyls, imines, and related polarized π bonds.

  19. As-cast uranium-molybdenum based metallic fuel candidates and the effects of carbon addition

    NASA Astrophysics Data System (ADS)

    Blackwood, Van Stephen

    The objective of this research was to develop and recommend a metallic nuclear fuel candidate that lowered the onset temperature of gamma phase formation comparable or better than the uranium-10 wt. pct. molybdenum alloy, offered a solidus temperature as high or higher than uranium-10 wt. pct. zirconium (1250°C), and stabilized the fuel phase against interaction with iron and steel at least as much as uranium-10 wt. pct. zirconium stabilized the fuel phase. Two new as-cast alloy compositions were characterized to assess thermal equilibrium boundaries of the gamma phase field and the effect of carbon addition up to 0.22 wt. pct. The first system investigated was uranium- x wt. pct. M where x ranged between 5-20 wt. pct. M was held at a constant ratio of 50 wt. pct. molybdenum, 43 wt. pct. titanium, and 7 wt. pct. zirconium. The second system investigated was the uranium-molybdenum-tungsten system in the range 90 wt. pct. uranium - 10 wt. pct. molybdenum - 0 wt. pct. tungsten to 80 wt. pct. uranium - 10 wt. pct. molybdenum - 10 wt. pct. tungsten. The results showed that the solidus temperature increased with increased addition of M up to 12.5 wt. pct. for the uranium-M system. Alloy additions of titanium and zirconium were removed from uranium-molybdenum solid solution by carbide formation and segregation. The uranium-molybdenum-tungsten system solidus temperature increased to 1218°C at 2.5 wt. pct. with no significant change in temperature up to 5 wt. pct. tungsten suggesting the solubility limit of tungsten had been reached. Carbides were observed with surrounding areas enriched in both molybdenum and tungsten. The peak solidus temperatures for the alloy systems were roughly the same at 1226°C for the uranium-M system and 1218°C for the uranium-molybdenum-tungsten system. The uranium-molybdenum-tungsten system required less alloy addition to achieve similar solidus temperatures as the uranium-M system.

  20. Origin of additional capacities in metal oxide lithium-ion battery electrodes.

    PubMed

    Hu, Yan-Yan; Liu, Zigeng; Nam, Kyung-Wan; Borkiewicz, Olaf J; Cheng, Jun; Hua, Xiao; Dunstan, Matthew T; Yu, Xiqian; Wiaderek, Kamila M; Du, Lin-Shu; Chapman, Karena W; Chupas, Peter J; Yang, Xiao-Qing; Grey, Clare P

    2013-12-01

    Metal fluorides/oxides (MF(x)/M(x)O(y)) are promising electrodes for lithium-ion batteries that operate through conversion reactions. These reactions are associated with much higher energy densities than intercalation reactions. The fluorides/oxides also exhibit additional reversible capacity beyond their theoretical capacity through mechanisms that are still poorly understood, in part owing to the difficulty in characterizing structure at the nanoscale, particularly at buried interfaces. This study employs high-resolution multinuclear/multidimensional solid-state NMR techniques, with in situ synchrotron-based techniques, to study the prototype conversion material RuO2. The experiments, together with theoretical calculations, show that a major contribution to the extra capacity in this system is due to the generation of LiOH and its subsequent reversible reaction with Li to form Li2O and LiH. The research demonstrates a protocol for studying the structure and spatial proximities of nanostructures formed in this system, including the amorphous solid electrolyte interphase that grows on battery electrodes.

  1. Evaluation of laser ultrasonic testing for inspection of metal additive manufacturing

    NASA Astrophysics Data System (ADS)

    Everton, Sarah; Dickens, Phill; Tuck, Chris; Dutton, Ben

    2015-03-01

    Additive Manufacturing (AM) offers a number of benefits over conventional processes. However, in order for these benefits to be realised, further development and integration of suitable monitoring and closed loop control systems are needed. Laser Ultrasonic Testing (LUT) is an inspection technology which shows potential for in-situ monitoring of metallic AM processes. Non-contact measurements can be performed on curved surfaces and in difficult to reach areas, even at elevated temperatures. Interrogation of each build layer generates defect information which can be used to highlight processing errors and allow for real-time modification of processing parameters, enabling improved component quality and yield. This study evaluates the use of laser-generated surface waves to detect artificially generated defects in titanium alloy (Ti- 6Al-4V) samples produced by laser-based Powder Bed Fusion. The trials undertaken utilise the latest LUT equipment, recently installed at Manufacturing Technology Centre which is capable of being controlled remotely. This will allow the system to optimise or adapt "on-the-fly", simplifying the eventual integration of the system within an AM machine.

  2. Extremely strong organic-metal oxide electronic coupling caused by nucleophilic addition reaction.

    PubMed

    Fujisawa, Jun-ichi; Hanaya, Minoru

    2015-07-07

    Electronic interactions between organic materials and inorganic semiconductors play important roles in various electronic and optoelectronic functions and also provide new functions such as optical interfacial charge-transfer (ICT) transitions having the following features. ICT transitions enable the capture of lower-energy photons than HOMO-LUMO gaps or band gaps and allow one-step charge separation without loss of energy. The hybrid material generated by the nucleophilic addition reaction between TiO2 and TCNQ exclusively exhibits strong ICT transitions. In this study, we report that strong organic-metal oxide electronic coupling is caused by the nucleophilic addition reaction, which enhances the ICT transitions. The electronic coupling between TiO2 and TCNQ occurs according to a two-step mechanism. First, the lowest unoccupied molecular orbital (LUMO (π*)) of TCNQ is elevated by the nucleophilic attack of a deprotonated hydroxy group on TiO2 to TCNQ and the electron distribution is moved toward TiO2. By this elevation and redistribution, the LUMO (π*) strongly interacts with the d(t2g) orbitals of a surface Ti atom. From avoided-crossing behavior with a large splitting energy of ca. 0.95 eV, the coupling energy was estimated to be as much as 0.5 eV in the mono-Ti model complex. This strong d-π* electronic coupling leads to strong coupling between complete ICT excited states and partial ICT excited states with a large splitting energy of ca. 0.92 eV, which considerably increases the probabilities of ICT transition. This study clarified the mechanisms of the strong organic-inorganic electronic coupling and the enhancement of ICT absorption in the TiO2-TCNQ hybrid material.

  3. A multi-metal risk assessment strategy for natural freshwater ecosystems based on the additive inhibitory free metal ion concentration index.

    PubMed

    Alves, Cristina M; Ferreira, Carlos M H; Soares, Eduardo V; Soares, Helena M V M

    2017-04-01

    Scientifically sound risk assessment strategies and derivations of environmental quality standards for metals present in freshwater environments are currently hampered by insufficient chronic toxicity data collected from natural ecosystems, as well as inadequate information on metal speciation. Thus, the aim of the present study was to evaluate the impact of freshwater containing multiple metals (Cd, Cr, Cu, Ni, Pb and Zn) on the chronic toxicity (72h) to the alga Pseudokirchneriella subcapitata and compare the observed toxicity results to the total and free metal concentration of the samples. Based on the information obtained herein, an additive inhibitory free multi-metal ion concentration index, calculated as the sum of the equivalent toxicities to the free metal ion concentration of each sample, was developed. The proposed index was well correlated to the observed chronic toxicity results, indicating that the concentration addition, when expressed as the free-ion activity, can be considered a reliable indicator for the evaluation of ecological risk assessments for natural waters containing multiple metals. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Application of physical and chemical characterization techniques to metallic powders

    SciTech Connect

    Slotwinski, J. A.; Watson, S. S.; Stutzman, P. E.; Ferraris, C. F.; Peltz, M. A.; Garboczi, E. J.

    2014-02-18

    Systematic studies have been carried out on two different powder materials used for additive manufacturing: stainless steel and cobalt-chrome. The characterization of these powders is important in NIST efforts to develop appropriate measurements and standards for additive materials and to document the property of powders used in a NIST-led additive manufacturing material round robin. An extensive array of characterization techniques was applied to these two powders, in both virgin and recycled states. The physical techniques included laser diffraction particle size analysis, X-ray computed tomography for size and shape analysis, and optical and scanning electron microscopy. Techniques sensitive to chemistry, including X-ray diffraction and energy dispersive analytical X-ray analysis using the X-rays generated during scanning electron microscopy, were also employed. Results of these analyses will be used to shed light on the question: how does virgin powder change after being exposed to and recycled from one or more additive manufacturing build cycles? In addition, these findings can give insight into the actual additive manufacturing process.

  5. Improvement of an integrated system of membrane bioreactor and worm reactor by phosphorus removal using additional post-chemical treatment.

    PubMed

    Liu, Jia; Zuo, Wei; Tian, Yu; Zhang, Jun; Li, Hui; Li, Lipin

    2016-11-01

    A membrane bioreactor (MBR) coupled with a worm reactor (SSBWR) was designed as SSBWR-MBR for sewage treatment and excess sludge reduction. However, total phosphorus (TP) release caused by worm predation in the SSBWR could increase the effluent TP concentration in the SSBWR-MBR. To decrease the amount of TP excreted, chemical treatment reactor was connected after the SSBWR-MBR to remove the excess phosphorus (P). The effects of chemical treatment at different time intervals on the performance of the SSBWR-MBR were assessed. The results showed that a maximum TP removal efficiency of 21.5 ± 1.0% was achieved in the SSBWR-MBR after chemical treatment. More importantly, a higher sulfate concentration induced by chemical treatment could promote TP release in the SSBWR, which provided further TP removal from the SSBWR-MBR. Additionally, chemical oxygen demand (COD) removal efficiency of the SSBWR-MBR was increased by 1.3% after effective chemical treatment. In the SSBWR-MBR, the chemical treatment had little effects on NH3-N removal and sludge production. Eventually, chemical treatment also alleviated the membrane fouling in the SSBWR-MBR. In this work, the improvement on TP, COD removal and membrane fouling alleviation was achieved in the SSBWR-MBR using additional chemical treatment.

  6. An experimental study of steam explosions involving chemically reactive metal

    SciTech Connect

    Cho, D.H.; Armstrong, D.R.; Gunther, W.H.; Basu, S.

    1997-07-01

    An experimental study of molten zirconium-water explosions was conducted. A 1-kg mass of zirconium melt was dropped into a column of water. Explosions took place only when an external trigger was used. In the triggered tests, the extent of oxidation of the zirconium melt was very extensive. However, the explosion energetics estimated were found to be very small compared to the potential chemical energy available from the oxidation reaction. Zirconium is of particular interest, since it is a component of the core materials of the current nuclear power reactors. This paper describes the test apparatus and summarizes the results of four tests conducted using pure zirconium melt.

  7. Carbon-13 chemical shifts in solid metal sandwich compounds

    SciTech Connect

    Wemmer, D. E.; Pines, A.

    1981-01-01

    Chemical shielding parameters are reported, here in this paper, for the metallocenes of Fe, Ru, Mg, bis(cyclopentadionyl) complexes Cp2TiCl2, (CpMe5)2CoCl, and (CpMe5)2Fe and bis(benzene)chromium. The shielding tensor anisotropy seems to reflect the character of bonding. Also, motion detected in many of these compounds and has been used in some cases to assign the shielding tensor principle directions.

  8. 77 FR 71561 - Health and Safety Data Reporting; Addition of Certain Chemicals

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-12-03

    ... organic dyes and pigments, gum and wood chemicals, cyclic crudes and intermediates, and ethyl alcohol... Executive Order 13175, entitled ``Consultation and Coordination With Indian Tribal Governments'' (65...

  9. The Application of Metal Oxide Nanomaterials for Chemical Sensor Development

    NASA Technical Reports Server (NTRS)

    Xu, Jennifer C.; Hunter, Gary W.; Evans, Laura J.; VanderWal, Randy L.; Berger, Gordon M.

