Science.gov

Sample records for metal chemical addition

  1. 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.

  2. 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.

  3. Pharmacological and Chemical Effects of Cigarette Additives

    PubMed Central

    Rabinoff, Michael; Caskey, Nicholas; Rissling, Anthony; Park, Candice

    2007-01-01

    We investigated tobacco industry documents and other sources for evidence of possible pharmacological and chemical effects of tobacco additives. Our findings indicated that more than 100 of 599 documented cigarette additives have pharmacological actions that camouflage the odor of environmental tobacco smoke emitted from cigarettes, enhance or maintain nicotine delivery, could increase the addictiveness of cigarettes, and mask symptoms and illnesses associated with smoking behaviors. Whether such uses were specifically intended for these agents is unknown. Our results provide a clear rationale for regulatory control of tobacco additives. PMID:17666709

  4. Metrology Needs for Metal Additive Manufacturing Powders

    NASA Astrophysics Data System (ADS)

    Slotwinski, John A.; Garboczi, Edward J.

    2015-03-01

    Additive manufacturing (AM) processes can produce highly complex and customized parts without the need for dedicated tooling and can produce parts directly from the part design information. These types of processes are poised to revolutionize the manufacturing industry, yet several challenges are currently preventing more widespread adoption of AM technologies. Among these challenges are metrology issues associated with the measurement and characterization of the metal powders used for AM systems. This article will describe the technical challenges and needs for characterizing metal AM powders, recent research efforts to address those needs, and current work to standardize characterization methods in ASTM and ISO, such as the recently released ASTM F3049, Standard Guide for Characterizing Properties of Metal Powders Used for Additive Manufacturing Processes.

  5. 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.

  6. Enhancing toxic metal removal from acidified sludge with nitrite addition.

    PubMed

    Du, Fangzhou; Freguia, Stefano; Yuan, Zhiguo; Keller, Jürg; Pikaar, Ilje

    2015-05-19

    The production of sludge (biosolids) during wastewater treatment is a major issue for water utilities. A main issue limiting its beneficial reuse on agricultural lands is the presence of toxic metals. The currently used metal reduction technologies achieve insufficient removal of metals that are bound to the organic fraction of the sludge. In this study, we propose and demonstrate a novel method that involves the addition of nitrite during sludge acidification to enhance metal removal. Using waste activated sludge collected from three full-scale wastewater treatment plants, we found that acidification to pH 2.0 achieved good Zn solubilization of around 70%, but only 3-7% of Cu was being dissolved. Nitrite addition to the acidified sludge at a concentration of 20 mg NO2(-)-N/L (equals to 19.2 mg HNO2-N/L), substantially enhanced Cu removal to 45-64%, while Zn removal was also increased to over 81%. Metal distribution analysis using sequential chemical extraction revealed that the improvement of Cu and Zn removal was mainly due to the release of the organically bound metal fraction. We hypothesize that free nitrous acid (HNO2, FNA) may assist in the (partial) disruption of extracellular polymeric substances (EPS) and the subsequent release and solubilization of fixed metals. PMID:25872418

  7. 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.

  8. 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.

    2016-05-01

    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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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...

  14. 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...

  15. 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...

  16. 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...

  17. 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...

  18. 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

    2008-02-01

    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. PMID:18209787

  19. Understanding composite explosive energetics: I, The role of metallic additives

    SciTech Connect

    Tao, W.C.; Tarver, C.M.; Breithaupt, D.R.; McGuire, R.R.; Ornellas, D.L.

    1990-01-01

    Composite explosives (CE) have found major applications in air blast, cratering, fragmentation, underwater applications, and other commercial and military systems in which prompt delivery of the available energy is not a primary requirement. In direct metal acceleration applications, composite explosives have not generally been effective because their potential energy is transformed to kinetic energy over time periods extending to tens of microseconds. We are interested in defining the rate determining steps and understanding the chemical interactions between different components in the composite explosive formulation in order to determine the partitioning of the available energy. In this study, we investigate the role of the metallic additive in a bicomponent composite explosive consisting of PETN and aluminum. Of specific interests are the early time performance of and the extent of aluminum reaction in the composite formulation. For formulations loaded with 5 wt% and 10 wt% of 5 micron spherical aluminum, we found that 100% of the aluminum reacted within the first microsecond of volume expansion. The extent of aluminum reaction with the PETN detonation products is reduced to about 65% for composite formulations loaded with 20 wt% aluminum. It is evident from the results of a series of scaling experiments that the detonation behavior of the PETN-aluminum bicomponent composite explosive is nonideal. 6 refs., 11 figs., 2 tabs.

  20. 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.

  1. 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.

  2. 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

  3. 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 sue chemical additives to manipulate the catalytic properties of Rh- and Ni-based catalysts for producing high yields of ethanol from syngas. (VC)

  4. 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.

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

    SciTech Connect

    Chuang, S.S.C.

    1988-11-14

    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 including temperature programmed desorption, infrared study of NO adsorption, reactive probing, steady 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.

  6. 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. PMID:25052592

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

    SciTech Connect

    Chuang, S.S.C.; Balakos, M.W.

    1991-09-20

    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 additives 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. 27 refs. 7 figs., 2 tabs.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

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

    SciTech Connect

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

    1992-07-01

    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 CTE's of conventional polyimides range from 30 to 60 ppm/C. Approaches that have been reported to lower their CTE's include linearizing the polymer molecular structure and orienting the polyimide film. This current study involves the incorporation of metal ion-containing additives into polyimides and has resulted in significantly lowered CTE's. 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% to over 100% depending on the choice of additive and its concentration.

  15. 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.

  16. 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.

  17. 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)…

  18. 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. PMID:23552653

  19. 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.

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

    SciTech Connect

    Chuang, S.S.C.

    1989-02-04

    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 will include S, P, Ag, Cu, Mn, and Na. 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 studies including temperature programmed desorption, infrared study of NO adsorption, reactive probing, steady state rate measurement, and transient kinetic study. A better understanding of the role of additive 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. CO insertion is known to be a key step to the formation of acetaldehyde and ethanol from CO hydrogenation over Rh catalysts. Ethylene hydroformylation has often served as a probe to determine CO insertion capabilities of Rh catalysts. The mechanism of CO insertion in ethylene hydroformylation over Rh/SiO{sub 2} was investigated.

  1. 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

  2. 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

  3. 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. PMID:26601041

  4. 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.

  5. Role of metal ferrocyanides in chemical evolution

    NASA Astrophysics Data System (ADS)

    Kamaluddin; Nath, Mala; Sharma, Archana

    1994-11-01

    Adsorption of several ribose and 2'-deoxyribose 5'-nucleotides on zinc- and copper ferrocyanides has been studied at a neutral pH of 7.01. The Langmuir adsorption isotherm was used to determine the values of KL and Xm. Both types of nucleotides, ribose and 2'-deoxyribose, showed similar adsorption behavior on zinc- and copper ferrocyanides. Zinc ferrocyanide showed larger adsorption as compared to copper ferrocyanide. Purine nucleotides adsorbed more than pyrimidine nucleotides on both the metal ferrocyanides probably because of an additional binding site in the imidazole ring in purines. Results of the present study suggest the importance of metal ferrocyanides and metal ions in stabilization of nucleotides during processes of prebiotic condensation reactions.

  6. Chemical tracers of high-metallicity environments

    NASA Astrophysics Data System (ADS)

    Bayet, E.; Davis, T. A.; Bell, T. A.; Viti, S.

    2012-08-01

    We present for the first time a detailed study of the properties of molecular gas in metal-rich environments such as early-type galaxies (ETGs). We have explored photon-dominated region chemistry for a wide range of physical conditions likely to be appropriate for these sources. We derive fractional abundances of the 20 most chemically reactive species as a function of the metallicity, as a function of the optical depth and for various volume number gas densities, far-ultraviolet (FUV) radiation fields and cosmic ray ionization rates. We also investigate the response of the chemistry to the changes in α-element enhancement as seen in ETGs. We find that the fractional abundances of CS, H2S, H2CS, H2O, H3O+, HCO+ and H2CN seem invariant to an increase of metallicity whereas C+, CO, C2H, CN, HCN, HNC and OCS appear to be the species most sensitive to this change. The most sensitive species to the change in the fractional abundance of α-elements are C+, C, CN, HCN, HNC, SO, SO2, H2O and CS. Finally, we provide line brightness ratios for the most abundant species, especially in the range observable with Atacama Large Millimeter Array (ALMA). Discussion of favourable line ratios to be used for the estimation of supersolar metallicities and α-elements are also provided.

