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Sample records for reactive metals processing

  1. Synthesis and processing of composites by reactive metal penetration

    Energy Technology Data Exchange (ETDEWEB)

    Loehman, R.E.; Ewsuk, K.G. [Sandia National Laboratories, Albuquerque, NM (United States); Tomsia, A.P. [Pask Research and Engineering, Berkeley, CA (United States)] [and others

    1995-05-01

    Ceramic-metal composites are being developed because their high stiffness-to weight ratios, good fracture toughness, and variable electrical and thermal properties give them advantages over more conventional materials. However, because ceramic-metal composite components presently are more expensive than monolithic materials, improvements in processing are required to reduce manufacturing costs. Reactive metal penetration is a promising new method for making ceramic- and metal-matrix composites that has the advantage of being inherently a net-shape process. This technique, once fully developed, will provide another capability for manufacturing the advanced ceramic composites that are needed for many light-weight structural and wear applications. The lower densities of these composites lead directly to energy savings in use. Near-net-shape fabrication of composite parts should lead to additional savings because costly and energy intensive grinding and machining operations are significantly reduced, and the waste generated from such finishing operations is minimized. The goals of this research program are: (1) to identify feasible compositional systems for making composites by reactive metal penetration; (2) to understand the mechanism(s) of composite formation by reactive metal penetration; and (3) to learn how to control and optimize reactive metal penetration for economical production of composites and composite coatings.

  2. Synthesis and processing of composites by reactive metal penetration

    Energy Technology Data Exchange (ETDEWEB)

    Loehman, R.E.; Ewsuk, K.G. [Sandia National Labs., Albuquerque, NM (United States); Tomsia, A.P. [Pask Research and Engineering, Berkeley, CA (United States)] [and others

    1997-04-01

    Achieving better performance in commercial products and processes often is dependent on availability of new and improved materials. Ceramic-metal composites have advantages over more conventional materials because of their high stiffness-to-weight ratios, good fracture toughness, and because their electrical and thermal properties can be varied through control of their compositions and microstructures. However, ceramic composites will be more widely used only when their costs are competitive with other materials and when designers have more confidence in their reliability. Over the past four years reactive metal penetration has been shown to be a promising technique for making ceramic and metal-matrix composites to near-net-shape with control of both composition and microstructure. It appears that, with sufficient development, reactive metal penetration could be an economical process for manufacturing many of the advanced ceramic composites that are needed for light-weight structural and wear applications for transportation and energy conversion devices. Near-net-shape fabrication of parts is a significant advantage because costly and energy intensive grinding and machining operations are substantially reduced, and the waste generated from such finishing operations is minimized. The most promising compositions to date consist of Al and Al{sub 2}O{sub 3}; thus, these composites should be of particular interest to the aluminum industry. The goals of this ceramic-metal composite research and development program are: (1) to identify compositions favorable for making composites by reactive metal penetration; (2) to understand the mechanism(s) by which these composites are formed; (3) to control and optimize the process so that composites and composite coatings can be made economically; and (4) to apply R&D results to problems of interest to the aluminum industry.

  3. Characterization of Transition Metal Carbide Layers Synthesized by Thermo-reactive Diffusion Processes

    DEFF Research Database (Denmark)

    Laursen, Mads Brink; Fernandes, Frederico Augusto Pires; Christiansen, Thomas Lundin

    2015-01-01

    Hard wear resistant surface layers of transition metal carbides can be produced by thermo-reactive diffusion processes where interstitial elements from a steel substrate together with external sources of transition metals (Ti, V, Cr etc.) form hard carbide and/or nitride layers at the steel surface...... electron microscopy, X-ray diffraction and Vickers hardness testing. The study shows that porosityfree, homogenous and very hard surface layers can be produced by thermo-reactive diffusion processes. The carbon availability of the substrate influences thickness of obtained layers, as Vanadis 6 tool steel...

  4. Particle beam experiments for the analysis of reactive sputtering processes in metals and polymer surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Corbella, Carles; Grosse-Kreul, Simon; Kreiter, Oliver; Arcos, Teresa de los; Benedikt, Jan; Keudell, Achim von [RD Plasmas with Complex Interactions, Ruhr-Universität Bochum, Universitätsstr. 150, 44780 Bochum (Germany)

    2013-10-15

    A beam experiment is presented to study heterogeneous reactions relevant to plasma-surface interactions in reactive sputtering applications. Atom and ion sources are focused onto the sample to expose it to quantified beams of oxygen, nitrogen, hydrogen, noble gas ions, and metal vapor. The heterogeneous surface processes are monitored in situ by means of a quartz crystal microbalance and Fourier transform infrared spectroscopy. Two examples illustrate the capabilities of the particle beam setup: oxidation and nitriding of aluminum as a model of target poisoning during reactive magnetron sputtering, and plasma pre-treatment of polymers (PET, PP)

  5. Particle beam experiments for the analysis of reactive sputtering processes in metals and polymer surfaces.

    Science.gov (United States)

    Corbella, Carles; Grosse-Kreul, Simon; Kreiter, Oliver; de los Arcos, Teresa; Benedikt, Jan; von Keudell, Achim

    2013-10-01

    A beam experiment is presented to study heterogeneous reactions relevant to plasma-surface interactions in reactive sputtering applications. Atom and ion sources are focused onto the sample to expose it to quantified beams of oxygen, nitrogen, hydrogen, noble gas ions, and metal vapor. The heterogeneous surface processes are monitored in situ by means of a quartz crystal microbalance and Fourier transform infrared spectroscopy. Two examples illustrate the capabilities of the particle beam setup: oxidation and nitriding of aluminum as a model of target poisoning during reactive magnetron sputtering, and plasma pre-treatment of polymers (PET, PP).

  6. Effect of process parameters on induction plasma reactive deposition of tungsten carbide from tungsten metal powder

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Tungsten carbide deposit was made directly from tungsten metal powder through the reaction with methane in radio frequency induction plasma. Effect of major process parameters on the induction plasma reactive deposition of tungsten carbide was studied by optical microscopy, scanning electron microscopy, X-ray diffraction analysis, water displacement method, and microhardness test. The results show that methane flow rate, powder feed rate, particle size, reaction chamber pressure and deposition distance have significant influences on the phase composition, density, and microhardness of the deposit. Extra carbon is necessary to ensure the complete conversion of tungsten metal into the carbide.

  7. Coinage Metal Hydrides: Synthesis, Characterization, and Reactivity.

    Science.gov (United States)

    Jordan, Abraham J; Lalic, Gojko; Sadighi, Joseph P

    2016-08-10

    Hydride complexes of copper, silver, and gold encompass a broad array of structures, and their distinctive reactivity has enabled dramatic recent advances in synthesis and catalysis. This Review summarizes the synthesis, characterization, and key stoichiometric reactions of isolable or observable coinage metal hydrides. It discusses catalytic processes in which coinage metal hydrides are known or probable intermediates, and presents mechanistic studies of selected catalytic reactions. The purpose of this Review is to convey how developments in coinage metal hydride chemistry have led to new organic transformations, and how developments in catalysis have in turn inspired the synthesis of reactive new complexes.