    2007-01-01

    NASA Glenn Research Center (GRC) has been developing miniature chemical sensors for a variety of applications including fire detection, emissions monitoring, fuel leak detection, and environmental monitoring. Smart Lick and Stick sensor technology which integrates a sensor array, electronics, telemetry, and power into one microsystem are being developed. These microsystems require low power consumption for long-term aerospace applications. One approach to decreasing power consumption is the use of nanotechnology. Nanocrystalline tin oxide (SnO2) carbon monoxide (CO) sensors developed previously by this group have been successfully used for fire detection and emissions monitoring. This presentation will briefly review the overall NASA GRC chemical sensor program and discuss our further effort in nanotechnology applications. New carbon dioxide (CO2) sensing material using doped nanocrystalline SnO2 will be discussed. Nanocrystalline SnO2 coated solid electrolyte CO2 sensors and SnO2 nanorod and nanofiber hydrogen (H2) sensors operated at reduced or room temperatures will also be discussed.

  10. Nonspherical noble metal nanoparticles: colloid-chemical synthesis and morphology control.

    PubMed

    Sau, Tapan K; Rogach, Andrey L

    2010-04-22

    Metal nanoparticles have been the subject of widespread research over the past two decades. In recent years, noble metals have been the focus of numerous studies involving synthesis, characterization, and applications. Synthesis of an impressive range of noble metal nanoparticles with varied morphologies has been reported. Researchers have made a great progress in learning how to engineer materials on a nanometer length scale that has led to the understanding of the fundamental size- and shape-dependent properties of matter and to devising of new applications. In this article, we review the recent progress in the colloid-chemical synthesis of nonspherical nanoparticles of a few important noble metals (mainly Ag, Au, Pd, and Pt), highlighting the factors that influence the particle morphology and discussing the mechanisms behind the nonspherical shape evolution. The article attempts to present a thorough discussion of the basic principles as well as state-of-the-art morphology control in noble metal nanoparticles.

  11. GaN nanowire arrays by a patterned metal-assisted chemical etching

    NASA Astrophysics Data System (ADS)

    Wang, K. C.; Yuan, G. D.; Wu, R. W.; Lu, H. X.; Liu, Z. Q.; Wei, T. B.; Wang, J. X.; Li, J. M.; Zhang, W. J.

    2016-04-01

    We developed an one-step and two-step metal-assisted chemical etching method to produce self-organized GaN nanowire arrays. In one-step approach, GaN nanowire arrays are synthesized uniformly on GaN thin film surface. However, in a two-step etching processes, GaN nanowires are formed only in metal uncovered regions, and GaN regions with metal-covering show nano-porous sidewalls. We propose that nanowires and porous nanostructures are tuned by sufficient and limited etch rate, respectively. PL spectra shows a red-shift of band edge emission in GaN nanostructures. The formation mechanism of nanowires was illustrated by two separated electrochemical reactions occur simultaneously. The function of metals and UV light was illustrated by the scheme of potential relationship between energy bands in Si, GaN and standard hydrogen electrode potential of solution and metals.

  12. Bilayer-metal assisted chemical etching of silicon microwire arrays for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Wu, R. W.; Yuan, G. D.; Wang, K. C.; Wei, T. B.; Liu, Z. Q.; Wang, G. H.; Wang, J. X.; Li, J. M.

    2016-02-01

    Silicon microwires with lateral dimension from 5 μm to 20 μm and depth as long as 20 μm are prepared by bilayer metal assisted chemical etching (MaCE). A bilayer metal configuration (Metal 1 / Metal 2) was applied to assist etching of Si where metal 1 acts as direct catalyst and metal 2 provides mechanical support. Different metal types were investigated to figure out the influence of metal catalyst on morphology of etched silicon. We find that silicon microwires with vertical side wall are produced when we use Ag/Au bilayer, while cone-like and porous microwires formed when Pt/Au is applied. The different micro-/nano-structures in as-etched silicon are demonstrated to be due to the discrepancy of work function of metal catalyst relative to Si. Further, we constructed a silicon microwire arrays solar cells in a radial p-n junction configurations in a screen printed aluminum paste p-doping process.

  13. Metallic sulfide additives for positive electrode material within a secondary electrochemical cell

    DOEpatents

    Walsh, William J.; McPheeters, Charles C.; Yao, Neng-ping; Koura, Kobuyuki

    1976-01-01

    An improved active material for use within the positive electrode of a secondary electrochemical cell includes a mixture of iron disulfide and a sulfide of a polyvalent metal. Various metal sulfides, particularly sulfides of cobalt, nickel, copper, cerium and manganese, are added in minor weight proportion in respect to iron disulfide for improving the electrode performance and reducing current collector requirements.

  14. Students' Predictions about the Sensory Properties of Chemical Compounds: Additive versus Emergent Frameworks

    ERIC Educational Resources Information Center

    Talanquer, Vicente

    2008-01-01

    We investigated general chemistry students' intuitive ideas about the expected properties of the products of a chemical reaction. In particular, we analyzed college chemistry students' predictions about the color, smell, and taste of the products of chemical reactions represented at the molecular level. The study was designed to explore the extent…

  15. Students' Predictions about the Sensory Properties of Chemical Compounds: Additive versus Emergent Frameworks

    ERIC Educational Resources Information Center

    Talanquer, Vicente

    2008-01-01

    We investigated general chemistry students' intuitive ideas about the expected properties of the products of a chemical reaction. In particular, we analyzed college chemistry students' predictions about the color, smell, and taste of the products of chemical reactions represented at the molecular level. The study was designed to explore the extent…

  16. Teachers' Misconceptions about the Effects of Addition of More Reactants or Products on Chemical Equilibrium

    ERIC Educational Resources Information Center

    Cheung, Derek; Ma, Hong-jia; Yang, Jie

    2009-01-01

    The importance of research on misconceptions about chemical equilibrium is well recognized by educators, but in the past, researchers' interest has centered on student misconceptions and has neglected teacher misconceptions. Focusing on the effects of adding more reactants or products on chemical equilibrium, this article discusses the various…

  17. Teachers' Misconceptions about the Effects of Addition of More Reactants or Products on Chemical Equilibrium

    ERIC Educational Resources Information Center

    Cheung, Derek; Ma, Hong-jia; Yang, Jie

    2009-01-01

    The importance of research on misconceptions about chemical equilibrium is well recognized by educators, but in the past, researchers' interest has centered on student misconceptions and has neglected teacher misconceptions. Focusing on the effects of adding more reactants or products on chemical equilibrium, this article discusses the various…

  18. Determination of the Pb, Cr, and Cd distribution patterns with various chlorine additives in the bottom ashes of a low-temperature two-stage fluidized bed incinerator by chemical sequential extraction.

    PubMed

    Peng, Tzu-Huan; Lin, Chiou-Liang; Wey, Ming-Yen

    2015-09-15

    A novel low-temperature two-stage fluidized bed (LTTSFB) incinerator has been successfully developed to control heavy-metal emissions during municipal solid waste (MSW) treatment. However, the characteristics of the residual metal patterns during this process are still unclear. The aim of this study was to investigate the metal patterns in the different partitions of the LTTSFB bottom ash by chemical sequential extraction. Artificial waste was used to simulate the MSW. Different parameters including the first-stage temperature, chloride additives, and operating gas velocity were also considered. Results indicated that during the low-temperature treatment process, a high metal mobility phase exists in the first-stage sand bed. The main patterns of Cd, Pb, and Cr observed were the water-soluble, exchangeable, and residual forms, respectively. With the different Cl additives, the results showed that polyvinyl chloride addition increased metal mobility in the LTTSFB bottom ash, while, sodium chloride addition may have reduced metal mobility due to the formation of eutectic material. The second-stage sand bed was found to have a lower risk of metal leaching. The results also suggested that, the residual ashes produced by the LTTSFB system must be taken into consideration given their high metal mobility.

  19. A Four-Step and Four-Criteria Approach for Evaluating Evidence of Dose Addition in Chemical Mixture Toxicity

    EPA Science Inventory

    Dose addition is the most frequently-used component-based approach for predicting dose response for a mixture of toxicologically-similar chemicals and for statistical evaluation of whether the mixture response is consistent with dose additivity and therefore predictable from the ...

  20. A Four-Step and Four-Criteria Approach for Evaluating Evidence of Dose Addition in Chemical Mixture Toxicity

    EPA Science Inventory

    Dose addition is the most frequently-used component-based approach for predicting dose response for a mixture of toxicologically-similar chemicals and for statistical evaluation of whether the mixture response is consistent with dose additivity and therefore predictable from the ...

  1. Catalyst accessibility to chemical reductants in metal-organic frameworks.

    PubMed

    Roy, Souvik; Pascanu, Vlad; Pullen, Sonja; González Miera, Greco; Martín-Matute, Belén; Ott, Sascha

    2017-03-18

    A molecular H2-evolving catalyst, [Fe2(cbdt)(CO)6] ([FeFe], cbdt = 3-carboxybenzene-1,2-dithiolate), has been attached covalently to an amino-functionalized MIL-101(Cr) through an amide bond. Chemical reduction experiments reveal that the MOF channels can be clogged by ion pairs that are formed between the oxidized reductant and the reduced catalyst. This effect is lessened in MIL-101-NH-[FeFe] with lower [FeFe] loadings. On longer timescales, it is shown that large proportions of the [FeFe] catalysts within the MOF engage in photochemical hydrogen production and the amount of produced hydrogen is proportional to the catalyst loading.

  2. Refractive index chemical sensing with noble metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Blake, Phillip

    Chemical sensing is a key component in modern society, especially in engineering applications. Because of their widespread impact, improvements to chemical sensors are a significant area of research. One class of sensors, plasmonic sensors, is being heavily researched because of their ability to detect low levels of analyte in near real time without destroying the analyte. This work studies a new class of plasmonic sensor that utilizes diffractive coupling to improve sensor performance. Specifically, this work outlines the first study of diffractive coupling sensors with typical nanoparticle shapes. Sensitivity of this new class of sensor is directly compared to typical localized surface plasmon resonance sensors. Spectral peak location sensitivity was found to be equal to or greater than typical plasmonic sensors. These results were corroborated with numerical simulation with and without nanoparticle interaction to demonstrate the power of harnessing diffractive coupling in nanoparticle sensors. The sensing results were then extended to analyze ordered arrays of nanorings. Nanorings were chosen because they have the highest reported sensitivity of any plasmonic shape (880 nm/RIU) in the literature and have a high surface area to volume ratio, which is a key parameter for plasmonic sensors. Theoretical simulations of diffractive coupling nanorings indicate that sensitivity is comparable to non-coupling nanorings in the literature (890 nm/RIU vs. 880 nm/RIU, respectively). Another metric of sensor performance, the figure of merit, was much higher (34) than the non-coupling ring (2). Ordered nanoring arrays which exhibit diffractive coupling improve upon current refractive index based plasmonic sensors. Further improvements to nanoring sensors' figure of merit are possible based on simulation results for nanosphere arrays.

  3. Chemical and Physical Reactions of Wellbore Cement under CO2 Storage Conditions: Effects of Cement Additives

    NASA Astrophysics Data System (ADS)

    Kutchko, B. G.; Strazisar, B. R.; Huerta, N.; Lowry, G. V.; Dzombak, D. A.; Thaulow, N.