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. The metallurgy and processing science of metal additive manufacturing

    DOE PAGESBeta

    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 developedmore » for commercial production, but recent development efforts are presented as a path for the ongoing development of new materials for AM processes.« less

  12. 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

    2014-01-01

    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

  13. 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

    2016-01-01

    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.

  14. Epoxy nanocomposites with two-dimensional transition metal dichalcogenide additives.

    PubMed

    Eksik, Osman; Gao, Jian; Shojaee, S Ali; Thomas, Abhay; Chow, Philippe; Bartolucci, Stephen F; Lucca, Don A; Koratkar, Nikhil

    2014-05-27

    Emerging two-dimensional (2D) materials such as transition metal dichalcogenides offer unique and hitherto unavailable opportunities to tailor the mechanical, thermal, electronic, and optical properties of polymer nanocomposites. In this study, we exfoliated bulk molybdenum disulfide (MoS2) into nanoplatelets, which were then dispersed in epoxy polymers at loading fractions of up to 1% by weight. We characterized the tensile and fracture properties of the composite and show that MoS2 nanoplatelets are highly effective at enhancing the mechanical properties of the epoxy at very low nanofiller loading fractions (below 0.2% by weight). Our results show the potential of 2D sheets of transition metal dichalcogenides as reinforcing additives in polymeric composites. Unlike graphene, transition metal dichalcogenides such as MoS2 are high band gap semiconductors and do not impart significant electrical conductivity to the epoxy matrix. For many applications, it is essential to enhance mechanical properties while also maintaining the electrical insulation properties and the high dielectric constant of the polymer material. In such applications, conductive carbon based fillers such as graphene cannot be utilized. This study demonstrates that 2D transition metal dichalcogenide additives offer an elegant solution to such class of problems. PMID:24754702

  15. Effects of chemical additives on microbial enhanced oil recovery processes

    SciTech Connect

    Bryant, R.S.; Chase, K.L.; Bertus, K.M.; Stepp, A.K.

    1989-12-01

    An extensive laboratory study has been conducted to determine (1) the role of the microbial cells and products in oil displacement, (2) the relative rates of transport of microbial cells and chemical products from the metabolism of nutrient in porous media, and (3) the effects of chemical additives on the oil recovery efficiency of microbial formulations. This report describes experiments relating to the effects of additives on oil recovery efficiency of microbial formulations. The effects of additives on the oil recovery efficiency of microbial formulations were determined by conducting oil displacement experiments in 1-foot-long Berea sandstone cores. Sodium tripolyphosphate (STPP), a low-molecular-weight polyacrylamide polymer, a lignosulfonate surfactant, and sodium bicarbonate were added to a microbial formulation at a concentration of 1%. The effects of using these additives in a preflush prior to injection of the microbial formulation were also evaluated. Oil-displacement experiments with and without a sodium bicarbonate preflush were conducted in 4-foot-long Berea sandstone cores, and samples of in situ fluids were collected at various times at four intermediate points along the core. The concentrations of metabolic products and microbes in the fluid samples were determined. 9 refs., 22 figs., 8 tabs.

  16. 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

  17. 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

  18. 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.

  19. Chemical treatment of chelated metal finishing wastes.

    PubMed

    McFarland, Michael J; Glarborg, Christen; Ross, Mark A

    2012-12-01

    This study evaluated two chemical approaches for treatment of commingled cadmium-cyanide (Cd-CN) and zinc-nickel (Zn-Ni) wastewaters. The first approach, which involved application of sodium hypochlorite (NaOCl), focused on elimination of chelating substances. The second approach evaluated the use of sodium dimethyldithiocarbamate (DMDTC) to specifically target and precipitate regulated heavy metals. Results demonstrated that by maintaining a pH of 10.0 and an oxidation-reduction potential (ORP) value of +600 mV, NaOCl treatment was effective in eliminating all chelating substances. Cadmium, chromium, nickel, and zinc solution concentrations were reduced from 0.27, 4.44, 0.06, and 0.10 ppm to 0.16, 0.17, 0.03, and 0.06 ppm, respectively. Similarly, a 1% DMDTC solution reduced these same metal concentrations in commingled wastewater to 0.009, 1.142, 0.036, and 0.320 ppm. Increasing the DMDTC concentration to 2% improved the removal of all regulated heavy metals except zinc, the removal of which at high pH values is limited by its amphotericity. PMID:23342939

  20. Automated determination of chemical functionalisation addition routes based on magnetic susceptibility and nucleus independent chemical shifts

    NASA Astrophysics Data System (ADS)

    Van Lier, G.; Ewels, C. P.; Geerlings, P.

    2008-07-01

    We present a modified version of our previously reported meta-code SACHA, for systematic analysis of chemical addition. The code automates the generation of structures, running of quantum chemical codes, and selection of preferential isomers based on chosen selection rules. While the selection rules for the previous version were based on the total system energy, predicting purely thermodynamic addition patterns, we examine here the possibility of using other system parameters, notably magnetic susceptibility as a descriptor of global aromaticity, and nucleus independent chemical shifts (NICS) as local aromaticity descriptor.

  1. 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.

  2. 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).

  3. 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.

  4. 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.

  5. 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.

  6. Thyroid disrupting chemicals in plastic additives and thyroid health.

    PubMed

    Andra, Syam S; Makris, Konstantinos C

    2012-01-01

    The globally escalating thyroid nodule incidence rates may be only partially ascribed to better diagnostics, allowing for the assessment of environmental risk factors on thyroid disease. Endocrine disruptors or thyroid-disrupting chemicals (TDC) like bisphenol A, phthalates, and polybrominated diphenyl ethers are widely used as plastic additives in consumer products. This comprehensive review studied the magnitude and uncertainty of TDC exposures and their effects on thyroid hormones for sensitive subpopulation groups like pregnant women, infants, and children. Our findings qualitatively suggest the mixed, significant (α = 0.05) TDC associations with natural thyroid hormones (positive or negative sign). Future studies should undertake systematic meta-analyses to elucidate pooled TDC effect estimates on thyroid health indicators and outcomes. PMID:22690712

  7. 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.

  8. Metal-ceramic microstructures in the Fe-Mn-O system -- Morphology control by impurity addition

    SciTech Connect

    Subramanian, R.; Uestuendag, E.; Sass, S.L.; Dieckmann, R.

    1995-10-01

    The influence of the addition of impurities and changes in the oxygen partial pressure on the formation of metal-ceramic microstructures by partial reduction of ternary or higher ceramic oxides was experimentally investigated in the model system Fe-Mn-O at constant temperature and total pressure. Electron microscopy studies were performed for microstructural characterization, phase identification and chemical analysis. It was observed that the addition of dopants such as BaO, CaO, MgO, SrO, Al{sub 2}O{sub 3}, Cr{sub 2}O{sub 3} or ZrO{sub 2} to the initial, polycrystalline oxide solid solution (Fe{sub 1{minus}x}Mn{sub x}){sub 1{minus}{Delta}}O strongly influences the location and rate of metal precipitation during reduction. Experimental observations are discussed based on solubility limits and the segregation of dopants.

  9. Metallic taste from electrical and chemical stimulation.

    PubMed

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

    2005-03-01

    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

  10. Enhanced metal removal from wastewater by coagulant addition

    SciTech Connect

    Karthikeyan, K.G.; Elliott, H.A.; Cannon, F.S.

    1996-11-01

    Besides metallurgical industries, metal-containing wastewaters are generated in the manufacturing/processing of batteries, petroleum, photographic materials, paints, inks, leather, and wood. The toxic nature of the heavy metals has resulted in the promulgation of standards requiring very low concentration of metals in the treated effluent. To comply with the strict regulatory requirements, it is necessary to treat the wastewaters (both industrial and municipal) before discharging them into natural water bodies. The objective of this study was to compare the pH-dependent Cu and Cd removal profiles for simple precipitation, adsorption, and coprecipitation in the presence of freshly-formed hydrous oxides of Fe and Al. Because of the significantly different pH at which hydrolysis/precipitation occurs, Cu and Cd were chosen as representative heavy metals. The results have been interpreted in the context of investing the use of coagulants to achieve low metal concentrations in wastewater effluents.