  8. Metallic corrosion processes reactivation sustained by iron-reducing bacteria: Implication on long-term stability of protective layers

    Science.gov (United States)

    Esnault, L.; Jullien, M.; Mustin, C.; Bildstein, O.; Libert, M.

    In deep geological environments foreseen for the disposal of radioactive waste, metallic containers will undergo anaerobic corrosion. In this context, the formation of corrosion products such as magnetite may reduce the rate of corrosion processes through the formation of a protective layer. This study aims at determining the direct impact of iron-reducing bacteria (IRB) activity on the stability of corrosion protective layers. Batch experiments investigating iron corrosion processes including the formation of secondary magnetite and its subsequent alteration in the presence of IRB show the bacteria ability to use structural Fe(III) for respiration which leads to the sustainment of a high corrosion rate. With the bio-reduction of corrosion products such as magnetite, and H 2 as electron donor, IRB promote the reactivation of corrosion processes in corrosive environments by altering the protective layer. This phenomenon could have a major impact on the long-term stability of metallic compounds involved in multi-barrier system for high-level radioactive waste containment.

  9. Development of a Waste Treatment Process to Deactivate Reactive Uranium Metal and Produce a Stable Waste Form

    Energy Technology Data Exchange (ETDEWEB)

    Gates-Anderson, D D; Laue, C A; Fitch, T E

    2002-01-17

    This paper highlights the results of initial investigations conducted to support the development of an integrated treatment process to convert pyrophoric metallic uranium wastes to a non-pyrophoric waste that is acceptable for land disposal. Several dissolution systems were evaluated to determine their suitability to dissolve uranium metal and that yield a final waste form containing uranium specie(s) amenable to precipitation, stabilization, adsorption, or ion exchange. During initial studies, one gram aliquots of uranium metal or the uranium alloy U-2%Mo were treated with 5 to 60 mL of selected reagents. Treatment systems screened included acids, acid mixtures, and bases with and without addition of oxidants. Reagents used included hydrochloric, sulfuric, nitric, and phosphoric acids, sodium hypochlorite, sodium hydroxide and hydrogen peroxide. Complete dissolution of the uranium turnings was achieved with the H{sub 3}PO{sub 4}/HCI system at room temperature within minutes. The sodium hydroxide/hydrogen peroxide, and sodium hypochlorite systems achieved complete dissolution but required elevated temperatures and longer reaction times. A ranking system based on criteria, such as corrosiveness, temperature, dissolution time, off-gas type and amount, and liquid to solid ratio, was designed to determine the treatment systems that should be developed further for a full-scale process. The highest-ranking systems, nitric acid/sulfuric acid and hydrochloric acid/phosphoric acid, were given priority in our follow-on investigations.

  10. New avenues for ligand-mediated processes--expanding metal reactivity by the use of redox-active catechol, o-aminophenol and o-phenylenediamine ligands.

    Science.gov (United States)

    Broere, Daniël L J; Plessius, Raoul; van der Vlugt, Jarl Ivar

    2015-10-01

    Redox-active ligands have evolved from being considered spectroscopic curiosities - creating ambiguity about formal oxidation states in metal complexes - to versatile and useful tools to expand on the reactivity of (transition) metals or to even go beyond what is generally perceived possible. This review focusses on metal complexes containing either catechol, o-aminophenol or o-phenylenediamine type ligands. These ligands have opened up a new area of chemistry for metals across the periodic table. The portfolio of ligand-based reactivity invoked by these redox-active entities will be discussed. This ranges from facilitating oxidative additions upon d(0) metals or cross coupling reactions with cobalt(iii) without metal oxidation state changes - by functioning as an electron reservoir - to intramolecular ligand-to-substrate single-electron transfer to create a reactive substrate-centered radical on a Pd(ii) platform. Although the current state-of-art research primarily consists of stoichiometric and exploratory reactions, several notable reports of catalysis facilitated by the redox-activity of the ligand will also be discussed. In conclusion, redox-active ligands containing catechol, o-aminophenol or o-phenylenediamine moieties show great potential to be exploited as reversible electron reservoirs, donating or accepting electrons to activate substrates and metal centers and to enable new reactivity with both early and late transition as well as main group metals.

  11. New avenues for ligand-mediated processes: expanding metal reactivity by the use of redox-active catechol, o-aminophenol and o-phenylenediamine ligands

    NARCIS (Netherlands)

    D.L.J. Broere; R. Plessius; J.I. van der Vlugt

    2015-01-01

    Redox-active ligands have evolved from being considered spectroscopic curiosities - creating ambiguity about formal oxidation states in metal complexes - to versatile and useful tools to expand on the reactivity of (transition) metals or to even go beyond what is generally perceived possible. This r

  12. Miniplant technology for heavy-metal precipitation by means of reactive extraction processes; Miniplanttechnik zur Schwermetallentfernung mittels reaktiver Extraktionsverfahren

    Energy Technology Data Exchange (ETDEWEB)

    Bart, H.J.; Schoeneberger, A. [Kaiserslautern Univ. (Germany). Lehrstuhl Thermische Verfahrenstechnik

    1999-07-01

    The development of novel techniques and their apparatus nowadays involves increasingly laboratory-scale technical systems (miniplant) in combination with simulation programs. For the precipitation of pollutants, especially heavy metals, from watery solutions, selective-action liquid ion exchangers are excellently suited, which are used in systems of various technical designs. The paper discusses their potential of application, the advantages and shortcomings of liquid-liquid extraction (counter-flow technique), of non-dispersive extraction (membrane technique) and of extractant-impregnated resins (packed-bed process) as well as their integration in miniplant systems. (orig.) [German] Bei der Entwicklung neuer Verfahren und bei deren apparativer Umsetzung werden heutzutage verstaerkt Anlagen im Labormassstab (Miniplant) in Kombination mit Simulationsprogrammen eingesetzt. Zur Entfernung von Schadstoffen, insbesondere Schwermetallen, aus waessrigen Loesungen eignen sich hervorragend selektiv wirkende fluessige Ionentauscher, die in unterschiedlicher Apparatetechnik zur Anwendung kommen. Das Einsatzpotential sowie Vor- und Nachteile der fluessig-fluessig Extraktion (Gegenstromverfahren), der nicht-dispersiven Extraktion (Membranverfahren), von extraktionsmittel-impraegnierten Harzen (Festbettverfahren) und die Einbindung in Miniplants werden diskutiert. (orig.)

  13. Modeling and stability analysis of the nonlinear reactive sputtering process

    Directory of Open Access Journals (Sweden)

    György Katalin

    2011-12-01

    Full Text Available The model of the reactive sputtering process has been determined from the dynamic equilibrium of the reactive gas inside the chamber and the dynamic equilibrium of the sputtered metal atoms which form the compound with the reactive gas atoms on the surface of the substrate. The analytically obtained dynamical model is a system of nonlinear differential equations which can result in a histeresis-type input/output nonlinearity. The reactive sputtering process has been simulated by integrating these differential equations. Linearization has been applied for classical analysis of the sputtering process and control system design.