    2008-12-01

    Sequestration of CO2 into geologic formations requires long-term storage and low leakage rates to be effective. Active and abandoned wells in candidate storage formations must be evaluated as potential leakage points. Wellbore integrity is an important part of an overall integrated assessment program being developed at NETL to assess potential risks at CO2 storage sites. Such a program is needed for ongoing policy and regulatory decisions for geologic carbon sequestration. The permeability and integrity of the cement in the well is a primary factor affecting its ability to prevent leakage. Cement must be able to maintain low permeability over lengthy exposure to reservoir conditions in a CO2 injection and storage scenario. Although it is known that cement may be altered by exposure to CO2, the results of ongoing research indicate that cement curing conditions, fluid properties, and cement additives play a significant role in the rate of alteration and reaction. The objective of this study is to improve understanding of the factors affecting wellbore cement integrity for large-scale geologic carbon sequestration projects. Due to the high frequency use of additives (pozzolan) in wellbore cement, it is also essential to understand the reaction of these cement-pozzolan systems upon exposure to CO2 under sequestration conditions (15.5 MPa and 50°C). Laboratory experiments were performed to determine the physical and chemical changes, as well as the rate of alteration of commonly used pozzolan-cement systems under simulated sequestration reservoir conditions, including both supercritical CO2 and CO2-saturated brine. The rate of alteration of the cement-pozzolan systems is considerably faster than with neat cement. However, the alteration of physical properties is much less significant with the pozzolanic blends. Permeability of a carbonated pozzolanic cement paste remains sufficiently small to block significant vertical migration of CO2 in a wellbore. All of the

  4. Dihydrogen addition in a dinuclear rare-earth metal hydride complex supported by a metalated TREN ligand.

    PubMed

    Venugopal, Ajay; Fegler, Waldemar; Spaniol, Thomas P; Maron, Laurent; Okuda, Jun

    2011-11-09

    The dinuclear lutetium dihydride dication supported by metalated tripodal ligands undergoes facile hydrogenolysis with H(2) to form a trihydride dication. Molecular orbital analysis shows that the LUMO is a bonding Lu···Lu orbital that is poised to activate dihydrogen.

  5. Biological and chemical characterization of metal bioavailability in sediments from Lake Roosevelt, Columbia River, Washington, USA

    USGS Publications Warehouse

    Besser, J.M.; Brumbaugh, W.G.; Ivey, C.D.; Ingersoll, C.G.; Moran, P.W.

    2008-01-01

    We studied the bioavailability and toxicity of copper, zinc, arsenic, cadmium, and lead in sediments from Lake Roosevelt (LR), a reservoir on the Columbia River in Washington, USA that receives inputs of metals from an upstream smelter facility. We characterized chronic sediment toxicity, metal bioaccumulation, and metal concentrations in sediment and pore water from eight study sites: one site upstream in the Columbia River, six sites in the reservoir, and a reference site in an uncontaminated tributary. Total recoverable metal concentrations in LR sediments generally decreased from upstream to downstream in the study area, but sediments from two sites in the reservoir had metal concentrations much lower than adjacent reservoir sites and similar to the reference site, apparently due to erosion of uncontaminated bank soils. Concentrations of acid-volatile sulfide in LR sediments were too low to provide strong controls on metal bioavailability, and selective sediment extractions indicated that metals in most LR sediments were primarily associated with iron and manganese oxides. Oligochaetes (Lumbriculus variegatus) accumulated greatest concentrations of copper from the river sediment, and greatest concentrations of arsenic, cadmium, and lead from reservoir sediments. Chronic toxic effects on amphipods (Hyalella azteca; reduced survival) and midge larvae (Chironomus dilutus; reduced growth) in whole-sediment exposures were generally consistent with predictions of metal toxicity based on empirical and equilibrium partitioning-based sediment quality guidelines. Elevated metal concentrations in pore waters of some LR sediments suggested that metals released from iron and manganese oxides under anoxic conditions contributed to metal bioaccumulation and toxicity. Results of both chemical and biological assays indicate that metals in sediments from both riverine and reservoir habitats of Lake Roosevelt are available to benthic invertebrates. These findings will be used as

  6. Cyclic catalytic upgrading of chemical species using metal oxide materials

    DOEpatents

    White, James H.; Schutte, Erick J.; Rolfe, Sara L.

    2010-11-02

    Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having one of the following formulas: (a) Ce.sub.xB.sub.yB'.sub.zB''O.sub..delta., wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, or Fe; B''=Cu; 0.01

  7. Cyclic catalytic upgrading of chemical species using metal oxide materials

    NASA Technical Reports Server (NTRS)

    White, James H. (Inventor); Schutte, Erick J. (Inventor); Rolfe, Sara L. (Inventor)

    2010-01-01

    Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having one of the following formulas: (a) Ce.sub.xB.sub.yB'.sub.zB''O.sub..delta., wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, or Fe; B''=Cu; 0.01

  8. Ecotoxicity of chemically stabilised metal(loid)s in shooting range soils.

    PubMed

    Sanderson, Peter; Naidu, Ravi; Bolan, Nanthi

    2014-02-01

    Five chemical amendments (soft rock phosphate, lime, commercial phosphate amendment, red mud and magnesium oxide) were applied across four different shooting range soils to chemically stabilise metal(loid)s in the soils. Soils were contaminated with Pb between 2330 and 12,167 mg/kg, Sb from 7.4 to 325 mg/kg and soil pH ranged from 5.43 to 9.29. Amendments were tested for their ability to reduce the bioavailability of Pb, Sb, Zn, Ni, Cu and As in the soils to soil organisms after one year of aging, by measuring a series of ecotoxicological endpoints for earthworms and plants and soil microbial activity. Growth-based endpoints for earthworms and plants were not significantly affected by amendment addition, except in the most contaminated soil. Per cent survival and weight-loss reduction of earthworms was enhanced by amendment addition in only the most contaminated soil. Plant biomass and root elongation was not significantly affected by amendment addition (p=<0.05). Red mud and magnesium oxide appeared toxic to plants and earthworms, probably due to highly alkaline pH (9-12). Lead in soil organisms was relatively low despite the high concentrations of Pb in the soils, suggesting low bioavailability of Pb. Uptake of Pb by earthworms was reduced by between 40 and 96 per cent by amendments, but not across all soils. Amendments reduced Sb in earthworms in Townsville soil by up to 92 per cent. For lettuce the average uptake of Pb was reduced by 40 to 70 per cent with amendment addition in Townsville, Darwin and Perth soil. The effect of amendments on the uptake of Sb, Zn, Ni, Cu and As was variable between soils and amendments. Microbial activity was increased by greater than 50 per cent with amendments addition, with soft rock phosphate and lime being the most effective in Murray Bridge and TV soils and commercial phosphate and MgO being the most effective in Darwin and Perth soils.

  9. Chemical characteristic and functional properties of arenga starch-taro (Colocasia esculanta L.) flour noodle with turmeric extracts addition

    NASA Astrophysics Data System (ADS)

    Ervika Rahayu N., H.; Ariani, Dini; Miftakhussolikhah, E., Maharani P.; Yudi, P.

    2017-01-01

    Arenga starch-taro (Colocasia esculanta L.) flour noodle is an alternative carbohydrate source made from 75% arenga starch and 25% taro flour, but it has a different color with commercial noodle product. The addition of natural color from turmeric may change the consumer preference and affect chemical characteristic and functional properties of noodle. This research aims to identify chemical characteristic and functional properties of arenga starch-taro flour noodle with turmeric extract addition. Extraction was performed using 5 variances of turmeric rhizome (0.06; 0.12; 0.18; 0.24; and 0.30 g (fresh weight/ml water). Then, noodle was made and chemical characteristic (proximate analysis) as well as functional properties (amylose, resistant starch, dietary fiber, antioxidant activity) were then evaluated. The result showed that addition of turmeric extract did not change protein, fat, carbohydrate, amylose, and resistant starch content significantly, while antioxidant activity was increased (23,41%) with addition of turmeric extract.

  10. Invited Review Article: Review of post-process optical form metrology for industrial-grade metal additive manufactured parts.

    PubMed

    Stavroulakis, P I; Leach, R K

    2016-04-01

    The scope of this review is to investigate the main post-process optical form measurement technologies available in industry today and to determine whether they are applicable to industrial-grade metal additive manufactured parts. An in-depth review of the operation of optical three-dimensional form measurement technologies applicable to metal additive manufacturing is presented, with a focus on their fundamental limitations. Looking into the future, some alternative candidate measurement technologies potentially applicable to metal additive manufacturing will be discussed, which either provide higher accuracy than currently available techniques but lack measurement volume, or inversely, which operate in the appropriate measurement volume but are not currently accurate enough to be used for industrial measurement.

  11. Invited Review Article: Review of post-process optical form metrology for industrial-grade metal additive manufactured parts

    NASA Astrophysics Data System (ADS)

    Stavroulakis, P. I.; Leach, R. K.

    2016-04-01

    The scope of this review is to investigate the main post-process optical form measurement technologies available in industry today and to determine whether they are applicable to industrial-grade metal additive manufactured parts. An in-depth review of the operation of optical three-dimensional form measurement technologies applicable to metal additive manufacturing is presented, with a focus on their fundamental limitations. Looking into the future, some alternative candidate measurement technologies potentially applicable to metal additive manufacturing will be discussed, which either provide higher accuracy than currently available techniques but lack measurement volume, or inversely, which operate in the appropriate measurement volume but are not currently accurate enough to be used for industrial measurement.

  12. Chemical Cartography with APOGEE: Metallicity Distribution Functions and the Chemical Structure of the Milky Way Disk

    NASA Astrophysics Data System (ADS)

    Hayden, Michael R.; Bovy, Jo; Holtzman, Jon A.; Nidever, David L.; Bird, Jonathan C.; Weinberg, David H.; Andrews, Brett H.; Majewski, Steven R.; Allende Prieto, Carlos; Anders, Friedrich; Beers, Timothy C.; Bizyaev, Dmitry; Chiappini, Cristina; Cunha, Katia; Frinchaboy, Peter; García-Herńandez, D. A.; García Pérez, Ana E.; Girardi, Léo; Harding, Paul; Hearty, Fred R.; Johnson, Jennifer A.; Mészáros, Szabolcs; Minchev, Ivan; O'Connell, Robert; Pan, Kaike; Robin, Annie C.; Schiavon, Ricardo P.; Schneider, Donald P.; Schultheis, Mathias; Shetrone, Matthew; Skrutskie, Michael; Steinmetz, Matthias; Smith, Verne; Wilson, John C.; Zamora, Olga; Zasowski, Gail

    2015-08-01

    Using a sample of 69,919 red giants from the SDSS-III/APOGEE Data Release 12, we measure the distribution of stars in the [α/Fe] versus [Fe/H] plane and the metallicity distribution functions (MDFs) across an unprecedented volume of the Milky Way disk, with radius 3 < R < 15 kpc and height | z| \\lt 2 kpc. Stars in the inner disk (R < 5 kpc) lie along a single track in [α/Fe] versus [Fe/H], starting with α-enhanced, metal-poor stars and ending at [α/Fe] ˜ 0 and [Fe/H] ˜ +0.4. At larger radii we find two distinct sequences in [α/Fe] versus [Fe/H] space, with a roughly solar-α sequence that spans a decade in metallicity and a high-α sequence that merges with the low-α sequence at super-solar [Fe/H]. The location of the high-α sequence is nearly constant across the disk however, there are very few high-α stars at R > 11 kpc. The peak of the midplane MDF shifts to lower metallicity at larger R, reflecting the Galactic metallicity gradient. Most strikingly, the shape of the midplane MDF changes systematically with radius, from a negatively skewed distribution at 3 < R < 7 kpc, to a roughly Gaussian distribution at the solar annulus, to a positively skewed shape in the outer Galaxy. For stars with | z| \\gt 1 kpc or [α/Fe] > 0.18, the MDF shows little dependence on R. The positive skewness of the outer-disk MDF may be a signature of radial migration; we show that blurring of stellar populations by orbital eccentricities is not enough to explain the reversal of MDF shape, but a simple model of radial migration can do so.