  11. Chemical Fracturing of Refractory-Metal Vessels

    NASA Technical Reports Server (NTRS)

    Campana, R. J.

    1986-01-01

    Localized reactions cause refractory-metal vessels to break up at predetermined temperatures. Device following concept designed to break up along predetermined lines into smaller pieces at temperature significantly below melting point of metal from which made. Possible applications include fire extinguishers that breakup to release extinguishing gas in enclosed areas, pressure vessels that could otherwise burst dangerously in fire, and self-destroying devices. Technique particularly suitable modification to already existing structures.

  12. 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.

  13. 75 FR 53867 - Additions to Listing of Exempt Chemical Mixtures

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-09-02

    ...Under this Direct Final Rule, the Drug Enforcement Administration (DEA) is updating the Table of Exempt Chemical Mixtures. This action is in response to DEA's review of new applications for exemption. Having reviewed applications and relevant information, DEA finds that these 21 preparations meet the applicable exemption criteria. Therefore, these products are exempted from the application of......

  14. 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.

  15. EXPOSURE TO CHEMICAL ADDITIVES FROM POLYVINYL CHLORIDE POLYMER EXTRUSION PROCESSING

    EPA Science Inventory

    This report presents a model to predict worker inhalation exposure due to off-gassing of additives during polyvinyl chloride (PVC) extrusion processing. ata on off-gassing of additives were reviewed in the literature, the off-gassing at normal PVC processing temperatures was stud...

  16. 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.

  17. 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.

  18. 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…

  19. 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. PMID:26040502

  20. 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)

  1. 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... announcing that Sun Chemical Corp. has filed a petition proposing that the color additive regulations for D&C... been filed by Sun Chemical Corp., 5020 Spring Grove Ave., Cincinnati, OH 45232. The petition...

  2. 15 CFR 714.3 - Advance declaration requirements for additionally planned production of Schedule 3 chemicals.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 3 CHEMICALS § 714.3 Advance... a Schedule 3 chemical above the declaration threshold; (ii) You plan to produce at a plant declared under § 714.1(a)(1)(ii) of the CWCR an additional Schedule 3 chemical above the declaration...

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

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 3 CHEMICALS § 714.3 Advance... a Schedule 3 chemical above the declaration threshold; (ii) You plan to produce at a plant declared under § 714.1(a)(1)(ii) of the CWCR an additional Schedule 3 chemical above the declaration...

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

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 3 CHEMICALS § 714.3 Advance... a Schedule 3 chemical above the declaration threshold; (ii) You plan to produce at a plant declared under § 714.1(a)(1)(ii) of the CWCR an additional Schedule 3 chemical above the declaration...

  5. 15 CFR 714.3 - Advance declaration requirements for additionally planned production of Schedule 3 chemicals.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 3 CHEMICALS § 714.3 Advance... a Schedule 3 chemical above the declaration threshold; (ii) You plan to produce at a plant declared under § 714.1(a)(1)(ii) of the CWCR an additional Schedule 3 chemical above the declaration...

  6. 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.

  7. 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.

  8. Investigation of DOTA-Metal Chelation Effects on the Chemical Shift of (129) Xe.

    PubMed

    Jeong, Keunhong; Slack, Clancy C; Vassiliou, Christophoros C; Dao, Phuong; Gomes, Muller D; Kennedy, Daniel J; Truxal, Ashley E; Sperling, Lindsay J; Francis, Matthew B; Wemmer, David E; Pines, Alexander

    2015-12-01

    Recent work has shown that xenon chemical shifts in cryptophane-cage sensors are affected when tethered chelators bind to metals. Here, we explore the xenon shifts in response to a wide range of metal ions binding to diastereomeric forms of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) linked to cryptophane-A. The shifts induced by the binding of Ca(2+) , Cu(2+) , Ce(3+) , Zn(2+) , Cd(2+) , Ni(2+) , Co(2+) , Cr(2+) , Fe(3+) , and Hg(2+) are distinct. In addition, the different responses of the diastereomers for the same metal ion indicate that shifts are affected by partial folding with a correlation between the expected coordination number of the metal in the DOTA complex and the chemical shift of (129) Xe. These sensors may be used to detect and quantify many important metal ions, and a better understanding of the basis for the induced shifts could enhance future designs. PMID:26376768

  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. Effect of Copper and Other Trace Metal Addition to Pulp and Paper Wastewater.

    PubMed

    Barnett, Jason; Richardson, Desmond; Stack, Karen; Lewis, Trevor

    2015-12-01

    Porous pots were used to mimic, on a laboratory scale, an industrial activated sludge plant from a thermomechanical pulp and news print paper mill. Trace metal additions of Ca, Co, Cu, Fe(III), and Mg were found to improve chemical oxygen demand removal from 82% to 86 to 87%. Copper (0.1 to 1.0 mg/L) was also found to be beneficial in significantly inhibiting the growth of filamentous bacteria, contributing to a reduction of 20 to 45% in sludge volume index (SVI) with improved settle ability and decreased bulking. However, at levels of 1.0 mg/L and higher, the concentration of Cu in the porous pot effluent would potentially exceed guidelines for receiving waters. The fate and impact of Cu was affected by the presence of other trace metals, in particular Mg and Ca. The addition of Mg or Ca along with 0.5 mg/L Cu increased the amount of Cu in the aqueous phase to levels that would potentially exceed government environmental guidelines. Calcium addition was also found to inhibit the effect of Cu in reducing filamentous bacteria and SVI. PMID:26652119

  11. 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.

  12. Metal-air cell with performance enhancing additive

    SciTech Connect

    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.

  13. 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.

  14. 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.

  15. 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.

  16. Chemical behaviour of metallic inclusions in glass melts

    NASA Astrophysics Data System (ADS)

    Stachel, Dörte; Zangenberg, Frauke; Müller, Thomas E.

    2007-05-01

    Inclusions of all kinds cannot be accepted in glass articles. Most of them are non-metallic stones, silicon spheres, cords, bubbles, and sometimes metallic inclusions. Identification of every appearance is not possible, since body structure and chemical composition do not compare. Laboratory experiments regarding the behaviour of the metals copper, brass and iron and their dissolution mechanisms in glass melts at technological relevant temperatures were analysed. Besides partial oxidation processes, sulphidic species were found. The experiments have been compared with thermodynamic calculations of several reaction mechanisms.

  17. Influence of clinoptilolite rock on chemical speciation of selected heavy metals in sewage sludge.

    PubMed

    Sprynskyy, M; Kosobucki, P; Kowalkowski, T; Buszewski, B

    2007-10-22

    The chemical speciation of Cd, Cu, Pb, Cr and Ni in Torun municipal sewage sludge is investigated with addition of a natural sorbent (clinoptilolite rock). The total contents of the heavy metals in the sludge are substantially lower than the corresponding limits established by European or Polish legislation excepting nickel only. But the metals concentrations excepting lead exceed significantly the natural background (average contents in soils and in the Earth's crust) in dozens. Application of the sequential chemical extraction indicated that the metals in the sewage sludge are bound mainly (over 50%) in the residual fraction. The metals form the following order by parts of the mobile form: Ni> Cd> Cr> Cu> Pb. Addition of the clinoptilolite to the sludge leads to the metals contents fall in all four fractions of the sequential procedure. Concentrations of mobile forms of cadmium, chromium, copper and nickel decrease by 87, 64, 35 and 24%, respectively, as a result of addition of 9.09% of the clinoptilolite. The total decreases of the metals amount after 9.09% clinoptilolite addition to the sludge are around 11, 15, 25, 41 and 51% for copper, nickel, chromium, cadmium and lead, respectively. PMID:17513045

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Additive Mixture Effects of Estrogenic Chemicals in Human Cell-Based Assays Can Be Influenced by Inclusion of Chemicals with Differing Effect Profiles