  14. Football Pools and the Reactivity Series of Metals.

    Science.gov (United States)

    Heselden, Russ

    2001-01-01

    Describes an activity which presents the reactivity of metals series as a football pool with more reactive metals at the top of the table and unreactive metals at the bottom. Describes how the activity can be applied in different ways for different ability groups. (Author/MM)

  15. Process intensification technologies for biodiesel production reactive separation processes

    CERN Document Server

    Kiss, A A

    2014-01-01

    This book is among the first to address the novel process intensification technologies for biodiesel production, in particular the integrated reactive separations. It provides a comprehensive overview illustrated with many industrially relevant examples of novel reactive separation processes used in the production of biodiesel (e.g. fatty acid alkyl esters): reactive distillation, reactive absorption, reactive extraction, membrane reactors, and centrifugal contact separators. Readers will also learn about the working principles, design and control of integrated processes, while also getting a

  16. Reactive metal-oxide interfaces: A microscopic view

    Science.gov (United States)

    Picone, A.; Riva, M.; Brambilla, A.; Calloni, A.; Bussetti, G.; Finazzi, M.; Ciccacci, F.; Duò, L.

    2016-03-01

    Metal-oxide interfaces play a fundamental role in determining the functional properties of artificial layered heterostructures, which are at the root of present and future technological applications. Magnetic exchange and magnetoelectric coupling, spin filtering, metal passivation, catalytic activity of oxide-supported nano-particles are just few examples of physical and chemical processes arising at metal-oxide hybrid systems, readily exploited in working devices. These phenomena are strictly correlated with the chemical and structural characteristics of the metal-oxide interfacial region, making a thorough understanding of the atomistic mechanisms responsible of its formation a prerequisite in order to tailor the device properties. The steep compositional gradient established upon formation of metal-oxide heterostructures drives strong chemical interactions at the interface, making the metal-oxide boundary region a complex system to treat, both from an experimental and a theoretical point of view. However, once properly mastered, interfacial chemical interactions offer a further degree of freedom for tuning the material properties. The goal of the present review is to provide a summary of the latest achievements in the understanding of metal/oxide and oxide/metal layered systems characterized by reactive interfaces. The influence of the interface composition on the structural, electronic and magnetic properties will be highlighted. Particular emphasis will be devoted to the discussion of ultra-thin epitaxial oxides stabilized on highly oxidizable metals, which have been rarely exploited as oxide supports as compared to the much more widespread noble and quasi noble metallic substrates. In this frame, an extensive discussion is devoted to the microscopic characterization of interfaces between epitaxial metal oxides and the Fe(001) substrate, regarded from the one hand as a prototypical ferromagnetic material and from the other hand as a highly oxidizable metal.

  17. Nonferrous Metal Processing Plants

    Data.gov (United States)

    Department of Homeland Security — This map layer includes nonferrous metal processing plants in the United States. The data represent commodities covered by the Minerals Information Team (MIT) of the...

  18. Ferrous Metal Processing Plants

    Data.gov (United States)

    Department of Homeland Security — This map layer includes ferrous metal processing plants in the United States. The data represent commodities covered by the Minerals Information Team (MIT) of the...

  19. (Electronic structure and reactivities of transition metal clusters)

    Energy Technology Data Exchange (ETDEWEB)

    1992-01-01

    The following are reported: theoretical calculations (configuration interaction, relativistic effective core potentials, polyatomics, CASSCF); proposed theoretical studies (clusters of Cu, Ag, Au, Ni, Pt, Pd, Rh, Ir, Os, Ru; transition metal cluster ions; transition metal carbide clusters; bimetallic mixed transition metal clusters); reactivity studies on transition metal clusters (reactivity with H{sub 2}, C{sub 2}H{sub 4}, hydrocarbons; NO and CO chemisorption on surfaces). Computer facilities and codes to be used, are described. 192 refs, 13 figs.

  20. Improving Metal Casting Process

    Science.gov (United States)

    1998-01-01

    Don Sirois, an Auburn University research associate, and Bruce Strom, a mechanical engineering Co-Op Student, are evaluating the dimensional characteristics of an aluminum automobile engine casting. More accurate metal casting processes may reduce the weight of some cast metal products used in automobiles, such as engines. Research in low gravity has taken an important first step toward making metal products used in homes, automobiles, and aircraft less expensive, safer, and more durable. Auburn University and industry are partnering with NASA to develop one of the first accurate computer model predictions of molten metals and molding materials used in a manufacturing process called casting. Ford Motor Company's casting plant in Cleveland, Ohio is using NASA-sponsored computer modeling information to improve the casting process of automobile and light-truck engine blocks.

  1. Integrated Process Design and Control of Reactive Distillation Processes

    DEFF Research Database (Denmark)

    Mansouri, Seyed Soheil; Sales-Cruz, Mauricio; Huusom, Jakob Kjøbsted

    2015-01-01

    In this work, integrated design and control of reactive distillation processes is presented. Simple graphical design methods that are similar in concept to non-reactive distillation processes are used, such as reactive McCabe-Thiele method and driving force approach. The methods are based...... of this approach, it is shown that designing the reactive distillation process at the maximum driving force results in an optimal design in terms of controllability and operability. It is verified that the reactive distillation design option is less sensitive to the disturbances in the feed at the highest driving...

  2. Predictive modeling of reactive wetting and metal joining.

    Energy Technology Data Exchange (ETDEWEB)

    van Swol, Frank B.

    2013-09-01

    The performance, reproducibility and reliability of metal joints are complex functions of the detailed history of physical processes involved in their creation. Prediction and control of these processes constitutes an intrinsically challenging multi-physics problem involving heating and melting a metal alloy and reactive wetting. Understanding this process requires coupling strong molecularscale chemistry at the interface with microscopic (diffusion) and macroscopic mass transport (flow) inside the liquid followed by subsequent cooling and solidification of the new metal mixture. The final joint displays compositional heterogeneity and its resulting microstructure largely determines the success or failure of the entire component. At present there exists no computational tool at Sandia that can predict the formation and success of a braze joint, as current capabilities lack the ability to capture surface/interface reactions and their effect on interface properties. This situation precludes us from implementing a proactive strategy to deal with joining problems. Here, we describe what is needed to arrive at a predictive modeling and simulation capability for multicomponent metals with complicated phase diagrams for melting and solidification, incorporating dissolutive and composition-dependent wetting.