  13. Physical and chemical characterization techniques for metallic powders

    SciTech Connect

    Slotwinski, J. A.; Stutzman, P. E.; Ferraris, C. F.; Watson, S. S.; Peltz, M. A.; Garboczi, E. J.

    2014-02-18

    Systematic studies have been carried out on two different powder materials used for additive manufacturing: stainless steel and cobalt-chrome. An extensive array of characterization techniques were applied to these two powders. The physical techniques included laser-diffraction particle-size analysis, X-ray computed tomography for size and shape analysis, and optical and scanning electron microscopy. Techniques sensitive to chemistry included X-ray diffraction and energy-dispersive analytical X-ray analysis. The background of these techniques will be summarized and some typical findings comparing different samples of virgin additive manufacturing powders, taken from the same lot, will be given. The techniques were used to confirm that different samples of powder from the same lot were essentially identical, within the uncertainty of the measurements.

  14. Effects of heavy metal and other elemental additives to activated sludge on growth of Eisenia foetida

    SciTech Connect

    Hartenstein, R.; Neuhauser, E.F.; Narahara, A.

    1981-09-01

    The approximate level at which added concentrations of certain elements would cause an activated sludge to induce a toxic effect upon the growth of Eisenia foetida was determined. During 43 trials on sludge samples obtained throughout 1 year of study, earthworms grew from 3 to 10 mg live wt at hatching to 792 mg +- 18% (mean +- C.V.) in 8 weeks, when sludge was 24/sup 0/C and contained no additives. None of several elements commonly used in microbial growth media enhanced the growth rate of the earthworm. At salt concentrations up to about 6.6% on a dry wt basis, none of six anions tested was in and of itself toxic, while five of 15 cations - Co, Hg, Cu, Ni, and Cd - appeared specifically to inhibit growth rate or cause death. Manganese, Cr, and Pb were innocuous even at the highest levels of application - 22,000, 46,000, and 52,000 mg/kg, respectively. Neither the anionic nor cationic component of certain salts, such as NaCl or NH/sub 4/Cl, could be said to inhibit growth, which occurred only at high concentrations of these salts (about 3.3 and/or 6.6%). Below 7 mmho/cm, toxicity could not be correlated with electrolytic conductance, though higher values may help to explain the nonspecific growth inhibitory effects of salts like NaCl and KCl. Nor could toxicity ever be ascribed to hydrogen ion activity, since sludge pH was not altered even at the highest salt dose. It is concluded that except under very extreme conditions, the levels of heavy metals and salts generally found in activated sludges will not have an adverse affect on the growth of E. foetida.

  15. Problems of Development and Application of Metal Matrix Composite Powders for Additive Technologies

    NASA Astrophysics Data System (ADS)

    Korosteleva, Elena N.; Pribytkov, Gennadii A.; Krinitcyn, Maxim G.; Baranovskii, Anton V.; Korzhova, Victoria V.

    2016-07-01

    The paper considers the problem of structure formation in composites with carbide phase and a metal binder under self-propagating high-temperature synthesis (SHS) of powder mixtures. The relation between metal binder content and their structure and wear resistance of coatings was studied. It has been shown that dispersion of the carbide phase and volume content of metal binder in the composite powders structure could be regulated purposefully for all of studied composites. It was found that the structure of surfaced coating was fully inherited of composite powders. Modification or coarsening of the structure at the expense of recrystallization or coagulation carbide phase during deposition and sputtering does not occur.

  16. Substrate Vibrations as Promoters of Chemical Reactivity on Metal Surfaces.

    PubMed

    Campbell, Victoria L; Chen, Nan; Guo, Han; Jackson, Bret; Utz, Arthur L

    2015-12-17

    Studies exploring how vibrational energy (Evib) promotes chemical reactivity most often focus on molecular reagents, leaving the role of substrate atom motion in heterogeneous interfacial chemistry underexplored. This combined theoretical and experimental study of methane dissociation on Ni(111) shows that lattice atom motion modulates the reaction barrier height during each surface atom's vibrational period, which leads to a strong variation in the reaction probability (S0) with surface temperature (Tsurf). State-resolved beam-surface scattering studies at Tsurf = 90 K show a sharp threshold in S0 at translational energy (Etrans) = 42 kJ/mol. When Etrans decreases from 42 kJ/mol to 34 kJ/mol, S0 decreases 1000-fold at Tsurf = 90 K, but only 2-fold at Tsurf = 475 K. Results highlight the mechanism for this effect, provide benchmarks for DFT calculations, and suggest the potential importance of surface atom induced barrier height modulation in heterogeneously catalyzed reactions, particularly on structurally labile nanoscale particles and defect sites.

  17. Metal film deposition by laser breakdown chemical vapor deposition

    SciTech Connect

    Jervis, T. R.; Newkirk, L. R.

    1986-06-01

    Dielectric breakdown of gas mixtures can be used to deposit thin films by chemical vapor deposition with appropriate control of flow and pressure conditions to suppress gas-phase nucleation and particle formation. Using a pulsed CO/sub 2/ laser operating at 10.6 ..mu.. where there is no significant resonant absorption in any of the source gases, homogeneous films from several gas-phase precursors have been sucessfully deposited by gas-phase laser pyrolysis. Nickel and molybdenum from the respective carbonyls representing decomposition chemistry and tungsten from the hexafluoride representing reduction chemistry have been demonstrated. In each case the gas precursor is buffered with argon to reduce the partial pressure of the reactants and to induce breakdown. Films have been characterized by Auger electron spectroscopy, x-ray diffraction, transmission electron microscopy, pull tests, and resistivity measurements. The highest quality films have resulted from the nickel depositions. Detailed x-ray diffraction analysis of these films yields a very small domain size consistent with the low temperature of the substrate and the formation of metastable nickel carbide. Transmission electron microscopy supports this analysis.

  18. Interim Action Proposed Plan for the Chemicals, Metals, and Pesticides (CMP) Pits Operable Unit

    SciTech Connect

    Bradley, J.

    2002-06-18

    The purpose of this Interim Action Proposed Plan (IAPP) is to describe the preferred interim remedial action for addressing the Chemicals, Metals, and Pesticides (CMP) Pits Operable Unit and to provide an opportunity for public input into the remedial action selection process.

  19. Disappearance of Barrier Metal during Cu Chemical Mechanical Planarization Processing and Its Mechanism

    NASA Astrophysics Data System (ADS)

    Asano, Hiroshi; Yasui, Akihito; Hirano, Tatsuhiko; Tamai, Kazusei; Morinaga, Hitoshi

    2011-05-01

    The bald disappearance of barrier metal had been observed on the wafer after Cu chemical mechanical planarization (CMP) processing. It was speculated that this phenomenon occurs because the excessively oxidized Ta by electrochemical reaction with Cu ion was removed more easily than the normal Ta oxide around it. The inhibition of the electrochemical reaction is necessary to solve this phenomenon.

  20. Sequential Aldol Condensation – Transition Metal-Catalyzed Addition Reactions of Aldehydes, Methyl Ketones and Arylboronic Acids

    PubMed Central

    Liao, Yuan-Xi; Xing, Chun-Hui; Israel, Matthew; Hu, Qiao-Sheng

    2011-01-01

    Sequential aldol condensation of aldehydes with methyl ketones followed by transition metal-catalyzed addition reactions of arylboronic acids to form β-substituted ketones is described. By using the 1,1′-spirobiindane-7,7′-diol (SPINOL)-based phosphite, an asymmetric version of this type of sequential reaction, with up to 92% ee, was also realized. Our study provided an efficient method to access β-substituted ketones and might lead to the development of other sequential/tandem reactions with transition metal-catalyzed addition reactions as the key step. PMID:21417359

  1. Synergistic effect of rice husk addition on hydrothermal treatment of sewage sludge: fate and environmental risk of heavy metals.

    PubMed

    Shi, Wansheng; Liu, Chunguang; Shu, Youju; Feng, Chuanping; Lei, Zhongfang; Zhang, Zhenya

    2013-12-01

    Hydrothermal treatment (HTT) at 200°C was applied to immobilize heavy metals (HMs) and the effect of rice husk (RH) addition was investigated based on total HMs concentration, fractionation and leaching tests. The results indicated that a synergistic effect of RH addition and HTT could be achieved on reducing the risk of HMs from medium and low risk to no risk. Metals were redistributed and transformed from weakly bounded state to stable state during the HTT process under RH addition. Notably at a RH/sludge ratio of 1/1.75 (d.w.), all the HMs showed no eco-toxicity and no leaching toxicity, with the concentrations of leachable Cr, Ni, Cu and Cd decreased by 17%, 89%, 95% and 93%, respectively. This synergistic effect of RH addition and HTT on the risk reduction of HMs implies that HTT process with RH addition could be a promising and safe disposal technology for sewage sludge treatment in practice.

  2. Assessing the effects of adsorptive polymeric resin additions on fungal secondary metabolite chemical diversity

    PubMed Central

    González-Menéndez, Víctor; Asensio, Francisco; Moreno, Catalina; de Pedro, Nuria; Monteiro, Maria Candida; de la Cruz, Mercedes; Vicente, Francisca; Bills, Gerald F.; Reyes, Fernando; Genilloud, Olga; Tormo, José R.

    2014-01-01

    Adsorptive polymeric resins have been occasionally described to enhance the production of specific secondary metabolites (SMs) of interest. Methods that induce the expression of new chemical entities in fungal fermentations may lead to the discovery of new bioactive molecules and should be addressed as possible tools for the creation of new microbial chemical libraries for drug lead discovery. Herein, we apply both biological activity and chemical evaluations to assess the use of adsorptive resins as tools for the differential expression of SMs in fungal strain sets. Data automation approaches were applied to ultra high performance liquid chromatography analysis of extracts to evaluate the general influence in generating new chemical entities or in changing the production of specific SMs by fungi grown in the presence of resins and different base media. PMID:25379340

  3. Chemical bonding and aromaticity in trinuclear transition-metal halide clusters.

    PubMed

    Weck, Philippe F; Sergeeva, Alina P; Kim, Eunja; Boldyrev, Alexander I; Czerwinski, Kenneth R

    2011-02-07

    Trinuclear transition-metal complexes such as Re(3)X(9) (X = Cl, Br, I), with their uniquely featured structure among metal halides, have posed intriguing questions related to multicenter electron delocalization for several decades. Here we report a comprehensive study of the technetium halide clusters [Tc(3)(μ-X)(3)X(6)](0/1-/2-) (X = F, Cl, Br, I), isomorphous with their rhenium congeners, predicted from density functional theory calculations. The chemical bonding and aromaticity in these clusters are analyzed using the recently developed adaptive natural density partitioning method, which indicates that only [Tc(3)X(9)](2-) clusters exhibit aromatic character, stemming from a d-orbital-based π bond delocalized over the three metal centers. We also show that standard methods founded on the nucleus-independent chemical shift concept incorrectly predict the neutral Tc(3)X(9) clusters to be aromatic.

  4. The influence of Si addition in 55AlZn bath on the coating structures obtained in the batch hot-dip metallization

    NASA Astrophysics Data System (ADS)

    Mendala, J.