    PubMed Central

    Evans, Richard Mark; Scholze, Martin; Kortenkamp, Andreas

    2012-01-01

    A growing body of experimental evidence indicates that the in vitro effects of mixtures of estrogenic chemicals can be well predicted from the estrogenicity of their components by the concentration addition (CA) concept. However, some studies have observed small deviations from CA. Factors affecting the presence or observation of deviations could include: the type of chemical tested; number of mixture components; mixture design; and assay choice. We designed mixture experiments that address these factors, using mixtures with high numbers of components, chemicals from diverse chemical groups, assays with different in vitro endpoints and different mixture designs and ratios. Firstly, the effects of mixtures composed of up to 17 estrogenic chemicals were examined using estrogenicity assays with reporter-gene (ERLUX) and cell proliferation (ESCREEN) endpoints. Two mixture designs were used: 1) a ‘balanced’ design with components present in proportion to a common effect concentration (e.g. an EC10) and 2) a ‘non-balanced’ design with components in proportion to potential human tissue concentrations. Secondly, the individual and simultaneous ability of 16 potential modulator chemicals (each with minimal estrogenicity) to influence the assay outcome produced by a reference mixture of estrogenic chemicals was examined. Test chemicals included plasticizers, phthalates, metals, PCBs, phytoestrogens, PAHs, heterocyclic amines, antioxidants, UV filters, musks, PBDEs and parabens. In all the scenarios tested, the CA concept provided a good prediction of mixture effects. Modulation studies revealed that chemicals possessing minimal estrogenicity themselves could reduce (negatively modulate) the effect of a mixture of estrogenic chemicals. Whether the type of modulation we observed occurs in practice most likely depends on the chemical concentrations involved, and better information is required on likely human tissue concentrations of estrogens and of potential modulators

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

    NASA Astrophysics Data System (ADS)

    Yae, Shinji; Morii, Yuma; Fukumuro, Naoki; Matsuda, Hitoshi

    2012-06-01

    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.

  5. 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.

  6. 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.

  7. 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.

  8. The effect of additives and substrates on nonferrous metal electrodeposition

    NASA Astrophysics Data System (ADS)

    Zhou, Zeyang

    Electrodeposits play an important role in science and industry today. Control of the quality of electrodeposits becomes more critical. One of the major factors which can lead to better products is the ability to control the electrocrystallization process to obtain smooth, dense and coherent deposits with good mechanical and physical properties, such as corrosion resistance, ductility and less internal stress. Many parameters may play a prominent role in electrodeposition. Two of the more important parameters is the control of impurities/additives present in the solution and cathode condition. In this study, the effects of small concentrations of tin additions on the composition, structure and surface morphology of Zn-Ni alloy deposits were studied. Electrochemical impedance spectroscopy (EIS) were conducted to study the role of tin in changing the charge transfer resistance of the reaction. The results obtained were promising in elucidating some basic factors which influence Zn-Ni alloy electrocrystallization mechanisms. The effects of thermal oxidation of stainless steel cathodes used in copper electrodeposition were studied. Particular emphasis was given to the initial stages of copper nucleation and growth. The copper electrocrystallization process was strongly influenced by the temperature applied in oxidizing the stainless steel. In this research, the effects of the impurities Alsp{3+} and Crsp{3+} using two stainless steels as cathodes during Ni electrowinning from a sulfate bath were studied. The current efficiency decreased in the presence of the impurities over the concentration range studied. Certain changes in the surface morphology, internal stress, crystallographic orientation and polarization behavior were observed. The changes were different for two stainless steel substrates.

  9. 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.

  10. 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. PMID:25774952

  11. 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.

  12. 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. PMID:22793962

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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

    2014-01-01

    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

  18. 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.

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

    NASA Astrophysics Data System (ADS)

    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-C5H4)Rh(CO)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 C60 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 C60 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.

  20. Chemical Abundances of Metal-poor stars in Dwarf Galaxies

    NASA Astrophysics Data System (ADS)

    Venn, Kim A.; Jablonka, Pascale; Hill, Vanessa; Starkenburg, Else; Lemasle, Bertrand; Shetrone, Matthew; Irwin, Mike; Norris, John; Yong, David; Gilmore, Gerry; Salvadori, Stephania; Skuladottir, Asa; Tolstoy, Eline

    2016-08-01

    Stars in low-mass dwarf galaxies show a larger range in their chemical properties than those in the Milky Way halo. The slower star formation efficiency make dwarf galaxies ideal systems for testing nucleosynthetic yields. Not only are alpha-poor stars found at lower metallicities, and a higher fraction of carbon-enhanced stars, but we are also finding stars in dwarf galaxies that appear to be iron-rich. These are compared with yields from a variety of supernova predictions.

  1. 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. PMID:26423076

  2. 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. PMID:25833637

  3. 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.

  4. 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

  5. Chemically reversible reactions of hydrogen sulfide with metal phthalocyanines.

    PubMed

    Hartle, Matthew D; Sommer, Samantha K; Dietrich, Stephen R; Pluth, Michael D

    2014-08-01

    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 [Co(I)Pc](-), 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

  6. 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...

  7. 15 CFR 714.3 - Advance declaration requirements for additionally planned production of Schedule 3 chemicals.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 15 Commerce and Foreign Trade 2 2011-01-01 2011-01-01 false Advance declaration requirements for 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...

  8. Heat-Resistant Co-W Catalytic Metals for Multilayer Graphene Chemical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Ueno, Kazuyoshi; Karasawa, Yusuke; Kuwahara, Satoru; Baba, Shotaro; Hanai, Hitoshi; Yamazaki, Yuichi; Sakuma, Naoshi; Kajita, Akihiro; Sakai, Tadashi

    2013-04-01

    Multilayer graphene (MLG) is expected to be a low-resistance and high-reliability interconnect material replacing copper (Cu) in nanoscale interconnects. Chemical vapor deposition (CVD) on catalytic metals is expected as a practical method for MLG deposition. To obtain high-quality MLG films without catalyst agglomeration by CVD, heat-resistant Co-W catalytic metals were investigated. The agglomeration of the Co-W catalytic metals was suppressed by increasing the W composition; however, MLG deposition was suppressed at the same time. The effects of W addition on the MLG growth were discussed from the viewpoints of the crystallographic change of the Co-W catalysts and chemical reactions. It was found that the Co grain size was reduced and the fcc Co formation was suppressed by W addition. In addition, graphite formation was supposed to be suppressed by W addition owing to the formation of phases other than fcc Co according to the Co-W-C phase diagram. With the optimum W concentration, MLG crystallinity was improved by high-temperature CVD using the heat-resistant Co-W catalytic metals (0.7 at. %) without agglomeration, compared with that in the case of using pure-Co catalysts.

  9. 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

    2016-05-01

    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.

  10. 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.

  11. Evaluation of the effectiveness of various amendments on trace metals stabilization by chemical and biological methods.

    PubMed

    Lee, Sang-Hwan; Park, Hyun; Koo, Namin; Hyun, Seunghun; Hwang, Anna

    2011-04-15

    We evaluated the effects of five different kinds of amendments on heavy metals stabilization. The five amendments were: zero valent iron, limestone, acid mine drainage treatment sludge, bone mill, and bottom ash. To determine bioavailability of the heavy metals, different chemical extraction procedures were used such as, extraction with (Ca(NO(3))(2), DTPA; toxic characteristic leaching procedure (TCLP), physiologically based extraction test (PBET) that simulates gastric juice, and sequential extraction test. Bioavailability was also determined by measuring uptake of the heavy metals by lettuce (Lactuca sativa L.) and earthworms (Eisenia fetida). In addition, dehydrogenase activity was measured to determine microbial activity in the soil with the different amendments. The addition of amendments, especially limestone and bottom ash, resulted in a significant reduction in extractable metal contents. Biological assays using lettuce, earthworm, and enzyme activity were found as appropriate indicators of available metal fraction after in situ stabilization of heavy metals. In conclusion, TCLP and sequential extraction test appear to be promising surrogate measure of metal bioavailability in soils for several environment endpoints. PMID:21333442

  12. 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.

  13. 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.

  14. 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. PMID:26808460

  15. 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.