  3. Reactivity of metal-oxalate EUV resists as a function of the central metal

    Science.gov (United States)

    Grzeskowiak, Steven; Narasimhan, Amrit; Murphy, Michael; Napolitano, Lee; Freedman, Daniel A.; Brainard, Robert L.; Denbeaux, Greg

    2017-03-01

    the microelectronics industry. Traditional EUV photoresists have been composed of organic compounds which are moderately transparent to EUV. Resist stochastics and sensitivity can be improved by increasing the number of photons absorbed. Molecular organometallic resists are a type of metal containing resist aimed at improving EUV absorption. This work focuses on studying the role of the metal center (Metal = Co, Fe, Cr) in an oxalate complex by comparing the number of absorbed photons and the photoelectron reactivity in each compound. In the study presented here, the EUV absorption coefficients are determined experimentally by measuring the transmission through a resist coated on a silicon nitride membrane using an Energetiq EQ-10M xenon plasma EUV source. Additionally, the photochemistry is evaluated by monitoring outgassing reaction products. This particular resist platform eliminates oxalate ligands when exposed to electrons or EUV photons resulting in a solubility difference between the exposed and unexposed regions. In the process, carbon dioxide is produced and is monitored using mass spectrometry, where quantitative values are obtained using a calibration technique. For the metal oxalate complexes studied, the absorption of EUV changed minimally due to the low concentrations of metal atoms. However, EUV and electron reactivity greatly changed between the three compounds likely due to the reducibility of the metal center. A correlation is shown between Esize and the reducibility of each photoresist.

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

    Science.gov (United States)

    Özen, Alimet Sema; Akdeniz, Zehra

    2016-06-30

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

  5. Designing reactive distillation processes with improved efficiency

    NARCIS (Netherlands)

    Almeida-Rivera, C.P.

    2005-01-01

    In this dissertation a life-span inspired perspective is taken on the conceptual design of grassroots reactive distillation processes. Attention was paid to the economic performance of the process and to potential losses of valuable resources over the process life span. The research was cast in a se

  6. Integrated Process Design and Control of Reactive Distillation Processes

    DEFF Research Database (Denmark)

    Mansouri, Seyed Soheil; Sales-Cruz, Mauricio; Huusom, Jakob Kjøbsted

    2015-01-01

    In this work, integrated process design and control of reactive distillation processes is presented. Simple graphical design methods that are similar in concept to non-reactive distillation processes are used, such as reactive McCabe-Thiele method and driving force approach. The methods are based...... on the element concept, which is used to translate a system of compounds into elements. The operation of the reactive distillation column at the highest driving force and other candidate points is analyzed through analytical solution as well as rigorous open-loop and closed-loop simulations. By application...... of this approach, it is shown that designing the reactive distillation process at the maximum driving force results in an optimal design in terms of controllability and operability. It is verified that the reactive distillation design option is less sensitive to the disturbances in the feed at the highest driving...

  7. Separation of heavy metals from landfill leachate by reactive liquid-liquid extraction

    Energy Technology Data Exchange (ETDEWEB)

    Mickler, W. [Potsdam Univ. (Germany). Inst. fuer Anorganische Chemie und Didaktik der Chemie

    2001-05-01

    The objective of this work was to investigate the decontamination of a model landfill leachate by simultaneous separation of heavy metals from alkaline earth metals and iron in order to obtain a leachate that can be led back to the landfill. Reactive extraction as a separation process offers the possibility of selectively separating cations, that is, of separating toxic components from less problematic ones, and also includes the possibility of electrolysis and further processes to obtain the desired metals. (orig.)

  8. Reactivity of metals for marine phytoplankton

    Energy Technology Data Exchange (ETDEWEB)

    Fisher, N.S.

    1986-03-01

    The concentration of metals by marine phytoplankton, assessed for diverse species in laboratory culture experiments with radiotracer methodology and taken together with literature values for other metals, was analyzed in light of geochemical models describing particle surface chemistry. Concentration factors vary among the metals from approx. ordered 0 to approx. ordered 10/sup 6/. Regression analyses show that, at equilibrium, the logs of the concentration factors are exponentially related to solubility products of metal hydroxides and to cytotoxicity and are linearly related to the log of the mean oceanic residence times (years) of the metals. It would appear that concentration factors and toxicity of metals in marine phytoplankton and oceanic residence times of metals can be predicted to within an order of magnitude from the chemical literature.

  9. Local Chemical Reactivity of a Metal Alloy Surface

    DEFF Research Database (Denmark)

    Hammer, Bjørk; Scheffler, Matthias

    1995-01-01

    The chemical reactivity of a metal alloy surface is studied by density functional theory investigating the interaction of H2 with NiAl(110). The energy barrier for H2 dissociation is largely different over the Al and Ni sites without, however, reflecting the barriers over the single component metal...

  10. Taming reactive phenol tautomers and o-quinone methides with transition metals: a structure-reactivity relationship.

    Science.gov (United States)

    Amouri, Hani; Le Bras, Jean

    2002-07-01

    Quinone methides act as important intermediates in organic syntheses, as well as in chemical and biological processes; however, examples of such isolated species are scarce as a result of their high reactivity. Phenol tautomers (keto form of phenol) are also important intermediates in several organic and organometallic reactions; nevertheless, isolated complexes are rare. This Account reviews the recent progress on the synthesis and reactivity of iridium and rhodium o-quinone methide complexes as well as on iridium-mediated ortho functionalization of phenols. This reaction was at the origin of the discovery of a general synthetic procedure to prepare the first metal-stabilized o-quinone methide.

  11. Reactive boundary layers in metallic rolling contacts

    Energy Technology Data Exchange (ETDEWEB)

    Burbank, John

    2016-05-01

    In order to meet the goal of reducing CO{sub 2} emissions, automotive industry places significant importance on downsizing components to achieve greater efficiency through lower weight and reduced friction. As friction reductions are associated with energy efficiency and wear protection with resource conservation, ever greater attention has been given to adamantine carbon- based coatings and high-alloyed steels. Such applications are, however, associated with high production costs and energy expenditures, as well as many technical difficulties. Therefore a key issue in meeting the goals of friction reduction, wear protection and development of comprehensive lightweight strategies is whether or not the functional profiles of state-of-the art alloys can be enhanced by affordable solutions. The running-in phase of mechanical systems is inevitable and, from a tribological standpoint, critical for the lifetime of such systems, though receives little attention and is poorly understood. The growth of micro-cracks accelerates premature material failure and wear during this phase of heightened friction. With this in mind, the ultimate goal of this current work is to transfer the running-in phase into the final step of the mechanical finishing process through the targeted pre-conditioning of novel, high toughness steel bearings without thermo-chemical treatments and compare these to conventional, case-hardened steels. Two mechanisms were investigated: a. Cold work hardening and b. Chemical tribofilm formation. Steels that showed a tendency toward work hardening and tribofilm formation in previous testing were chosen for this investigation. Thorough characterization of the chosen steels was carried out before any pre-conditioning techniques were applied. The widely used 20MnCr5, seen as a reference gear steel, underwent case-hardening and subsequent deep freezing treatments in an attempt to yield discrete sample groups with respect to residual austenite. This allowed for a

  12. Reactivity of metal catalysts in glucose-fructose conversion.

    Science.gov (United States)