    2011-05-01

    One of the methods of increasing the corrosion resistance of zinc coatings is the application of zinc and aluminium alloy baths in the metallization process. The coatings obtained are characterized by much better corrosion resistance thanks to the combination of aluminium properties, i.e. the barrier protection provided by naturally created aluminium oxides, with the capacity to protect the steel substrate, which is characteristic of zinc coatings. Zinc coatings with 55 wt. % Al and an addition of Si have gained industrial importance. The introduction of a third alloying component into the metallization bath is a technological addition, the aim of which is to reduce and possibly inhibit the aluminium diffusion towards the substrate. The article presents the results of the examination of coatings obtained in a 55AlZn bath at varied parameters of the technological process, as well as the specification of silicon addition influence on the structure and chemical composition of the coatings, and on the kinetics of growth. The coatings were obtained in three temperatures: 620, 640 and 660°C, and the process was conducted in a 55 wt. % Al bath with Si content of 0, 0.8 and 1.6 wt. % respectively, the remaining content was Zn. For the purposes of evaluating the microstructure and thickness of the coatings obtained, examinations on a light microscope were conducted. In order to determine the chemical composition of the coatings obtained, an EDS analysis was conducted. Quantitative examination of the chemical composition was carried out on the selected cross-sections of samples with coatings considered to be representative ones, using a SEM with a microanalysis system. Moreover, the linear distribution of elements on the cross-sections of the chosen coatings was determined. It is possible to state that the addition of silicon to 55AlZn baths allows reducing the uncontrolled growth of a layer. The layers obtained are more uniform, continuous and they show good adhesion to

  5. Characterization of a multi-metal binding biosorbent: Chemical modification and desorption studies.

    PubMed

    Abdolali, Atefeh; Ngo, Huu Hao; Guo, Wenshan; Zhou, John L; Du, Bin; Wei, Qin; Wang, Xiaochang C; Nguyen, Phuoc Dan

    2015-10-01

    This work attends to preparation and characterization of a novel multi-metal binding biosorbent after chemical modification and desorption studies. Biomass is a combination of tea waste, maple leaves and mandarin peels with a certain proportion to adsorb cadmium, copper, lead and zinc ions from aqueous solutions. The mechanism involved in metal removal was investigated by SEM, SEM/EDS and FTIR. SEM/EDS showed the presence of different chemicals and adsorbed heavy metal ions on the surface of biosorbent. FTIR of both unmodified and modified biosorbents revealed the important role of carboxylate groups in heavy metal biosorption. Desorption using different eluents and 0.1 M HCl showed the best desorption performance. The effectiveness of regeneration step by 1 M CaCl2 on five successive cycles of sorption and desorption displays this multi-metal binding biosorbent (MMBB) can effectively be utilized as an adsorbent to remove heavy metal ions from aqueous solutions in five cycles of sorption/desorption/regeneration. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. The chemical origin and catalytic activity of coinage metals: from oxidation to dehydrogenation.

    PubMed

    Syu, Cih-Ying; Yang, Hao-Wen; Hsu, Fu-Hsing; Wang, Jeng-Han

    2014-04-28

    The high oxidation activity of coinage metals (Cu, Ag and Au) has been widely applied in various important reactions, such as oxidation of carbon monoxide, alkenes or alcohols. The catalytic behavior of those inert metals has mostly been attributable to their size effect, the physical effect. In the present study, the chemical effects on their high oxidation activity have been investigated. We mechanistically examine the direct and oxidative dehydrogenation (partial oxidation) reactions of ethanol to acetaldehyde on a series of transition metals (groups 9, 10 and 11) with identical physical characteristics and varied chemical origins using density functional theory (DFT) calculations and electronic structure analyses at the GGA-PW91 level. The energetic results show that coinage metals have much lower activation energies and higher exothermicities for the oxidative dehydrogenation steps although they have higher energy for the direct dehydrogenation reaction. In the electronic structure analyses, coinage metals with saturated d bands can efficiently donate electrons to O* and OH*, or other electronegative adspecies, and better promote their p bands to higher energy levels. The negatively charged O* and OH* with high-lying p bands are responsible for lowering the energies in oxidative steps. The mechanistic understanding well explains the better oxidation activity of coinage metals and provides valuable information on their utilization in other useful applications, for example, the dehydrogenation process.

  7. Chemical and microstructural analyses for heavy metals removal from water media by ceramic membrane filtration.

    PubMed

    Ali, Asmaa; Ahmed, Abdelkader; Gad, Ali

    2017-01-01

    This study aims to investigate the ability of low cost ceramic membrane filtration in removing three common heavy metals namely; Pb(2+), Cu(2+), and Cd(2+) from water media. The work includes manufacturing ceramic membranes with dimensions of 15 by 15 cm and 2 cm thickness. The membranes were made from low cost materials of local clay mixed with different sawdust percentages of 0.5%, 2.0%, and 5.0%. The used clay was characterized by X-ray diffraction (XRD) and X-ray fluorescence analysis. Aqueous solutions of heavy metals were prepared in the laboratory and filtered through the ceramic membranes. The influence of the main parameters such as pH, initial driving pressure head, and concentration of heavy metals on their removal efficiency by ceramic membranes was investigated. Water samples were collected before and after the filtration process and their heavy metal concentrations were determined by chemical analysis. Moreover, a microstructural analysis using scanning electronic microscope (SEM) was performed on ceramic membranes before and after the filtration process. The chemical analysis results showed high removal efficiency up to 99% for the concerned heavy metals. SEM images approved these results by showing adsorbed metal ions on sides of the internal pores of the ceramic membranes.

  8. A Differential Chemical Element Analysis of the Metal-poor Globular Cluster NGC 6397

    NASA Astrophysics Data System (ADS)

    Koch, Andreas; McWilliam, Andrew

    2011-08-01

    We present chemical abundances in three red giants and two turnoff (TO) stars in the metal-poor Galactic globular cluster (GC) NGC 6397 based on spectroscopy obtained with the Magellan Inamori Kyocera Echelle high-resolution spectrograph on the Magellan 6.5 m Clay telescope. Our results are based on a line-by-line differential abundance analysis relative to the well-studied red giant Arcturus and the Galactic halo field star Hip 66815. At a mean of -2.10 ± 0.02 (stat.) ±0.07 (sys.), the differential iron abundance is in good agreement with other studies in the literature based on gf-values. As in previous differential works we find a distinct departure from ionization equilibrium in that the abundances of Fe I and Fe II differ by ~0.1 dex, with opposite signs for the red giant branch (RGB) and TO stars. The α-element ratios are enhanced to 0.4 (RGB) and 0.3 dex (TO), respectively, and we also confirm strong variations in the O, Na, and Al/Fe abundance ratios. Accordingly, the light-element abundance patterns in one of the red giants can be attributed to pollution by an early generation of massive Type II supernovae. TO and RGB abundances are not significantly different, with the possible exception of Mg and Ti, which are, however, amplified by the patterns in one TO star additionally belonging to this early generation of GC stars. We discuss interrelations of these light elements as a function of the GC metallicity. This paper includes data gathered with the 6.5 m Magellan Telescopes located at Las Campanas Observatory, Chile.

  9. Light-emitting silicon nanowires obtained by metal-assisted chemical etching

    NASA Astrophysics Data System (ADS)

    Irrera, Alessia; Josè Lo Faro, Maria; D’Andrea, Cristiano; Alessio Leonardi, Antonio; Artoni, Pietro; Fazio, Barbara; Picca, Rosaria Anna; Cioffi, Nicola; Trusso, Sebastiano; Franzò, Giorgia; Musumeci, Paolo; Priolo, Francesco; Iacona, Fabio

    2017-04-01

    This review reports on a new process for the synthesis of Si nanowires (NWs), based on the wet etching of Si substrates assisted by a thin metal film. The approach exploits the thickness-dependent morphology of the metal layers to define uncovered nanometric Si regions, which behave as precursor sites for the formation of very dense (up to 1 × 1012 NW cm‑2) arrays of long (up to several μm) and ultrathin (diameter of 5–9 nm) NWs. Intense photoluminescence (PL) peaks, characterized by maxima in the 640–750 nm range and by an external quantum efficiency of 0.5%, are observed when the Si NWs are excited at room temperature. The spectra show a blueshift if the size of the NW is decreased, in agreement with the occurrence of quantum confinement effects. The same etching process can be used to obtain ultrathin Si/Ge NWs from a Si/Ge multi-quantum well. The Si/Ge NWs exhibit—in addition to the Si-related PL peak—a signal at about 1240 nm due to Ge nanostructures. The huge surface area of the Si NW arrays can be exploited for sensing and analytical applications. The dependence of the PL intensity on the chemical composition of the surface indeed suggests interesting perspectives for the detection of gaseous molecules. Moreover, Si NWs decorated with Ag nanoparticles can be effectively employed in the interference-free laser desorption-ionization mass spectrometry of low-molecular-weight analytes. A device based on conductive Si NWs, showing intense and stable electroluminescence at an excitation voltage as low as 2 V, is also presented. The unique features of the proposed synthesis (the process is cheap, fast, maskless and compatible with Si technology) and the unusual optical properties of the material open the route towards new and unexpected perspectives for semiconductor NWs in photonics.

  10. CHEMICAL ABUNDANCES IN NGC 5053: A VERY METAL-POOR AND DYNAMICALLY COMPLEX GLOBULAR CLUSTER

    SciTech Connect

    Boberg, Owen M.; Friel, Eileen D.; Vesperini, Enrico

    2015-05-10

    NGC 5053 provides a rich environment to test our understanding of the complex evolution of globular clusters (GCs). Recent studies have found that this cluster has interesting morphological features beyond the typical spherical distribution of GCs, suggesting that external tidal effects have played an important role in its evolution and current properties. Additionally, simulations have shown that NGC 5053 could be a likely candidate to belong to the Sagittarius dwarf galaxy (Sgr dSph) stream. Using the Wisconsin–Indiana–Yale–NOAO–Hydra multi-object spectrograph, we have collected high quality (signal-to-noise ratio ∼ 75–90), medium-resolution spectra for red giant branch stars in NGC 5053. Using these spectra we have measured the Fe, Ca, Ti, Ni, Ba, Na, and O abundances in the cluster. We measure an average cluster [Fe/H] abundance of −2.45 with a standard deviation of 0.04 dex, making NGC 5053 one of the most metal-poor GCs in the Milky Way (MW). The [Ca/Fe], [Ti/Fe], and [Ba/Fe] we measure are consistent with the abundances of MW halo stars at a similar metallicity, with alpha-enhanced ratios and slightly depleted [Ba/Fe]. The Na and O abundances show the Na–O anti-correlation found in most GCs. From our abundance analysis it appears that NGC 5053 is at least chemically similar to other GCs found in the MW. This does not, however, rule out NGC 5053 being associated with the Sgr dSph stream.

  11. Chemical Abundances in NGC 5053: A Very Metal-poor and Dynamically Complex Globular Cluster

    NASA Astrophysics Data System (ADS)

    Boberg, Owen M.; Friel, Eileen D.; Vesperini, Enrico

    2015-05-01

    NGC 5053 provides a rich environment to test our understanding of the complex evolution of globular clusters (GCs). Recent studies have found that this cluster has interesting morphological features beyond the typical spherical distribution of GCs, suggesting that external tidal effects have played an important role in its evolution and current properties. Additionally, simulations have shown that NGC 5053 could be a likely candidate to belong to the Sagittarius dwarf galaxy (Sgr dSph) stream. Using the Wisconsin-Indiana-Yale-NOAO-Hydra multi-object spectrograph, we have collected high quality (signal-to-noise ratio ˜ 75-90), medium-resolution spectra for red giant branch stars in NGC 5053. Using these spectra we have measured the Fe, Ca, Ti, Ni, Ba, Na, and O abundances in the cluster. We measure an average cluster [Fe/H] abundance of -2.45 with a standard deviation of 0.04 dex, making NGC 5053 one of the most metal-poor GCs in the Milky Way (MW). The [Ca/Fe], [Ti/Fe], and [Ba/Fe] we measure are consistent with the abundances of MW halo stars at a similar metallicity, with alpha-enhanced ratios and slightly depleted [Ba/Fe]. The Na and O abundances show the Na-O anti-correlation found in most GCs. From our abundance analysis it appears that NGC 5053 is at least chemically similar to other GCs found in the MW. This does not, however, rule out NGC 5053 being associated with the Sgr dSph stream.