  16. 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

  17. Effect of chemical composition and ferrite content on room temperature SCC behavior of austenitic weld metals

    SciTech Connect

    Raghunatha Rao, B.; Prasad Rao, K.; Iyer, K.J.L. )

    1993-03-01

    Austenitic stainless steels are widely used in the welded condition especially in chemical, petrochemical, thermal power, and nuclear industries where they are subjected to stresses in corrosive environments. Since austenitic stainless steel weld metals invariably contain some delta ferrite to avoid hot cracking, the effect of ferrite on the stress corrosion cracking behavior is important. Austenitic weld metals with different alloy additions and different ferrite contents were investigated for their resistance to room temperature stress corrosion cracking (SCC) in 5 N H[sub 2]SO[sub 4] + 0.5 N NaCl solution. It was found that the delta ferrite content in the weld metals had a predominant effect on the SCC resistance. Higher ferrite contents increased the tendency for SCC. Post-weld heat treatment of weld metals resulted in the improvement of the SCC resistance.

  18. 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. PMID:27434304

  19. 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. PMID:25853630

  20. 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. PMID:26134580

  1. Thyroid-hormone-disrupting chemicals: evidence for dose-dependent additivity or synergism.

    PubMed

    Crofton, Kevin M; Craft, Elena S; Hedge, Joan M; Gennings, Chris; Simmons, Jane E; Carchman, Richard A; Carter, W Hans; DeVito, Michael J

    2005-11-01

    Endocrine disruption from environmental contaminants has been linked to a broad spectrum of adverse outcomes. One concern about endocrine-disrupting xenobiotics is the potential for additive or synergistic (i.e., greater-than-additive) effects of mixtures. A short-term dosing model to examine the effects of environmental mixtures on thyroid homeostasis has been developed. Prototypic thyroid-disrupting chemicals (TDCs) such as dioxins, polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers have been shown to alter thyroid hormone homeostasis in this model primarily by up-regulating hepatic catabolism of thyroid hormones via at least two mechanisms. Our present effort tested the hypothesis that a mixture of TDCs will affect serum total thyroxine (T4) concentrations in a dose-additive manner. Young female Long-Evans rats were dosed via gavage with 18 different polyhalogenated aromatic hydrocarbons [2 dioxins, 4 dibenzofurans, and 12 PCBs, including dioxin-like and non-dioxin-like PCBs] for 4 consecutive days. Serum total T4 was measured via radioimmunoassay in samples collected 24 hr after the last dose. Extensive dose-response functions (based on seven to nine doses per chemical) were determined for individual chemicals. A mixture was custom synthesized with the ratio of chemicals based on environmental concentrations. Serial dilutions of this mixture ranged from approximately background levels to 100-fold greater than background human daily intakes. Six serial dilutions of the mixture were tested in the same 4-day assay. Doses of individual chemicals that were associated with a 30% TH decrease from control (ED30), as well as predicted mixture outcomes were calculated using a flexible single-chemical-required method applicable to chemicals with differing dose thresholds and maximum-effect asymptotes. The single-chemical data were modeled without and with the mixture data to determine, respectively, the expected mixture response (the additivity model

  2. 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.

  3. 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. PMID:26429595

  4. 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

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

    SciTech Connect

    Bannochie, C; Damon Click, D

    2009-02-26

    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-1 (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

  6. 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.

  7. 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.

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

    DOEpatents

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

    2004-03-23

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

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

    DOEpatents

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

    2007-07-17

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

  10. 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.

  11. 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. PMID:10819205

  12. Methods and additives for delaying the release of chemicals in aqueous fluids

    SciTech Connect

    Burnham, J.W.; Briscoe, J.E.; Elphingstone, E.A.

    1980-05-13

    Additives are provided for bringing about the delayed release of a chemical such as a gel breaker or demulsifier in an aqueous fluid such as a gelled oil well hydraulic fracturing or fracture-acidizing fluid. The additives are pelletized solids consisting of the chemical to be released such as sodium laryl sulfate. A gelling agent capable of being hydrated such as a polysaccharide, and a breaker for the gel produced by the gelling agent when hydrated such as a persulfate or an enzyme. 33 claims.

  13. Chemical Reactivity at Metal Oxide-Aqueous Solution Interfaces

    NASA Astrophysics Data System (ADS)

    Brown, Gordon E., Jr.

    2005-03-01

    The chemical reactivity of metal oxide surfaces in contact with aqueous solutions, with respect to cations and anions, is controlled by the composition, structure, and charging properties of the surface, the dielectric properties of the bulk oxide, and the stability of the aqueous cation or anion complex versus its sorption complex. These points will be illustrated for selected cations, anions, and metal oxides using macroscopic uptake and EXAFS spectroscopy results, x-ray standing wave data, and crystal truncation rod diffraction data. The reactivity of metal oxide surfaces with respect to low molecular weight (LMW) carboxylic acids is also dependent on the types of ring structures formed between surface functional groups and the LMW organic molecules. These types of interactions will be illustrated using ATR-FTIR data and dissolution measurements as a function of pH for oxalate, maleate, phthalate, and pyromellitate interacting with boehmite (AlOOH). Co-Authors are Tae Hyun Yoon, Stephen B. Johnson, Dept. of Geological & Environmental Sciences, Stanford University, Stanford CA 94305-2115; Thomas P. Trainor, Dept. of Chemistry and Biochemistry, University of Alaska Fairbanks, Fairbanks, AK 99775; Anne M. Chaka, National Institute of Standards and Technology, Gaithersburg, MD 20899

  14. Laser nanolithography and chemical metalization for the manufacturing of 3D metallic interconnects

    NASA Astrophysics Data System (ADS)

    Jonavičius, Tomas; RekštytÄ--, Sima; Žukauskas, Albertas; Malinauskas, Mangirdas

    2014-03-01

    We present a developed method based on direct laser writing (DLW) and chemical metallization (CM) for microfabrication of three-dimensional (3D) metallic structures. Such approach enables manufacturing of free­-form electro conductive interconnects which can be used in integrated electric circuits such micro-opto-electro mechanical systems (MOEMS). The proposed technique employing ultrafast high repetition rate laser enables efficient fabrication of 3D microstructures on dielectric as well as conductive substrates. The produced polymer links out of organic-inorganic composite matrix after CM serve as interconnects of separate metallic contacts, their dimensions are: height 15μm, width 5μm, length 35-45 μm and could provide 300 nΩm resistivity measured in a macroscopic way. This proves the techniques potential for creating integrated 3D electric circuits at microscale.

  15. Tests of proprietary chemical additives as antiscalants for hypersaline geothermal brine. Final report

    SciTech Connect

    Harrar, J.E.; Locke, F.E.; Otto, C.H. Jr.; Deutscher, S.B.; Frey, W.P.; Lorensen, L.E.; Snell, E.O.; Lim, R.; Ryon, R.W.; Quong, R.

    1980-01-01

    The Lawrence Livermore Laboratory brine treatment test system has been used to carry out a short-term evaluation of a number of proprietary chemical additives as antiscalants for the hypersaline brine of the Salton Sea Geothermal Field. In addition, a test of sludge seeding was conducted as a technique for scale control. The effect of each additive on the rate of precipitation of silica from the effluent brine at 90/sup 0/C was measured, and scaling rates of brine treated with nine of the additives were measured at 125 and 210/sup 0/C. Corrosion rates of mild steel in the treated brines were estimated using Petrolite linear polarization resistance equipment. None of the additives had a direct effect on the rates of silica precipitation, and none had a beneficial effect on the scale formed at 210/sup 0/C. At 125/sup 0/C, two additives, Drewsperse 747 (Drew Chemical) and SC-210 (Southwest Specialty Chemicals) afforded a marginal degree of scale reduction. The Austral-Erwin additive diminished the adherence of scale formed at points of high velocity fluid flow but increased solids accumulation at other points. Sludge seeding shows some promise because it reduces the degree of silica supersaturation of the brine. Results of analyses of solids precipitated from effluent brines (Woolsey No. 1 and acidified Magmamax No. 1) are presented.

  16. 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. PMID:26773669

  17. Synthetic metallic dialkydithiocarbamates as antiwear and extreme-pressure additives for lubricating oils: Role of metal on their effectiveness

    SciTech Connect

    Tuli, D.K.; Sarin, R.; Gupta, A.K.