    Loerbroks, Claudia; van Rijn, Jeaphianne; Ruby, Marc-Philipp; Tong, Qiong; Schüth, Ferdi; Thiel, Walter

    2014-09-15

    A joint experimental and computational study on the glucose-fructose conversion in water is reported. The reactivity of different metal catalysts (CrCl3, AlCl3, CuCl2, FeCl3, and MgCl2) was analyzed. Experimentally, CrCl3 and AlCl3 achieved the best glucose conversion rates, CuCl2 and FeCl3 were only mediocre catalysts, and MgCl2 was inactive. To explain these differences in reactivity, DFT calculations were performed for various metal complexes. The computed mechanism consists of two proton transfers and a hydrogen-atom transfer; the latter was the rate-determining step for all catalysts. The computational results were consistent with the experimental findings and rationalized the observed differences in the behavior of the metal catalysts. To be an efficient catalyst, a metal complex should satisfy the following criteria: moderate Brønsted and Lewis acidity (pKa = 4-6), coordination with either water or weaker σ donors, energetically low-lying unoccupied orbitals, compact transition-state structures, and the ability for complexation of glucose. Thus, the reactivity of the metal catalysts in water is governed by many factors, not just the Lewis acidity.

  13. Bonding, aromaticity and reactivity patterns in some all-metal and non-metal clusters

    Indian Academy of Sciences (India)

    S Duley; S Giri; A Chakraborty; P K Chattaraj

    2009-09-01

    Several sandwich-like metal clusters have been studied at the B3LYP/6-311 + G∗ level of theory. Bonding and reactivity have been analysed through various geometrical parameters and conceptual density functional theory based global reactivity descriptors. Aromaticity patterns have been understood in terms of the associated nucleus independent chemical shift values. Possibility of bond-stretch isomerism in some doped clusters is explored. Preferable sites for electrophilic and nucleophilic attacks have been identified using different local reactivity descriptors.

  14. Heavy metal removal capacity of individual components of permeable reactive concrete

    Science.gov (United States)

    Holmes, Ryan R.; Hart, Megan L.; Kevern, John T.

    2017-01-01

    Permeable reactive barriers (PRBs) are a well-known technique for groundwater remediation using industrialized reactive media such as zero-valent iron and activated carbon. Permeable reactive concrete (PRC) is an alternative reactive medium composed of relatively inexpensive materials such as cement and aggregate. A variety of multimodal, simultaneous processes drive remediation of metals from contaminated groundwater within PRC systems due to the complex heterogeneous matrix formed during cement hydration. This research investigated the influence coarse aggregate, portland cement, fly ash, and various combinations had on the removal of lead, cadmium, and zinc in solution. Absorption, adsorption, precipitation, co-precipitation, and internal diffusion of the metals are common mechanisms of removal in the hydrated cement matrix and independent of the aggregate. Local aggregates can be used as the permeable structure also possessing high metal removal capabilities, however calcareous sources of aggregate are preferred due to improved removal with low leachability. Individual adsorption isotherms were linear or curvilinear up, indicating a preferred removal process. For PRC samples, metal saturation was not reached over the range of concentrations tested. Results were then used to compare removal against activated carbon and aggregate-based PRBs by estimating material costs for the remediation of an example heavy metal contaminated Superfund site located in the Midwestern United States, Joplin, Missouri.

  15. Effect of Strain on the Reactivity of Metal Surfaces

    DEFF Research Database (Denmark)

    Mavrikakis, Manos; Hammer, Bjørk; Nørskov, Jens Kehlet

    1998-01-01

    Self-consistent density functional calculations for the adsorption of O and CO, and the dissociation of CO on strained and unstrained Ru(0001) surfaces are used to show how strained metal surfaces have chemical properties that are significantly different from those of unstrained surfaces. Surface...... reactivity increases with lattice expansion, following a concurrent up-shift of the metal d states. Consequences for the catalytic activity of thin metal overlayers are discussed.......Self-consistent density functional calculations for the adsorption of O and CO, and the dissociation of CO on strained and unstrained Ru(0001) surfaces are used to show how strained metal surfaces have chemical properties that are significantly different from those of unstrained surfaces. Surface...

  16. Semisolid Metal Processing Consortium

    Energy Technology Data Exchange (ETDEWEB)

    Apelian,Diran

    2002-01-10

    Mathematical modeling and simulations of semisolid filling processes remains a critical issue in understanding and optimizing the process. Semisolid slurries are non-Newtonian materials that exhibit complex rheological behavior. There the way these slurries flow in cavities is very different from the way liquid in classical casting fills cavities. Actually filling in semisolid processing is often counter intuitive

  17. The chemical and mechanical behaviors of polymer / reactive metal systems under high strain rates

    Science.gov (United States)

    Shen, Yubin

    As one category of energetic materials, impact-initiated reactive materials are able to release a high amount of stored chemical energy under high strain rate impact loading, and are used extensively in civil and military applications. In general, polymers are introduced as binder materials to trap the reactive metal powders inside, and also act as an oxidizing agent for the metal ingredient. Since critical attention has been paid on the metal / metal reaction, only a few types of polymer / reactive metal interactions have been studied in the literature. With the higher requirement of materials resistant to different thermal and mechanical environments, the understanding and characterization of polymer / reactive metal interactions are in great demand. In this study, PTFE (Polytetrafluoroethylene) 7A / Ti (Titanium) composites were studied under high strain rates by utilizing the Taylor impact and SHPB tests. Taylor impact tests with different impact velocities, sample dimensions and sample configurations were conducted on the composite, equipped with a high-speed camera for tracking transient images during the sudden process. SHPB and Instron tests were carried out to obtain the stress vs. strain curves of the composite under a wide range of strain rates, the result of which were also utilized for fitting the constitutive relations of the composite based on the modified Johnson-Cook strength model. Thermal analyses by DTA tests under different flow rates accompanied with XRD identification were conducted to study the reaction mechanism between PTFE 7A and Ti when only heat was provided. Numerical simulations on Taylor impact tests and microstructural deformations were also performed to validate the constitutive model built for the composite system, and to investigate the possible reaction mechanism between two components. The results obtained from the high strain rate tests, thermal analyses and numerical simulations were combined to provide a systematic study on

  18. Dental metal-induced innate reactivity in keratinocytes.

    Science.gov (United States)

    Rachmawati, Dessy; Buskermolen, Jeroen K; Scheper, Rik J; Gibbs, Susan; von Blomberg, B Mary E; van Hoogstraten, Ingrid M W

    2015-12-25

    Gold, nickel, copper and mercury, i.e. four metals frequently used in dental applications, were explored for their capacity to induce innate immune activation in keratinocytes (KC). Due to their anatomical location the latter epithelial cells are key in primary local irritative responses of skin and mucosa. Fresh foreskin-derived keratinocytes and skin and gingiva KC cell lines were studied for IL-8 release as a most sensitive parameter for NF-kB activation. First, we verified that viral-defense mediating TLR3 is a key innate immune receptor in both skin- and mucosa derived keratinocytes. Second, we found that, in line with our earlier finding that ionized gold can mimic viral dsRNA in triggering TLR3, gold is very effective in KC activation. It would appear that epithelial TLR3 can play a key role in both skin- and mucosa localized irritation reactivities to gold. Subsequently we found that not only gold, but also nickel, copper and mercury salts can activate innate immune reactivity in keratinocytes, although the pathways involved remain unclear. Although current alloys have been optimized for minimal leakage of metal ions, secondary factors such as mechanical friction and acidity may still facilitate such leakage. Subsequently, these metal ions may create local irritation, itching and swelling by triggering innate immune reactions, potentially also facilitating the development of metal specific adaptive immunity.