  12. Chemical Abundances in NGC 5053: A Very Metal Poor and Dynamically Complex Globular Cluster

    NASA Astrophysics Data System (ADS)

    Boberg, Owen; Friel, Eileen D.; Vesperini, Enrico

    2015-01-01

    NGC 5053 provides a rich environment to test our understanding of the complex evolution of globular clusters (GCs). Recent studies have found that this cluster has interesting morphological features beyond the spherical distribution expected from GCs. These features include a ˜6° tidal stream (Lauchner et al. 2006), and a possible, but still debated, bridge-like structure between it and its nearby neighbor NGC 5024 (Chun et al. 2010). These features suggest that the evolution of these clusters has not only been greatly affected by their gravitational interaction with the Galaxy, but possibly each other. Additionally, simulations have shown that NGC 5053 could be a likely candidate to belong to the Sgr dSph stream (Law & Majewski 2010). Using the WIYN-Hydra multi-object spectrograph, we have collected high quality (S/N ˜75-90), medium-resolution spectra for red giant branch (RGB) stars in NGC 5053. Using these spectra we have measured the Fe, Ca, Ti, Ni, Ba, Na, and O abundances in the cluster. We measure an average cluster [Fe/H] abundance of -2.46 with a standard deviation of 0.05 dex, making NGC 5053 one of the most metal poor GCs in the Milky Way. The [Ca/Fe], [Ti/Fe], and [Ba/Fe] we measure are consistent with the abundances of Milky Way halo stars at a similar metallicity, with high alpha values and slightly depleted [Ba/Fe]. The Na and O abundances show the Na-O anti-correlation found in most GCs. From our abundance analysis it appears that NGC 5053 is at least chemically similar to other GCs found in the Milky Way. This does not, however, rule out NGC 5053 being a member of the Sgr dSph stream.

  13. A DIFFERENTIAL CHEMICAL ELEMENT ANALYSIS OF THE METAL-POOR GLOBULAR CLUSTER NGC 6397

    SciTech Connect

    Koch, Andreas; McWilliam, Andrew E-mail: andy@obs.carnegiescience.edu

    2011-08-15

    We present chemical abundances in three red giants and two turnoff (TO) stars in the metal-poor Galactic globular cluster (GC) NGC 6397 based on spectroscopy obtained with the Magellan Inamori Kyocera Echelle high-resolution spectrograph on the Magellan 6.5 m Clay telescope. Our results are based on a line-by-line differential abundance analysis relative to the well-studied red giant Arcturus and the Galactic halo field star Hip 66815. At a mean of -2.10 {+-} 0.02 (stat.) {+-}0.07 (sys.), the differential iron abundance is in good agreement with other studies in the literature based on gf-values. As in previous differential works we find a distinct departure from ionization equilibrium in that the abundances of Fe I and Fe II differ by {approx}0.1 dex, with opposite signs for the red giant branch (RGB) and TO stars. The {alpha}-element ratios are enhanced to 0.4 (RGB) and 0.3 dex (TO), respectively, and we also confirm strong variations in the O, Na, and Al/Fe abundance ratios. Accordingly, the light-element abundance patterns in one of the red giants can be attributed to pollution by an early generation of massive Type II supernovae. TO and RGB abundances are not significantly different, with the possible exception of Mg and Ti, which are, however, amplified by the patterns in one TO star additionally belonging to this early generation of GC stars. We discuss interrelations of these light elements as a function of the GC metallicity.

  14. (abstract) Studies on AB(sub 5) Metal Hydride Alloys with Sn Additives

    NASA Technical Reports Server (NTRS)

    Ratnakumar, B. V.; Surampudi, S.; Stefano, S. Di; Halpert, G.; Witham, C.; Fultz, B.

    1994-01-01

    The use of metal hydrides as negative electrodes in alkaline rechargeable cells is becoming increasingly popular, due to several advantages offered by the metal hydrides over conventional anode materials (such as Zn, Cd) in terms of specific energy environmental cycle life and compatibility. Besides, the similarities in the cell voltage pressure characteristics, and charge control methods of the Ni-MH cells to the commonly used Ni-Cd point to a projected take over of 25% of the Ni-Cd market for consumer electronics by the Ni-MH cells in the next couple of years. Two classes of metal hydrides alloys based on rare earth metals (AB(sub 5)) and titanium (AB(sub 2)) are being currently developed at various laboratories. AB(sub 2) alloys exhibit higher specific energy than the AB(sub 5) alloys but the state of the art commercial Ni-MH cells are predominately manufactured using AB(sub 5) alloys.

  15. (abstract) Studies on AB(sub 5) Metal Hydride Alloys with Sn Additives

    NASA Technical Reports Server (NTRS)

    Ratnakumar, B. V.; Surampudi, S.; Stefano, S. Di; Halpert, G.; Witham, C.; Fultz, B.

    1994-01-01

    The use of metal hydrides as negative electrodes in alkaline rechargeable cells is becoming increasingly popular, due to several advantages offered by the metal hydrides over conventional anode materials (such as Zn, Cd) in terms of specific energy environmental cycle life and compatibility. Besides, the similarities in the cell voltage pressure characteristics, and charge control methods of the Ni-MH cells to the commonly used Ni-Cd point to a projected take over of 25% of the Ni-Cd market for consumer electronics by the Ni-MH cells in the next couple of years. Two classes of metal hydrides alloys based on rare earth metals (AB(sub 5)) and titanium (AB(sub 2)) are being currently developed at various laboratories. AB(sub 2) alloys exhibit higher specific energy than the AB(sub 5) alloys but the state of the art commercial Ni-MH cells are predominately manufactured using AB(sub 5) alloys.

  16. Metal film deposition by laser breakdown chemical vapor deposition

    SciTech Connect

    Jervis, T.R.

    1985-01-01

    Dielectric breakdown of gas mixtures can be used to deposit homogeneous thin films by chemical vapor deposition with appropriate control of flow and pressure conditions to suppress gas phase nucleation and particle formation. Using a pulsed CO/sub 2/ laser operating at 10.6 microns where there is no significant resonant absorption in any of the source gases, we have succeeded in depositing homogeneous films from several gas phase precursors by gas phase laser pyrolysis. Nickel and molybdenum from the respective carbonyls and tungsten from the hexafluoride have been examined to date. In each case the gas precursor is buffered to reduce the partial pressure of the reactants and to induce breakdown. The films are spectrally reflective and uniform over a large area. Films have been characterized by Auger electron spectroscopy, x-ray diffraction, pull tests, and resistivity measurements. The highest quality films have resulted from the nickel depositions. Detailed x-ray diffraction analysis of these films yields a very small domain size (approx. 50 A) consistent with rapid quenching from the gas phase reaction zone. This analysis also shows nickel carbide formation consistent with the temperature of the reaction zone and the Auger electron spectroscopy results which show some carbon and oxygen incorporation (8% and 1% respectively). Gas phase transport and condensation of the molybdenum carbonyl results in substantial carbon and oxygen contamination of the molybdenum films requiring heated substrates, a requirement not consistent with the goals of the program to maximize the quench rate of the deposition. Results from tungsten deposition experiments representing a reduction chemistry instead of the decomposition chemistry involved in the carbonyl experiments are also reported.

  17. Metal film deposition by laser breakdown chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Jervis, T. R.

    1985-01-01

    Dielectric breakdown of gas mixtures can be used to deposit homogeneous thin films by chemical vapor deposition with appropriate control of flow and pressure conditions to suppress gas phase nucleation and particle formation. Using a pulsed CO2 laser operating at 10.6 microns where there is no significant resonant absorption in any of the source gases, we have succeeded in depositing homogeneous films from several gas phase precursors by gas phase laser pyrolysis. Nickel and molybdenum from the respective carbonyls and tungsten from the hexafluoride have been examined to date. In each case the gas precursor is buffered to reduce the partial pressure of the reactants and to induce breakdown. The films are spectrally reflective and uniform over a large area. Films have been characterized by Auger electron spectroscopy, X-ray diffraction, pull tests, and resistivity measurements. The highest quality films have resulted from the nickel depositions. Detailed X-ray diffraction analysis of these films yields a very small domain size (approx. 50 A) consistent with rapid quenching from the gas phase reaction zone. This analysis also shows nickel carbide formation consistent with the temperature of the reaction zone and the Auger electron spectroscopy results which show some carbon and oxygen incorporation (8% and 1% respectively). Gas phase transport and condensation of the molybdenum carbonyl results in substantial carbon and oxygen contamination of the molybdenum films requiring heated substrates, a requirement not consistent with the goals of the program to maximize the quench rate of the deposition. Results from tungsten deposition experiments representing a reduction chemistry instead of the decomposition chemistry involved in the carbonyl experiments are also reported.

  18. Cold interactions and chemical reactions of linear polyatomic anions with alkali-metal and alkaline-earth-metal atoms.

    PubMed

    Tomza, Michał

    2017-06-28

    We consider collisional studies of linear polyatomic ions immersed in ultracold atomic gases and investigate the intermolecular interactions and chemical reactions of several molecular anions (OH(-), CN(-), NCO(-), C2H(-), C4H(-)) with alkali-metal (Li, Na, K, Rb, Cs) and alkaline-earth-metal (Mg, Ca, Sr, Ba) atoms. State-of-the-art ab initio techniques are applied to compute the potential energy surfaces (PESs) for these systems. The coupled cluster method restricted to single, double, and noniterative triple excitations, CCSD(T), is employed and the scalar relativistic effects in heavier metal atoms are modeled within the small-core energy-consistent pseudopotentials. The leading long-range isotropic and anisotropic induction and dispersion interaction coefficients are obtained within the perturbation theory. The PESs are characterized in detail and their universal similarities typical for systems dominated by the induction interaction are discussed. The two-dimensional PESs are provided for selected systems and can be employed in scattering calculations. The possible channels of chemical reactions and their control are analyzed based on the energetics of the reactants. The present study of the electronic structure is the first step towards the evaluation of prospects for sympathetic cooling and controlled chemistry of linear polyatomic ions with ultracold atoms.

  19. The addition of organic carbon and nitrate affects reactive transport of heavy metals in sandy aquifers.

    PubMed

    Satyawali, Yamini; Seuntjens, Piet; Van Roy, Sandra; Joris, Ingeborg; Vangeel, Silvia; Dejonghe, Winnie; Vanbroekhoven, Karolien

    2011-04-25

    Organic carbon introduction in the soil to initiate remedial measures, nitrate infiltration due to agricultural practices or sulphate intrusion owing to industrial usage can influence the redox conditions and pH, thus affecting the mobility of heavy metals in soil and groundwater. This study reports the fate of Zn and Cd in sandy aquifers under a variety of plausible in-situ redox conditions that were induced by introduction of carbon and various electron acceptors in column experiments. Up to 100% Zn and Cd removal (from the liquid phase) was observed in all the four columns, however the mechanisms were different. Metal removal in column K1 (containing sulphate), was attributed to biological sulphate reduction and subsequent metal precipitation (as sulphides). In the presence of both nitrate and sulphate (K2), the former dominated the process, precipitating the heavy metals as hydroxides and/or carbonates. In the presence of sulphate, nitrate and supplemental iron (Fe(OH)(3)) (K3), metal removal was also due to precipitation as hydroxides and/or carbonates. In abiotic column, K4, (with supplemental iron (Fe(OH)(3)), but no nitrate), cation exchange with soil led to metal removal. The results obtained were modeled using the reactive transport model PHREEQC-2 to elucidate governing processes and to evaluate scenarios of organic carbon, sulphate and nitrate inputs.