    1995-04-01

    Dialkydithiocarbamates of five metals have been synthesized in pure form by following a simple general method. The alkyl chain in each of these compounds has been kept the same so as to observe the performance variations due to metal ions. The EP properties expressed as load wear index and weld load indicated the highest performance by Bi followed by Pb, Sb, Zn and Mo. The antiwear properties in terms of wear scar diameter, relative anti-wear effectiveness and mean average wear scar diameter show a performance order of Bi > Pb > Sb > Zn > Mo. The large ionic radius metals (Bi, Pb & Sb) had the best overall load-carrying performance and their effectiveness increased substantially when the additive concentration was more than 0.004 gm atom/Kg. The results suggest that Bi has good potential to replace toxic Pb and Sb from existing lubrication systems. 18 refs., 7 refs., 1 tab.

  18. 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.

  19. GENOTOXICITY IN MOUSE LYMPHOMA CELLS OF CHEMICAL CAPABLE OF MICHAEL ADDITION

    EPA Science Inventory

    Chemical agents that react via the Michael addition reaction have important industrial and consumer applications. ne of them, acrylamide, is used largely in the production of polymers as a flocculent in sewage and wastewater treatment, for coagulant treatment of potable water and...

  20. 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.

  1. 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.

  2. Growth mechanism and additional constraints on FeNi metal condensation in the solar nebula

    NASA Astrophysics Data System (ADS)

    Meibom, Anders; Petaev, Mikhail I.; Krot, Alexander N.; Keil, Klaus; Wood, John A.

    2001-12-01

    Chemically zoned FeNi metal grains in the metal-rich chondrites QUE 94411 and Hammadah at Hamra 237 formed by gas-solid condensation in the temperature range from ~1500 to 1400 K during highly energetic thermal events in the solar nebula. We observe a linear correlation between the apparent diameter of the zoned FeNi metal grains and their inferred condensation temperature interval, which indicates that the grain growth rate was essentially constant. This lends strong support for a kinetic ``hit-and-stick'' growth model that yields growth timescales of ~20-85 hours and gas cooling rates of ~1-2 Kh-1 for six representative zoned metal grains studied in QUE 94411. In the core regions of the zoned metal grains the Ni concentration is systematically lower than the thermodynamically predicted values, suggesting that solid-state diffusion played an important role in shaping the zoning profiles. Combined with existing data, our observations provide a set of constraints on the physics and chemistry of large-scale, high-temperature processes in the earliest solar nebula, which present astrophysicists with profound challenges.

  3. 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.

  4. Chemical Trends for Transition Metal Compound Bonding to Graphene

    NASA Astrophysics Data System (ADS)

    Lange, Bjoern; Blum, Volker

    2015-03-01

    Transition metal compounds are of interest as catalysts for the hydrogen evolution reaction (HER). However, a perfect candidate to replace expensive platinum has not yet been identified. To tailor a specific compound, several properties come into play. One is the bonding to the underlying substrate, for which π-bonded carbon nanostructures are promising candidates. Here we analyze the bonding of small transition metal compound nanoclusters to a graphene layer for a range of chemical compositions: MxAy (M = Mo, Ti; A = S, O, B, N, C). The clusters are generated by an unbiased random search algorithm. We perform total energy calculations based on density functional theory to identify lowest energy clusters. We calculate binding energies using the PBE and HSE functionals with explicit van der Waals treatment and benchmark those against RPA cluster calculations. Our results indicate that molybdenum-carbides and -nitrides tend to bond tightly to graphene. Mo-oxides and -sulfides show small binding energies, indicating van der Waals bonding.

  5. 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).

  6. 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. PMID:20411504

  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. 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.

  9. 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. PMID:25212818

  10. 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. PMID:26674593

  11. 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.

  12. 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.

  13. Physico-chemical characterization of grease interceptors with and without biological product addition.

    PubMed

    He, Xia; Osborne, Jason; de los Reyes, Francis L

    2012-03-01

    Hardened and insoluble fat, oil, and grease (FOG) deposits are the primary cause of sewer line blockages leading to sanitary sewer overflows (SSOs). However, there have been very few long-term assessments of the physico-chemical characteristics of full-scale grease interceptors (GIs), the first "line of defense" against FOG buildup in sewer lines. In this study, we assessed the physico-chemical characteristics of two full-scale GIs (at a restaurant and a retirement community kitchen) over a one-year period. Statistically significant differences between bioaugmented and untreated cycles were detected for several chemical and physical properties. The treated cycles had lower BOD and COD at the grease interceptor outlet. While the combined data for all treated cycles did not show lower FOG concentrations in the GI outlet compared to the combined data for all untreated cycles, comparison of specific individual treated and untreated cycles show a positive effect due to the addition of product. PMID:22755486

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

    NASA Astrophysics Data System (ADS)

    Gogotsi, Yury

    2015-11-01

    The unique properties of 2D materials, such as graphene or transition metal dichalcogenides, have been attracting much attention in the past decade. Now, metallically conductive and even superconducting transition metal carbides are entering the game.

  15. 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.

  16. 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.

  17. In Situ Chemical Synthesis of Lithium Fluoride/Metal Nanocomposite for High Capacity Prelithiation of Cathodes.

    PubMed

    Sun, Yongming; Lee, Hyun-Wook; Zheng, Guangyuan; Seh, Zhi Wei; Sun, Jie; Li, Yanbin; Cui, Yi

    2016-02-10

    The initial lithium loss during the formation stage is a critical issue that significantly reduces the specific capacity and energy density of current rechargeable lithium-ion batteries (LIBs). An effective strategy to solve this problem is using electrode prelithiation additives that can work as a secondary lithium source and compensate the initial lithium loss. Herein we show that nanocomposites of lithium fluoride and metal (e.g., LiF/Co and LiF/Fe) can be efficient cathode prelithiation materials. The thorough mixing of ultrafine lithium fluoride and metal particles (∼5 nm) allows lithium to be easily extracted from the nanocomposites via an inverse conversion reaction. The LiF/Co nanocomposite exhibits an open circuit voltage (OCV, 1.5 V) with good compatibility with that of existing cathode materials and delivers a high first-cycle "donor" lithium-ion capacity (516 mA h g(-1)). When used as an additive to a LiFePO4 cathode, the LiF/Co nanocomposite provides high lithium compensation efficiency. Importantly, the as-formed LiF/metal nanocomposites possess high stability and good compatibility with the regular solvent, binder, and existing battery processing conditions, in contrast with the anode prelithiation materials that usually suffer from issues of high chemical reactivity and instability. The facile synthesis route, high stability in ambient and battery processing conditions, and high "donor" lithium-ion capacity make the LiF/metal nanocomposites ideal cathode prelithiation materials for LIBs. PMID:26784146

  18. Etchant wettability in bulk micromachining of Si by metal-assisted chemical etching

    NASA Astrophysics Data System (ADS)

    Yoon, Sung-Soo; Lee, Yeong Bahl; Khang, Dahl-Young

    2016-05-01

    Wet bulk micromachining of Si by metal-assisted chemical etching (MaCE) has successfully been demonstrated. Based on the mechanism of defective etching results from Ag and Au metal catalyst experiments, the wettability of etchant solution, in addition to metal type, has been found to have profound effect on the etching process. Addition of low surface tension co-solvent, ethanol in this work, into conventional etchant formulation has enabled complete wetting of etchant on surface, which prevents hydrogen bubble attachment on sample surface during the etching. The complete elimination of bubble attachment guarantees very uniform etch rate on all over the sample surface, and thus prevents premature fragmentation/rupture of catalyst metal layer. Under the optimized etching conditions, the MaCE could be done for up to 12 h without any noticeable film rupture and thus etching defects. Thanks to very smooth surface of the etched patterns, conformal contact and direct bonding of elastomer on such surface has been easily accomplished. The method demonstrated here can pave the way for application of simple, low-cost MaCE process in the bulk micromachining of Si for various applications.