  19. Biodiesel by catalytic reactive distillation powered by metal oxides

    NARCIS (Netherlands)

    Kiss, A.A.; Dimian, A.C.; Rothenberg, G.

    2008-01-01

    The properties and use of biodiesel as a renewable fuel as well as the problems associated with its current production processes are outlined. A novel sustainable esterification process based on catalytic reactive distillation is proposed. The pros and cons of manufacturing biodiesel via fatty acid

  20. Biodiesel by catalytic reactive distillation powered by metal oxides

    NARCIS (Netherlands)

    Kiss, A.A.; Dimian, A.C.; Rothenberg, G.

    2008-01-01

    The properties and use of biodiesel as a renewable fuel as well as the problems associated with its current production processes are outlined. A novel sustainable esterification process based on catalytic reactive distillation is proposed. The pros and cons of manufacturing biodiesel via fatty acid

  1. Elementary surface processes during reactive magnetron sputtering of chromium

    Energy Technology Data Exchange (ETDEWEB)

    Monje, Sascha; Corbella, Carles, E-mail: carles.corbella@rub.de; Keudell, Achim von [Research Group Reactive Plasmas, Ruhr-University Bochum, Universitystr. 150, 44801 Bochum (Germany)

    2015-10-07

    The elementary surface processes occurring on chromium targets exposed to reactive plasmas have been mimicked in beam experiments by using quantified fluxes of Ar ions (400–800 eV) and oxygen atoms and molecules. For this, quartz crystal microbalances were previously coated with Cr thin films by means of high-power pulsed magnetron sputtering. The measured growth and etching rates were fitted by flux balance equations, which provided sputter yields of around 0.05 for the compound phase and a sticking coefficient of O{sub 2} of 0.38 on the bare Cr surface. Further fitted parameters were the oxygen implantation efficiency and the density of oxidation sites at the surface. The increase in site density with a factor 4 at early phases of reactive sputtering is identified as a relevant mechanism of Cr oxidation. This ion-enhanced oxygen uptake can be attributed to Cr surface roughening and knock-on implantation of oxygen atoms deeper into the target. This work, besides providing fundamental data to control oxidation state of Cr targets, shows that the extended Berg's model constitutes a robust set of rate equations suitable to describe reactive magnetron sputtering of metals.

  2. Electrochemistry of hexanitroazobenzene: reactivity with metals and synthetic implications

    Energy Technology Data Exchange (ETDEWEB)

    Firsich, D.W.

    1985-08-08

    The electrochemical properties of hexanitroazobenzene (HNAB) are defined as an aid towards understanding the general reactivity of this commonly used explosive. Cyclic voltammetry, controlled potential coulometry, and visible spectroscopy are used to characterize the anion, dianion, protonated dianion, and diprotonated dianion of HNAB. The acid/base relationships of these species are established, and their role in the present synthetic method for producing HNAB is clearly defined. The feasibility of an electrochemical synthesis for HNAB is demonstrated. It is shown that the reaction between aluminum metal and HNAB in solution produces the protonated dianion of HNAB, and that reactions between other common metals and HNAB do occur. The visible absorption maxima of a number of possible decomposition products of HNAB are compiled. Related chemistry involving a triazole oxide derivative is presented. 5 refs., 5 figs., 2 tabs.

  3. Composite Materials for Hazard Mitigation of Reactive Metal Hydrides.

    Energy Technology Data Exchange (ETDEWEB)

    Pratt, Joseph William; Cordaro, Joseph Gabriel; Sartor, George B.; Dedrick, Daniel E.; Reeder, Craig L.

    2012-02-01

    In an attempt to mitigate the hazards associated with storing large quantities of reactive metal hydrides, polymer composite materials were synthesized and tested under simulated usage and accident conditions. The composites were made by polymerizing vinyl monomers using free-radical polymerization chemistry, in the presence of the metal hydride. Composites with vinyl-containing siloxane oligomers were also polymerized with and without added styrene and divinyl benzene. Hydrogen capacity measurements revealed that addition of the polymer to the metal hydride reduced the inherent hydrogen storage capacity of the material. The composites were found to be initially effective at reducing the amount of heat released during oxidation. However, upon cycling the composites, the mitigating behavior was lost. While the polymer composites we investigated have mitigating potential and are physically robust, they undergo a chemical change upon cycling that makes them subsequently ineffective at mitigating heat release upon oxidation of the metal hydride. Acknowledgements The authors would like to thank the following people who participated in this project: Ned Stetson (U.S. Department of Energy) for sponsorship and support of the project. Ken Stewart (Sandia) for building the flow-through calorimeter and cycling test stations. Isidro Ruvalcaba, Jr. (Sandia) for qualitative experiments on the interaction of sodium alanate with water. Terry Johnson (Sandia) for sharing his expertise and knowledge of metal hydrides, and sodium alanate in particular. Marcina Moreno (Sandia) for programmatic assistance. John Khalil (United Technologies Research Corp) for insight into the hazards of reactive metal hydrides and real-world accident scenario experiments. Summary In an attempt to mitigate and/or manage hazards associated with storing bulk quantities of reactive metal hydrides, polymer composite materials (a mixture of a mitigating polymer and a metal hydride) were synthesized and tested

  4. Chemical thermodynamics as a predictive tool in the reactive metal brazing of ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Wang, G. [Edison Welding Inst., Columbus, OH (United States); Lannutti, J.J. [Ohio State Univ., Columbus, OH (United States)

    1995-06-01

    Thermodynamics have long been applied to the understanding of the reactive wetting phenomena in metal-ceramic joining. The authors postulate the existence of a ``solvent effect`` due to the interaction between the reactive element addition and the brazing alloy. This effect plays a significant role in reactive wetting. By taking this effect into account, more realistic reactivities of different reactive element additions into a given brazing base alloy are predicted. Irreversible thermodynamics are also used to characterize the driving forces for reactive metal-ceramic joining.

  5. Chemical thermodynamics as a predictive tool in the reactive metal brazing of ceramics

    Science.gov (United States)

    Wang, G.; Lannutti, J. J.