  20. Soluble metal pool as affected by soil addition with organic inputs.

    PubMed

    Hernandez-Soriano, Maria C; Peña, Aránzazu; Mingorance, Maria Dolores

    2013-04-01

    The potential impact of diverse inputs of organic matter (hay, maize straw, and peat) on the mobility and bioavailability of Cd, Cu, Pb, and Zn was examined at laboratory scale for three soils with contrasting properties and for two moisture regimes: field capacity and saturated conditions. Soil solution was characterized for total soluble metals, dissolved soil organic carbon, and ultraviolet absorbance at 254 nm. Speciation analyses were performed with WHAM VI. For field capacity conditions, metal mobility increased (Pb>Cu>Zn>Cd) for all soils and treatments compared with controls and was significantly correlated (p<0.05) with dissolved organic matter (r=0.540). Solubilization of organic matter was mostly driven by Al mobilization (r=0.580, p<0.05) and variations in solution pH. The bioavailable pool of metals, estimated as free ion activities, decreased with the increasing occurrence of metal-organic matter complexes, which was accompanied by an increase in solution of highly aromatic organic matter. Soil saturation generally decreased metal mobility and the ratio of metal-organo matter complexes in solution. Consistently, such effects were accompanied by a decrease in the solubilization of organic matter and lower mobilization of Al, Fe, and Mn. Copyright © 2013 SETAC.

  1. Chemically reduced graphene contains inherent metallic impurities present in parent natural and synthetic graphite

    PubMed Central

    Ambrosi, Adriano; Chua, Chun Kiang; Khezri, Bahareh; Sofer, Zdeněk; Webster, Richard D.; Pumera, Martin

    2012-01-01

    Graphene-related materials are in the forefront of nanomaterial research. One of the most common ways to prepare graphenes is to oxidize graphite (natural or synthetic) to graphite oxide and exfoliate it to graphene oxide with consequent chemical reduction to chemically reduced graphene. Here, we show that both natural and synthetic graphite contain a large amount of metallic impurities that persist in the samples of graphite oxide after the oxidative treatment, and chemically reduced graphene after the chemical reduction. We demonstrate that, despite a substantial elimination during the oxidative treatment of graphite samples, a significant amount of impurities associated to the chemically reduced graphene materials still remain and alter their electrochemical properties dramatically. We propose a method for the purification of graphenes based on thermal treatment at 1,000 °C in chlorine atmosphere to reduce the effect of such impurities on the electrochemical properties. Our findings have important implications on the whole field of graphene research. PMID:22826262

  2. Chemically reduced graphene contains inherent metallic impurities present in parent natural and synthetic graphite.

    PubMed

    Ambrosi, Adriano; Chua, Chun Kiang; Khezri, Bahareh; Sofer, Zdeněk; Webster, Richard D; Pumera, Martin

    2012-08-07

    Graphene-related materials are in the forefront of nanomaterial research. One of the most common ways to prepare graphenes is to oxidize graphite (natural or synthetic) to graphite oxide and exfoliate it to graphene oxide with consequent chemical reduction to chemically reduced graphene. Here, we show that both natural and synthetic graphite contain a large amount of metallic impurities that persist in the samples of graphite oxide after the oxidative treatment, and chemically reduced graphene after the chemical reduction. We demonstrate that, despite a substantial elimination during the oxidative treatment of graphite samples, a significant amount of impurities associated to the chemically reduced graphene materials still remain and alter their electrochemical properties dramatically. We propose a method for the purification of graphenes based on thermal treatment at 1,000 °C in chlorine atmosphere to reduce the effect of such impurities on the electrochemical properties. Our findings have important implications on the whole field of graphene research.

  3. Effect of Operating Parameters and Chemical Additives on Crystal Habit and Specific Cake Resistance of Zinc Hydroxide Precipitates

    SciTech Connect

    Alwin, Jennifer Louise

    1999-08-01

    The effect of process parameters and chemical additives on the specific cake resistance of zinc hydroxide precipitates was investigated. The ability of a slurry to be filtered is dependent upon the particle habit of the solid and the particle habit is influenced by certain process variables. The process variables studied include neutralization temperature, agitation type, and alkalinity source used for neutralization. Several commercially available chemical additives advertised to aid in solid/liquid separation were also examined in conjunction with hydroxide precipitation. A statistical analysis revealed that the neutralization temperature and the source of alkalinity were statistically significant in influencing the specific cake resistance of zinc hydroxide precipitates in this study. The type of agitation did not significantly effect the specific cake resistance of zinc hydroxide precipitates. The use of chemical additives in conjunction with hydroxide precipitation had a favorable effect on the filterability. The morphology of the hydroxide precipitates was analyzed using scanning electron microscopy.

  4. Occupational and Qualification Structures in the Field of Environmental Protection in the Metal and Chemical Industries in the United Kingdom.

    ERIC Educational Resources Information Center

    European Centre for the Development of Vocational Training, Berlin (Germany).

    A study analyzed the occupational structure and qualifications associated with the field of environmental protection in the metal and chemical industries in the United Kingdom. The analysis included nine case studies based on interviews with firms in the chemicals and metals sectors. Information was gathered within an analytical framework that…

  5. Photonic crystal membrane reflectors by magnetic field-guided metal-assisted chemical etching

    NASA Astrophysics Data System (ADS)

    Balasundaram, Karthik; Mohseni, Parsian K.; Shuai, Yi-Chen; Zhao, Deyin; Zhou, Weidong; Li, Xiuling

    2013-11-01

    Metal-assisted chemical etching (MacEtch) is a simple etching method that uses metal as the catalyst for anisotropic etching of semiconductors. However, producing nano-structures using MacEtch from discrete metal patterns, in contrast to interconnected ones, has been challenging because of the difficulties in keeping the discrete metal features in close contact with the semiconductor. We report the use of magnetic field-guided MacEtch (h-MacEtch) to fabricate periodic nanohole arrays in silicon-on-insulator (SOI) wafers for high reflectance photonic crystal membrane reflectors. This study demonstrates that h-MacEtch can be used in place of conventional dry etching to produce ordered nanohole arrays for photonic devices.

  6. Structural, chemical and biological aspects of antioxidants for strategies against metal and metalloid exposure

    PubMed Central

    2009-01-01

    Oxidative stress contributes to the pathophysiology of exposure to heavy metals/metalloid. Beneficial renal effects of some medications, such as chelation therapy depend at least partially on the ability to alleviate oxidative stress. The administration of various natural or synthetic antioxidants has been shown to be of benefit in the prevention and attenuation of metal induced biochemical alterations. These include vitamins, N-acetylcysteine, α-lipoic acid, melatonin, dietary flavonoids and many others. Human studies are limited in this regard. Under certain conditions, surprisingly, the antioxidant supplements may exhibit pro-oxidant properties and even worsen metal induced toxic damage. To date, the evidence is insufficient to recommend antioxidant supplements in subject with exposure to metals. Prospective, controlled clinical trials on safety and effectiveness of different therapeutic antioxidant strategies either individually or in combination with chelating agent are indispensable. The present review focuses on structural, chemical and biological aspects of antioxidants particularly related to their chelating properties. PMID:20716905

  7. Chemical fractionations in meteorites. VIII - Iron meteorites and the cosmochemical history of the metal phase

    NASA Technical Reports Server (NTRS)

    Kelly, W. R.; Larimer, J. W.

    1977-01-01

    The chemical composition of the metal phase of iron meteorites is traced through an idealized traditional history from condensation, oxidation, and accretion in the nebula to melting, segregation, and freezing in a parent body, considering the following fifteen elements: Au, Co, Cu, Fe, Ga, Ge, Ir, Mo, Ni, Os, Pd, Pt, Re, Rh, and Ru. Twelve iron meteorite groups resolved by Scott and Wasson (1975) are considered in the framework of cosmochemical historical analysis. The parent bodies of five of these groups seem to have had a traditional history. The others seem to have had more unusual histories. For example, the composition of the metal in group IVB matches that predicted for the metal condensate at 1270 K, implying accretion at high temperatures; and the metal in group IVA has a composition indicative of aggregates undergoing progressive stages of partial melting.

  8. Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy.

    PubMed

    Linic, Suljo; Christopher, Phillip; Ingram, David B

    2011-11-23

    Recent years have seen a renewed interest in the harvesting and conversion of solar energy. Among various technologies, the direct conversion of solar to chemical energy using photocatalysts has received significant attention. Although heterogeneous photocatalysts are almost exclusively semiconductors, it has been demonstrated recently that plasmonic nanostructures of noble metals (mainly silver and gold) also show significant promise. Here we review recent progress in using plasmonic metallic nanostructures in the field of photocatalysis. We focus on plasmon-enhanced water splitting on composite photocatalysts containing semiconductor and plasmonic-metal building blocks, and recently reported plasmon-mediated photocatalytic reactions on plasmonic nanostructures of noble metals. We also discuss the areas where major advancements are needed to move the field of plasmon-mediated photocatalysis forward.

  9. Effect of solvents on the chemical and physical properties of ionic polymer-metal composites

    NASA Astrophysics Data System (ADS)

    Nemat-Nasser, Sia; Zamani, Shahram; Tor, Yitzhak

    2006-05-01

    Ionic polymer-metal composites (IPMCs) consist of a perfluorinated ionomer membrane (usually Nafion® or Flemion®) plated on both faces with a noble metal such as gold or platinum and neutralized with a certain amount of counterions that balance the electrical charge of anions covalently fixed to the backbone ionomer. IPMCs are electroactive materials with potential applications as actuators and sensors. Their electrical-chemical-mechanical response is dependent on the cations used, the nature and the amount of solvent uptake, the morphology of the electrodes, the composition of the backbone ionomer, the geometry and boundary conditions of the composite element, and the magnitude and spatial and time variation of the applied potential. With water as the solvent, the applied electric potential must be limited to less than 1.3 V at room temperature, to avoid electrolysis. Moreover, water evaporation in open air presents additional problems. These and related factors limit the application of IPMCs with water as the solvent. We present the results of a series of tests on both Nafion- and Flemion-based IPMCs with ethylene glycol, glycerol, and crown ethers as solvents. IPMCs with these solvents have greater solvent uptake and can be subjected to relatively high voltages without electrolysis. They can be actuated in open air for rather long time periods, and at low temperatures. They may be good actuators when high-speed actuation is not necessary. In addition, their slow response in open air allows direct observation of the physical characteristics of the cathode and anode surfaces of a cantilever during actuations. This can provide additional clues for unraveling the underpinning micromechanisms of their actuation. Remarkably, solvents are found to have profound effects on the nature of the IPMCs' actuation. For example, Nafion-based IPMCs in Li+ form show very small back relaxation when hydrated, but extensive back relaxation with all other solvents that we have

  10. HIGH-RESOLUTION SPECTROSCOPY OF EXTREMELY METAL-POOR STARS FROM SDSS/SEGUE. I. ATMOSPHERIC PARAMETERS AND CHEMICAL COMPOSITIONS

    SciTech Connect

    Aoki, Wako; Suda, Takuma; Beers, Timothy C.; Lee, Young Sun; Honda, Satoshi; Ito, Hiroko; Takada-Hidai, Masahide; Frebel, Anna; Fujimoto, Masayuki Y.; Carollo, Daniela; Sivarani, Thirupathi E-mail: takuma.suda@nao.ac.jp E-mail: lee@pa.msu.edu E-mail: hidai@apus.rh.u-tokai.ac.jp E-mail: fujimoto@astro1.sci.hokudai.ac.jp E-mail: sivarani@iiap.res.in

    2013-01-01

    Chemical compositions are determined based on high-resolution spectroscopy for 137 candidate extremely metal-poor (EMP) stars selected from the Sloan Digital Sky Survey (SDSS) and its first stellar extension, the Sloan Extension for Galactic Understanding and Exploration (SEGUE). High-resolution spectra with moderate signal-to-noise (S/N) ratios were obtained with the High Dispersion Spectrograph of the Subaru Telescope. Most of the sample (approximately 80%) are main-sequence turnoff stars, including dwarfs and subgiants. Four cool main-sequence stars, the most metal-deficient such stars known, are included in the remaining sample. Good agreement is found between effective temperatures estimated by the SEGUE stellar parameter pipeline, based on the SDSS/SEGUE medium-resolution spectra, and those estimated from the broadband (V - K){sub 0} and (g - r){sub 0} colors. Our abundance measurements reveal that 70 stars in our sample have [Fe/H] < -3, adding a significant number of EMP stars to the currently known sample. Our analyses determine the abundances of eight elements (C, Na, Mg, Ca, Ti, Cr, Sr, and Ba) in addition to Fe. The fraction of carbon-enhanced metal-poor stars ([C/Fe] > +0.7) among the 25 giants in our sample is as high as 36%, while only a lower limit on the fraction (9%) is estimated for turnoff stars. This paper is the first of a series of papers based on these observational results. The following papers in this series will discuss the higher-resolution and higher-S/N observations of a subset of this sample, the metallicity distribution function, binarity, and correlations between the chemical composition and kinematics of extremely metal-poor stars.