  19. Heavy metal removal by chemical reduction with sodium borohydride. A pilot-plant study

    SciTech Connect

    Gomez-Lahoz, C.; Garcia-Herruzo, F.; Rodriguez-Maroto, J.M.; Rodriguez, J.J. )

    1992-10-01

    A 1,000/h continuous pilot-plant study dealing with Cu{sup 2+} and Co{sup 2+} removal from simulated industrial wastewater by means of chemical reduction with sodium borohydride is presented. Initial metal concentrations in the 25 to 40 mg range have been tested. Residual concentrations lower than 0.1 mg have been achieved when operating under optimal conditions. Prior addition of sodium dithionite was required to avoid reoxidation problems arising from dissolved oxygen. Flocculation-sedimentation and sand filtration have been studied for sludge separation.

  20. 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

  1. 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.

  2. 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. PMID:26471460

  3. 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.

  4. Deposition Technique For Chemical Free Black Coatings On Metals

    NASA Astrophysics Data System (ADS)

    Carton, J. G.; Cobbe, N.; O'Donoghue, J.; Pambaguian, L.; Norman, A.; Liedtke, V.; McCaul, T.

    2012-07-01

    Coatings having specific thermo-optical properties are necessary to manage the temperature equilibrium in space hardware. Incumbent black body coatings have a need to extend their operating temperature as well as increase the range of substrate materials that can be coated; in addition, issues relating to outgassing can limit the application of black body coatings. In this paper a relatively new coating technology, CoBlast, is used to deposit material on to titanium substrates, to produce a black body surface; SolarBlack. CoBlast, replaces the oxide layer of reactive metals with a fused thin surface. The process is uniquely non-complex, requiring no thermal input, no wet chemistry and is performed in an ambient temperature and pressure environment. Thermo optical and micro-structure analysis of SolarBlack was completed and the characterisation results including thermo cycling, up to 700°C, are discussed.

  5. 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.

  6. 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. PMID:23368781

  7. Chemical and Magnetic Order in Vapor-Deposited Metal Films

    NASA Astrophysics Data System (ADS)

    Rooney, Peter Wiliam

    1995-01-01

    A stochastic Monte Carlo model of vapor deposition and growth of a crystalline, binary, A_3 B metallic alloy with a negative energy of mixing has been developed which incorporates deposition and surface diffusion in a physically correct manner and allows the simulation of deposition rates that are experimentally realizable. The effects of deposition rate and growth temperature on the development of short range order (SRO) in vapor-deposited films have been examined using this model. SRO in the simulated films increases with growth temperature up to the point at which the temperature corresponds to the energy of mixing, but we see no corresponding development of anisotropic SRO (preferential ordering of A-B pairs along the growth direction). Epitaxial (100) and (111) CoPt_3 films have been deposited over a range of growth temperatures from -50^circ C to 800^circC. Curie temperature (T_{rm c}) and saturation magnetization are dramatically enhanced in those films grown near 400^circ C over the values expected for the chemically homogeneous alloy. Magnetization data indicates that the high T _{rm c} films are inhomogeneous. These phenomena are interpreted as evidence of a previously unobserved magnetically driven miscibility gap in the Co-Pt phase diagram. Films grown near 400^circ C exhibit large uniaxial perpendicular magnetic anisotropy that cannot be accounted for by strain. The observed anisotropy coincides with the chemical phase separation and it seems likely that these two phenomena are related. Long range order (LRO) in the as-deposited films peaks at a growth temperature of 630^circC and then decreases with decreasing growth temperature. The decrease in LRO is either due to kinetic frustration or to competition from magnetically induced Co clustering. Theoretical phase diagrams based on the appropriate Blume-Emery-Griffiths Hamiltonian suggest the latter.

  8. Effect of basic additives on sensitivity and diffusion of acid in chemical amplification resists

    NASA Astrophysics Data System (ADS)

    Asakawa, Koji; Ushirogouchi, Tohru; Nakase, Makoto

    1995-06-01

    The effect of amine additives in chemical amplification resists is discussed. Phenolic amines such as 4-aminophenol and 2-(4-aminophenyl)-2-(4-hydroxyphenyl) propane were investigated as model compounds from the viewpoint of sensitivity, diffusion and resolution. Equal molar amounts of acid and amine deactivated at the very beginning of post-exposure bake, and could not participate in decomposing the inhibitor as a catalyst. Only the acid which survived from the deactivation diffuses in the resist, decomposing the inhibitors from the middle to late stage of PEB. The basic additives reduce the diffusion range of the acid, especially for long-range diffusion, resulting in higher contrast at the interfaces between the exposed and unexposed areas. In addition, the amine concentration required is found to be less than the concentration which causes the resist sensitivity to start decreasing.

  9. 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.

  10. 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.

  11. 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

  12. Etching anisotropy mechanisms lead to morphology-controlled silicon nanoporous structures by metal assisted chemical etching.

    PubMed

    Jiang, Bing; Li, Meicheng; Liang, Yu; Bai, Yang; Song, Dandan; Li, Yingfeng; Luo, Jian

    2016-02-01

    The etching anisotropy induced by the morphology and rotation of silver particles controls the morphology of silicon nanoporous structures, through various underlying complex etching mechanisms. The level of etching anisotropy can be modulated by controlling the morphology of the silver catalyst to obtain silicon nanoporous structures with straight pores, cone-shaped pores and pyramid-shaped pores. In addition, the structures with helical pores are obtained by taking advantage of the special anisotropic etching, which is induced by the rotation and revolution of silver particles during the etching process. An investigation of the etching anisotropy during metal assisted chemical etching will promote a deep understanding of the chemical etching mechanism of silicon, and provide a feasible approach to fabricate Si nanoporous structures with special morphologies. PMID:26785718

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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). PMID:25666074

  19. 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. PMID:16632893

  20. 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.

  1. 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.

  2. Influence of metal surface and sulfur addition on coke deposition in the thermal cracking of hydrocarbons

    SciTech Connect

    Reyniers, M.F.S.G.; Froment, G.F.

    1995-03-01

    Coke formation in the thermal cracking of hydrocarbons was studied in a pilot plant unit and in a microreactor with complete mixing of the gas phase, containing a hollow cylinder suspended at the arm of an electrobalance. The morphology of the coke was studied by SEM, while EDX was used to determine the concentration of metals in the coke layer. The influence of the metal surface composition, of it pretreatment, and of the addition of various sulfur compounds on the coking rate and CO production was investigated for condition typical for those in the cracking coil. The CO yield is not a measure of the coking rate. Sulfur compounds are very efficient in reducing the CO yield but promote coke formation.

  3. Development of high capacity, high rate lithium ion batteries utilizing metal fiber conductive additives

    NASA Astrophysics Data System (ADS)

    Ahn, Soonho; Kim, Youngduk; Kim, Kyung Joon; Kim, Tae Hyung; Lee, Hyungkeun; Kim, Myung H.

    As lithium ion cells dominate the battery market, the performance improvement is an utmost concern among developers and researchers. Conductive additives are routinely employed to enhance electrode conductivity and capacity. Carbon particulates—graphite or carbon black powders—are conventional and popular choices as conductive fillers. However, percolation requirements of particles demand significant volumetric content of impalpable, and thereby high area conductive fillers. As might be expected, the electrode active surface area escalates unnecessarily, resulting in overall increase in reaction with electrolytes and organic solvents. The increased reactions usually manifest as an irreversible loss of anode capacity, gradual oxidation and consumption of electrolyte on the cathode—which causes capacity decline during cycling—and an increased threat to battery safety by gas evolution and exothermic solvent oxidation. In this work we have utilized high aspect ratio, flexible, micronic metal fibers as low active area and high conductivity additives. The metal fibers appear well dispersed within the electrode and to satisfy percolation requirements very efficiently at very low volumetric content compared to conventional carbon-based conductive additives. Results from 18650-type cells indicate significant enhancements in electrode capacity and high rate capability while the irreversible capacity loss is negligible.

  4. 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

  5. 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.

  6. 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.

  7. 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

    ... Guidance for Industry: Studies to Evaluate the Utility of Anti-Salmonella Chemical Food Additives in Feeds... HUMAN SERVICES Food and Drug Administration Guidance for Industry: Studies To Evaluate the Utility of Anti- Salmonella Chemical Food Additives in Feeds; Request for Comments AGENCY: Food and...

  8. 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.

  9. 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. PMID:27307438

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    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.

  11. 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.

  12. 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.

  13. 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

  14. Direct Visualization of Etching Trajectories in Metal-Assisted Chemical Etching of Si by the Chemical Oxidation of Porous Sidewalls.