    1995-06-01

    Thermodynamics have long been applied to our understanding of the reactive wetting phenomena in metal-ceramic joining. We postulate the existence of a “solvent effect” due to the interaction between the reactive element addition and the brazing alloy. This effect plays a significant role in reactive wetting. By taking this effect into account, more realistic reactivities of different reactive element additions into a given brazing base alloy are predicted. Irreversible thermodynamics are also used to characterize the driving forces for reactive metal-ceramic joining.

  6. S-S bond reactivity in metal-perthiocarboxylato compounds.

    Science.gov (United States)

    Mas-Ballesté, Rubén; Guijarro, Alejandro; González-Prieto, Rodrigo; Castillo, Oscar; Sanz Miguel, Pablo J; Zamora, Félix

    2010-02-14

    While M-percarboxylato species are elusive intermediates, their sulfur containing analogues are known in some cases. The feasibility of isolation of M-perthioacetato compounds allowed, in this work, to obtain new insights into the pathways that follow the reactivity of M-E-ER (E = O, S) fragments. Herein we report on the isolation of two new M-perthioacetato compounds: trans-[Pt(CH(3)CS(2)S)(2)] () and [Ni(CH(3)CSS)(CH(3)CS(2)S)] (), which have been fully characterized, including X-ray structures. Reactivity of these compounds towards PPh(3) has been studied combining UV-vis monitorization and NMR measurements. Overall the accumulated data suggest that the evolution of the perthioacetato ligand in complexes and by reaction with PPh(3) consists of a complex multistep pathway in which the sulfur transfer is preceded by electron transfer. Cyclic voltammetry measurements indicate that the transference of two electrons from the phosphorus to the sulfur atom is not concerted, suggesting that the first step of the reaction with PPh(3) is the monoelectronic electron transfer followed by P-S bond formation. The results presented here show a novel pathway in the field of S-S bond reactivity processes relevant in biological, synthetic systems and in hydrocarbon desulfurization processes.

  7. Control Rod Driveline Reactivity Feedback Model for Liquid Metal Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Young-Min; Jeong, Hae-Yong; Chang, Won-Pyo; Cho, Chung-Ho; Lee, Yong-Bum

    2008-01-15

    The thermal expansion of the control rod drivelines (CRDL) is one important passive mitigator under all unprotected accident conditions in the metal and oxide cores. When the CRDL are washed by hot sodium in the coolant outlet plenum, the CRDL thermally expands and causes the control rods to be inserted further down into the active core region, providing a negative reactivity feedback. Since the control rods are attached to the top of the vessel head and the core attaches to the bottom of the reactor vessel (RV), the expansion of the vessel wall as it heats will either lower the core or raise the control rods supports. This contrary thermal expansion of the reactor vessel wall pulls the control rods out of the core somewhat, providing a positive reactivity feedback. However this is not a safety factor early in a transient because its time constant is relatively large. The total elongated length is calculated by subtracting the vessel expansion from the CRDL expansion to determine the net control rod expansion into the core. The system-wide safety analysis code SSC-K includes the CRDL/RV reactivity feedback model in which control rod and vessel expansions are calculated using single-nod temperatures for the vessel and CRDL masses. The KALIMER design has the upper internal structures (UIS) in which the CRDLs are positioned outside the structure where they are exposed to the mixed sodium temperature exiting the core. A new method to determine the CRDL expansion is suggested. Two dimensional hot pool thermal hydraulic model (HP2D) originally developed for the analysis of the stratification phenomena in the hot pool is utilized for a detailed heat transfer between the CRDL mass and the hot pool coolant. However, the reactor vessel wall temperature is still calculated by a simple lumped model.

  8. Waste metal hydroxide sludge as adsorbent for a reactive dye.

    Science.gov (United States)

    Santos, Sílvia C R; Vílar, Vítor J P; Boaventura, Rui A R

    2008-05-30

    An industrial waste sludge mainly composed by metal hydroxides was used as a low-cost adsorbent for removing a reactive textile dye (Remazol Brilliant Blue) in solution. Characterization of this waste material included chemical composition, pH(ZPC) determination, particle size distribution, physical textural properties and metals mobility under different pH conditions. Dye adsorption equilibrium isotherms were determined at 25 and 35 degrees C and pH of 4, 7 and 10 revealing reasonably fits to Langmuir and Freundlich models. At 25 degrees C and pH 7, Langmuir fit indicates a maximum adsorption capacity of 91.0mg/g. An adsorptive ion-exchange mechanism was identified from desorption studies. Batch kinetic experiments were also conducted at different initial dye concentration, temperature, adsorbent dosage and pH. A pseudo-second-order model showed good agreement with experimental data. LDF approximation model was used to estimate homogeneous solid diffusion coefficients and the effective pore diffusivities. Additionally, a simulated real effluent containing the selected dye, salts and dyeing auxiliary chemicals, was also used in equilibrium and kinetic experiments and the adsorption performance was compared with aqueous dye solutions.

  9. Tuning reactivity of diphenylpropynone derivatives with metal-associated amyloid-β species via structural modifications.

    Science.gov (United States)

    Liu, Yuzhong; Kochi, Akiko; Pithadia, Amit S; Lee, Sanghyun; Nam, Younwoo; Beck, Michael W; He, Xiaoming; Lee, Dongkuk; Lim, Mi Hee

    2013-07-15

    A diphenylpropynone derivative, DPP2, has been recently demonstrated to target metal-associated amyloid-β (metal-Aβ) species implicated in Alzheimer's disease (AD). DPP2 was shown to interact with metal-Aβ species and subsequently control Aβ aggregation (reactivity) in vitro; however, its cytotoxicity has limited further biological applications. In order to improve reactivity toward Aβ species and lower cytotoxicity, along with gaining an understanding of a structure-reactivity-cytotoxicity relationship, we designed, prepared, and characterized a series of small molecules (C1/C2, P1/P2, and PA1/PA2) as structurally modified DPP2 analogues. A similar metal binding site to that of DPP2 was contained in these compounds while their structures were varied to afford different interactions and reactivities with metal ions, Aβ species, and metal-Aβ species. Distinct reactivities of our chemical family toward in vitro Aβ aggregation in the absence and presence of metal ions were observed. Among our chemical series, the compound (C2) with a relatively rigid backbone and a dimethylamino group was observed to noticeably regulate both metal-free and metal-mediated Aβ aggregation to different extents. Using our compounds, cell viability was significantly improved, compared to that with DPP2. Lastly, modifications on the DPP framework maintained the structural properties for potential blood-brain barrier (BBB) permeability. Overall, our studies demonstrated that structural variations adjacent to the metal binding site of DPP2 could govern different metal binding properties, interactions with Aβ and metal-Aβ species, reactivity toward metal-free and metal-induced Aβ aggregation, and cytotoxicity of the compounds, establishing a structure-reactivity-cytotoxicity relationship. This information could help gain insight into structural optimization for developing nontoxic chemical reagents toward targeting metal-Aβ species and modulating their reactivity in biological

  10. Effects of metal ions on the reactivity and corrosion electrochemistry of Fe/FeS nanoparticles.

    Science.gov (United States)