  11. Recovery of metal values from spent lithium-ion batteries with chemical deposition and solvent extraction

    NASA Astrophysics Data System (ADS)

    Nan, Junmin; Han, Dongmei; Zuo, Xiaoxi

    This paper describes a new recycling process of metal values from spent lithium-ion batteries (LIBs). After the dismantling of the spent batteries steel crusts, the leaching of battery internal substances with alkaline solution and the dissolving of the residues with H 2SO 4 solution were carried out. Then mass cobalt was chemically deposited as oxalate, and Acorga M5640 and Cyanex272 extracted the small quantities of copper and cobalt, respectively. Lithium was recovered as deposition of lithium carbonate. It is shown that about 90% cobalt was deposited as oxalate with less than 0.5% impurities, and Acorga M5640 and Cyanex272 were efficient and selective for the extraction of copper and cobalt in sulfate solution. Over 98% of the copper and 97% of the cobalt was recovered in the given process. In addition, the waste solution was treated innocuously, and LiCoO 2 positive electrode material with good electrochemical performance was also synthesized by using the recovered compounds of cobalt and lithium as precursors. The process is feasible for the recycling of spent LIBs in scale-up.

  12. Highly scalable, atomically thin WSe2 grown via metal-organic chemical vapor deposition.

    PubMed

    Eichfeld, Sarah M; Hossain, Lorraine; Lin, Yu-Chuan; Piasecki, Aleksander F; Kupp, Benjamin; Birdwell, A Glen; Burke, Robert A; Lu, Ning; Peng, Xin; Li, Jie; Azcatl, Angelica; McDonnell, Stephen; Wallace, Robert M; Kim, Moon J; Mayer, Theresa S; Redwing, Joan M; Robinson, Joshua A

    2015-02-24

    Tungsten diselenide (WSe2) is a two-dimensional material that is of interest for next-generation electronic and optoelectronic devices due to its direct bandgap of 1.65 eV in the monolayer form and excellent transport properties. However, technologies based on this 2D material cannot be realized without a scalable synthesis process. Here, we demonstrate the first scalable synthesis of large-area, mono and few-layer WSe2 via metal-organic chemical vapor deposition using tungsten hexacarbonyl (W(CO)6) and dimethylselenium ((CH3)2Se). In addition to being intrinsically scalable, this technique allows for the precise control of the vapor-phase chemistry, which is unobtainable using more traditional oxide vaporization routes. We show that temperature, pressure, Se:W ratio, and substrate choice have a strong impact on the ensuing atomic layer structure, with optimized conditions yielding >8 μm size domains. Raman spectroscopy, atomic force microscopy (AFM), and cross-sectional transmission electron microscopy (TEM) confirm crystalline monoto-multilayer WSe2 is achievable. Finally, TEM and vertical current/voltage transport provide evidence that a pristine van der Waals gap exists in WSe2/graphene heterostructures.

  13. Raman diagnostics of photoinduced heating of silicon nanowires prepared by metal-assisted chemical etching

    NASA Astrophysics Data System (ADS)

    Rodichkina, S. P.; Osminkina, L. A.; Isaiev, M.; Pavlikov, A. V.; Zoteev, A. V.; Georgobiani, V. A.; Gonchar, K. A.; Vasiliev, A. N.; Timoshenko, V. Yu.

    2015-12-01

    Raman spectroscopy was applied to investigate laser-induced heating of silicon nanowires (SiNWs) formed by metal-assisted chemical etching of lightly boron-doped crystalline silicon (c-Si) wafers. Low-frequency shift of the Raman peak from 520.5 cm-1 to about 517 cm-1 for SiNWs with length of 40-65 µm under laser irradiation with wavelengths of 632.8 or 488 nm was observed, and it was explained by an increase in the average temperature of SiNWs on about 150 K for the laser intensity about 1 kW/cm2. The same photoinduced heating was confirmed by analyzing the ratio between the Stokes and anti-Stokes components of the Raman scattering. The obtained experimental data allow us to estimate the thermal conductivity coefficient of SiNW array ~0.1 W/(m K), which is three orders of magnitude smaller than that of c-Si. Furthermore, the Raman spectra of SiNWs under excitation with intensity above 0.2-0.5 kW/cm2 consisted of an additional low-frequency peak, which is related to an overheated subsystem of well spatially separated fine SiNWs up to 600-700 K. The observed strong photoinduced heating can be used for local laser-induced treatment of SiNWs and biomedical applications.

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

    NASA Astrophysics Data System (ADS)

    Johnston, Jamin M.; Catledge, Shane A.

    2016-02-01

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

  15. Factors affecting the microbial and chemical composition of silage. III. Effect of urea additions on maize silage.

    PubMed

    Mahmoud, S A; Abd-el-Hafez, A; Zaki, M M; Saleh, E A

    1978-01-01

    The effect of urea additions on the microbiological and chemical properties of silage, produced from young maize plants (Darawa stage), was studied. Urea treatments, i.e., 0.25%, 0.50%, 0.75%, and 1.00%, stimulated higher densities of the desired microorganisms than the control, while undesired organisms showed lower counts (proteolytic and saccharolytic anaerobes). Addition of 0.25 to 0.50% or urea resulted in the production of high quality silage with pleasant small and high nutritive value, as confirmed by the various microbiological and chemical analyses conducted. Higher levels (0.75 and 1.00%) of urea decreased the quality of the product.

  16. Effect of metal oxide additions to quality on Ge/GeO2 interfaces

    NASA Astrophysics Data System (ADS)

    Li, Hongfei; Robertson, John; Okuno, Yasutoshi

    2016-10-01

    Alloying amorphous GeO2 with Y2O3 or related group IIIA oxides is known experimentally to improve its properties as a gate dielectric in field effect transistors. The mechanism of this is studied here by density functional calculations. The metal site coordination is found to be 6-7, by increasing the oxygen coordination to 3 or higher. The alloying is found to increase the bulk modulus. Alloying also increases the diffusion energy of the oxygen vacancies in GeO2 next to the metal and also increases the vacancy formation energy of oxygens that are second neighbors of the metal sites. In this way, a relatively small metal concentration can reduce the O vacancy diffusion rate and thereby the GeO evolution rate. Oxygen vacancies at the Ge/GeO2 interface next to a metal site are found to divide into two types, those which rebond across the vacancy (La, Hf) and those without rebonding (Y, Sc, Al), the latter being preferable as they do not give rise to interfacial gap states.

  17. Alkali-metal-catalyzed addition of primary and secondary phosphines to carbodiimides. A general and efficient route to substituted phosphaguanidines.

    PubMed

    Zhang, Wen-Xiong; Nishiura, Masayoshi; Hou, Zhaomin

    2006-09-28

    Organo alkali metal compounds such as (n)BuLi and (Me3Si)2NK act as excellent catalyst precursors for the addition of phosphine P-H bonds to carbodiimides, offering a general and atom-economical route to substituted phosphaguanidines, with excellent tolerability to aromatic C-Br and C-Cl bonds.

  18. Phytoremediation of heavy metal-contaminated soils: natural hyperaccumulation versus chemically enhanced phytoextraction.

    PubMed

    Lombi, E; Zhao, F J; Dunham, S J; McGrath, S P

    2001-01-01

    A pot experiment was conducted to compare two strategies of phytoremediation: natural phytoextraction using the Zn and Cd hyperaccumulator Thlaspi caerulescens J. Presl & C. Presl versus chemically enhanced phytoextraction using maize (Zea mays L.) treated with ethylenediaminetetraacetic acid (EDTA). The study used an industrially contaminated soil and an agricultural soil contaminated with metals from sewage sludge. Three crops of T. caerulescens grown over 391 d removed more than 8 mg kg(-1) Cd and 200 mg kg(-1) Zn from the industrially contaminated soil, representing 43 and 7% of the two metals in the soil. In contrast, the high concentration of Cu in the agricultural soil severely reduced the growth of T. caerulescens, thus limiting its phytoextraction potential. The EDTA treatment greatly increased the solubility of heavy metals in both soils, but this did not result in a large increase in metal concentrations in the maize shoots. Phytoextraction of Cd and Zn by maize + EDTA was much smaller than that by T. caerulescens from the industrially contaminated soil, and was either smaller (Cd) or similar (Zn) from the agricultural soil. After EDTA treatment, soluble heavy metals in soil pore water occurred mainly as metal-EDTA complexes, which were persistent for several weeks. High concentrations of heavy metals in soil pore water after EDTA treatment could pose an environmental risk in the form of ground water contamination.

  19. Evaluation of trace metals bioavailability in Japanese river waters using DGT and a chemical equilibrium model.

    PubMed

    Han, Shuping; Naito, Wataru; Hanai, Yoshimichi; Masunaga, Shigeki

    2013-09-15

    To develop efficient and effective methods of assessing and managing the risk posed by metals to aquatic life, it is important to determine the effects of water chemistry on the bioavailability of metals in surface water. In this study, we employed the diffusive gradients in thin-films (DGT) to determine the bioavailability of metals (Ni, Cu, Zn, and Pb) in Japanese water systems. The DGT results were compared with a chemical equilibrium model (WHAM 7.0) calculation to examine its robustness and utility to predict dynamic metal speciation. The DGT measurements showed that biologically available fractions of metals in the rivers impacted by mine drainage and metal industries were relatively high compared with those in urban rivers. Comparison between the DGT results and the model calculation indicated good agreement for Zn. The model calculation concentrations for Ni and Cu were higher than the DGT concentrations at most sites. As for Pb, the model calculation depended on whether the precipitated iron(III) hydroxide or precipitated aluminum(III) hydroxide was assumed to have an active surface. Our results suggest that the use of WHAM 7.0 combined with the DGT method can predict bioavailable concentrations of most metals (except for Pb) with reasonable accuracy.

  20. Chemical activation of molecules by metals: Experimental studies of electron distributions and bonding

    SciTech Connect

    Lichtenberger, D.L.

    1992-01-01

    Purpose of this research program is to obtain experimental information on the different fundamental ways metals bond and activate organic molecules. Our approach has been to directly probe the electronic interactions between metals and molecules through a wide variety of ionization spectroscopies and other techniques, and to investigate the relationships with bonding modes, structures, and chemical behavior. During this period, we have (1) characterized the electronic features of diphosphines and monophosphines in their coordination to metals, (2) carried out theoretical and experimental investigations of the bonding capabilities of C[sub 60] to transition metals, (3) developed techniques for the imaging of single molecules on gold substrates that emphasizes the electronic backbonding from the metal to the molecule, (4) obtained the high resolution photoelectron spectrum of pure C[sub 70] in the gas phase, (5) compared the bonding of [eta][sup 3]- acetylide ligands to the bonding of other small organic molecules with metals, and (6) reported the photoelectron spectra and bonding of [eta][sup 3]-cyclopropenyl groups to metals.