    PubMed

    Yoon, Sung-Soo; Khang, Dahl-Young

    2015-09-29

    We demonstrate a simple method for the visualization of trajectories traced by noble metal nanoparticles during metal-assisted chemical etching (MaCE) of Si. The nanoporous Si layer formed around drilled pores is converted into SiO2 by simple chemical oxidation. Etch removal of the remaining Si using alkali hydroxide leaves SiO2 nanostructures that are the exact replica of those drilled pores or etching trajectories. The differences in etching characteristics between Ag and Au have been investigated using the proposed visualization method. The shape and chemical stability of metal nanoparticles used for MaCE have been found to be critical in determining etching paths. The proposed method would be very helpful in studying the fundamental mechanism of MaCE as well as in micro/nanostructuring of the Si surface for various applications. This approach can also be used for the generation of straight or helical SiO2 nanotubes. PMID:26352208

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

    PubMed Central

    Yim, Dong-Gyun

    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. PMID:26761846

  16. 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

  17. 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

  18. 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

  19. 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. PMID:27040193

  20. 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.

  1. The capture of heavy metals from incineration using a spray dryer integrated with a fabric filter using various additives.

    PubMed

    Liu, Z S; Wey, M Y; Lin, C L

    2001-07-01

    This study investigated the effects of feedstock additives [polyvinyl chloride (PVC) and NaCl] and spray dryer additives (SiO2, CaCl2, NaHCO3) on heavy metal and fly ash removal efficiencies, and on particle size distribution of heavy metals. A spray dryer with an integrated fabric filter was used as an air pollution control device (APCD). Removal efficiencies for fly ash and heavy metals were greater than 95 and 90%, respectively. When additives of PVC or NaCl were used, the concentration of heavy metals distributed in fly ash apparently varied when the particle diameter was <1 microm. Although the effects of the additives SiO2, CaCl2, and NaHCO3 on the elemental size distribution of Cr were insignificant, these additives did slightly increase concentrations of Cd, Zn, and Pb partitioning in coarser particles (>1 microm). PMID:15658217

  2. Effects of chemical composition of fly ash on efficiency of metal separation in ash-melting of municipal solid waste.

    PubMed

    Okada, Takashi; Tomikawa, Hiroki

    2013-03-01

    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. PMID:22981781

  3. Experimental evaluation of water mist with metal chloride additives for suppressing CH4/air cup-burner flames

    NASA Astrophysics Data System (ADS)

    Liu, Jianghong; Cong, Beihua

    2013-06-01

    In order to investigate the fire suppression effectiveness of water mist with metal chloride additives, ultrafine water mists of these salts with diameters about 10μm were introduced into CH4/air non-premixed flame in the cup burner. Results showed that these droplets hard to make itself to the flame front under the cup burner flow conditions functioned as a carrier of the vaporized solid particles or its decomposed materials. The metal chloride improved fire suppression efficacy of water mist which were affected by the type and concentration of metal chloride. On a mass basis, there is a fire suppression effectiveness relationship of MgCl2metal chlorides improves as the concentration of metal chlorides increase. However, upper additive limits exist due to the associated limiting vapour pressure of the additive.

  4. Effect of chemical additives on Bacillus thuringiensis (Bacillales: Bacillaceae) against Plutella xylostella (Lepidoptera: Pyralidae).

    PubMed

    Zhang, L; Qiu, S; Huang, T; Huang, Z; Xu, L; Wu, C; Gelbic, I; Guan, X

    2013-06-01

    To examine the effect of chemical additives on Bacillus thuringiensis (Berliner) against Plutella xylostella (L.), inorganic salts, nitrogenous compounds, protein solubilizing agents, and organic acids were selected and tested. The chosen materials are low in cost and environmentally safe. Results show that many inorganic salts can increase the activity of B. thuringiensis in a range of 1.31- to 3.08-fold. These include calcium acetate, calcium chloride, calcium hydroxide, calcium sulfate, calcium carbonate, sodium carbonate, sodium acetate, potassium hydroxide, potassium carbonate, potassium acetate, magnesium chloride, magnesium sulfate, and zinc sulfate. Nitrogenous compounds, including peptone, sodium nitrate, and ammonium nitrate, can enhance the activity of B. thuringiensis 1.62-, 1.32-, and 1.37-fold, respectively. Among the protein solubilizing agents, EDTA, urea, mercaptoethanol and dipotassium hydrogen phosphate increased the activity of B. thuringiensis 1.62- to 2.34-fold. Among the organic acids, maleic and citric acids boosted the activity 1.45- and 1.55-fold, respectively. Meanwhile, sodium benzoate and resorcinol led to 1.74- and 1.44-fold activity gains, respectively. Use of appropriate additives could provide great benefit not only in reducing the costs for field applications of biological insecticides but also by boosting the efficacy of B. thuringiensis. PMID:23865169

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. 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

  10. Laser powder bed fusion additive manufacturing of metals; physics, computational, and materials challenges

    DOE PAGESBeta

    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 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

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Inhomogeneous halo collapse and early Galactic chemical evolution - Globular cluster metallicities

    NASA Technical Reports Server (NTRS)

    Malinie, G.; Hartmann, D. H.; Mathews, G. J.

    1991-01-01

    A new solution to the observed Galactic globular cluster metallicity distribution is proposed by considering inhomogeneous collapse of a centrally condensed proto-Galaxy. In contrast to the standard one-zone model, it is shown that, for inhomogeneous models, the metallicity distribution can be reproduced without the need to decrease the nucleosynthetic yield for metal-poor stars. Chemical evolution in free fall is calculated analytically. A hybrid hydroparticle code is developed to study the effect of supernova induced pressure.

  16. 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.

  17. 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.

  18. 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. PMID:18075217

  19. 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...

  20. Chemical transformations drive complex self-assembly of uracil on close-packed coinage metal surfaces.

    PubMed

    Papageorgiou, Anthoula C; Fischer, Sybille; Reichert, Joachim; Diller, Katharina; Blobner, Florian; Klappenberger, Florian; Allegretti, Francesco; Seitsonen, Ari P; Barth, Johannes V

    2012-03-27

    We address the interplay of adsorption, chemical nature, and self-assembly of uracil on the Ag(111) and Cu(111) surfaces as a function of molecular coverage (0.3 to 1 monolayer) and temperature. We find that both metal surfaces act as templates and the Cu(111) surface acts additionally as a catalyst for the resulting self-assembled structures. With a combination of STM, synchrotron XPS, and NEXAFS studies, we unravel a distinct polymorphism on Cu(111), in stark contrast to what is observed for the case of uracil on the more inert Ag(111) surface. On Ag(111) uracil adsorbs flat and intact and forms close-packed two-dimensional islands. The self-assembly is driven by stable hydrogen-bonded dimers with poor two-dimensional order. On Cu(111) complex structures are observed exhibiting, in addition, a strong annealing temperature dependence. We determine the corresponding structural transformations to be driven by gradual deprotonation of the uracil molecules. Our XPS study reveals unambiguously the tautomeric signature of uracil in the contact layer and on Cu(111) the molecule's deprotonation sites. The metal-mediated deprotonation of uracil and the subsequent electron localization in the molecule determine important biological reactions. Our data show a dependence between molecular coverage and molecule-metal interaction on Cu(111), as the molecules tilt at higher coverages in order to accommodate a higher packing density. After deprotonation of both uracil N atoms, we observe an adsorption geometry that can be understood as coordinative anchoring with a significant charge redistribution in the molecule. DFT calculations are employed to analyze the surface bonding and accurately describe the pertaining electronic structure. PMID:22356544

  1. 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.

  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. QUANTITATIVE ASSESSMENT OF THE EFFECTS OF METALS ON MICROBIAL DEGRADATION OF ORGANIC CHEMICALS

    EPA Science Inventory

    Biodegradation inhibition of a benchmark chemical, 2,4-dichloro-phenoxyacetic acid methyl ester (2,4-DME), was used to quantify the inhibitory effects of heavy metals on aerobic microbial degradation rates of organic chemicals. his procedure used lake sediments and aufwuchs (floa...

  5. 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. PMID:26595771

  6. 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.

  7. 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. PMID:25580627

  8. 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.

  9. 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.

  10. 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