    Kim, Eun-Ju; Kim, Jae-Hwan; Chang, Yoon-Seok; Turcio-Ortega, David; Tratnyek, Paul G

    2014-04-01

    Nano-zerovalent iron (nZVI) formed under sulfidic conditions results in a biphasic material (Fe/FeS) that reduces trichloroethene (TCE) more rapidly than nZVI associated only with iron oxides (Fe/FeO). Exposing Fe/FeS to dissolved metals (Pd(2+), Cu(2+), Ni(2+), Co(2+), and Mn(2+)) results in their sequestration by coprecipitation as dopants into FeS and FeO and/or by electroless precipitation as zerovalent metals that are hydrogenation catalysts. Using TCE reduction rates to probe the effect of metal amendments on the reactivity of Fe/FeS, it was found that Mn(2+) and Cu(2+) decreased TCE reduction rates, while Pd(2+), Co(2+), and Ni(2+) increased them. Electrochemical characterization of metal-amended Fe/FeS showed that aging caused passivation by growth of FeO and FeS phases and poisoning of catalytic metal deposits by sulfide. Correlation of rate constants for TCE reduction (kobs) with electrochemical parameters (corrosion potentials and currents, Tafel slopes, and polarization resistance) and descriptors of hydrogen activation by metals (exchange current density for hydrogen reduction and enthalpy of solution into metals) showed the controlling process changed with aging. For fresh Fe/FeS, kobs was best described by the exchange current density for activation of hydrogen, whereas kobs for aged Fe/FeS correlated with electrochemical descriptors of electron transfer.

  11. The addition of organic carbon and nitrate affects reactive transport of heavy metals in sandy aquifers

    KAUST Repository

    Satyawali, Yamini

    2011-04-01

    Organic carbon introduction in the soil to initiate remedial measures, nitrate infiltration due to agricultural practices or sulphate intrusion owing to industrial usage can influence the redox conditions and pH, thus affecting the mobility of heavy metals in soil and groundwater. This study reports the fate of Zn and Cd in sandy aquifers under a variety of plausible in-situ redox conditions that were induced by introduction of carbon and various electron acceptors in column experiments. Up to 100% Zn and Cd removal (from the liquid phase) was observed in all the four columns, however the mechanisms were different. Metal removal in column K1 (containing sulphate), was attributed to biological sulphate reduction and subsequent metal precipitation (as sulphides). In the presence of both nitrate and sulphate (K2), the former dominated the process, precipitating the heavy metals as hydroxides and/or carbonates. In the presence of sulphate, nitrate and supplemental iron (Fe(OH)3) (K3), metal removal was also due to precipitation as hydroxides and/or carbonates. In abiotic column, K4, (with supplemental iron (Fe(OH)3), but no nitrate), cation exchange with soil led to metal removal. The results obtained were modeled using the reactive transport model PHREEQC-2 to elucidate governing processes and to evaluate scenarios of organic carbon, sulphate and nitrate inputs. © 2010 Elsevier B.V.

  12. Processable Polyimides Containing APB and Reactive End Caps

    Science.gov (United States)

    Jensen, Brian J.

    2003-01-01

    Imide copolymers that contain 1,3- bis(3-aminophenoxy)benzene (APB) and other diamines and dianhydrides and that are terminated with appropriate amounts of reactive end caps have been invented. The reactive end caps investigated thus far include 4-phenylethynyl phthalic anhydride (PEPA), 3- aminophenoxy-4-phenylethynylbenzop henone (3-APEB), maleic anhydride (MA), and 5-norbornene-2,3-dicarboxylic anhydride [also known as nadic anhydride (NA)]. The advantage of these copolyimides terminated with reactive groups, relative to other polyimides terminated with reactive groups, is a combination of (1) higher values of desired mechanical-property parameters and (2) greater ease of processing into useful parts.

  13. Reactivity of diphenylpropynone derivatives toward metal-associated amyloid-β species.

    Science.gov (United States)

    Pithadia, Amit S; Kochi, Akiko; Soper, Molly T; Beck, Michael W; Liu, Yuzhong; Lee, Sanghyun; DeToma, Alaina S; Ruotolo, Brandon T; Lim, Mi Hee

    2012-12-01

    In Alzheimer's disease (AD), metal-associated amyloid-β (metal-Aβ) species have been suggested to be involved in neurotoxicity; however, their role in disease development is still unclear. To elucidate this aspect, chemical reagents have been developed as valuable tools for targeting metal-Aβ species, modulating the interaction between the metal and Aβ, and subsequently altering metal-Aβ reactivity. Herein, we report the design, preparation, characterization, and reactivity of two diphenylpropynone derivatives (DPP1 and DPP2) composed of structural moieties for metal chelation and Aβ interaction (bifunctionality). The interactions of these compounds with metal ions and Aβ species were confirmed by UV-vis, NMR, mass spectrometry, and docking studies. The effects of these bifunctional molecules on the control of in vitro metal-free and metal-induced Aβ aggregation were investigated and monitored by gel electrophoresis and transmission electron microscopy (TEM). Both DPP1 and DPP2 showed reactivity toward metal-Aβ species over metal-free Aβ species to different extents. In particular, DPP2, which contains a dimethylamino group, exhibited greater reactivity with metal-Aβ species than DPP1, suggesting a structure-reactivity relationship. Overall, our studies present a new bifunctional scaffold that could be utilized to develop chemical reagents for investigating metal-Aβ species in AD.

  14. Thermochemistry and Reactivity of Metals Engaged in Chemiionization

    Science.gov (United States)

    2015-12-03

    AFRL) Metal Oxide Space Cloud (MOSC) experiments have been conducted to test the efficiency of forming an artificial plasma cloud by this process...analysis methods have been extensively tested and further developed. 40-45 These studies demonstrate that a phase space theory (PST) approach in which...atmospheric tests. This result is also consistent with the original observations of both Fite and coworkers 65 and Dyke and coworkers 66 that the

  15. Systematic Integrated Process Design and Control of Reactive Distillation Processes Involving Multi-elements

    DEFF Research Database (Denmark)

    Mansouri, Seyed Soheil; Sales-Cruz, Mauricio; Huusom, Jakob Kjøbsted

    2016-01-01

    In this work, integrated process design and control of reactive distillation processes that involve multiple elements (more than two) is addressed through a computer-aided hierarchical decomposition-based framework. Multiple elements are encountered for reactive systems when four or more compounds...... (including inert compounds) are encountered. The reactive distillation design methods and tools which are similar in concept to design of binary non-reactive distillations and binary reactive distillations are used for design of multi-element reactive distillation processes, such as driving force approach...

  16. Heavy-metal-induced reactive oxygen species: phytotoxicity and physicochemical changes in plants.

    Science.gov (United States)

    Shahid, Muhammad; Pourrut, Bertrand; Dumat, Camille; Nadeem, Muhammad; Aslam, Muhammad; Pinelli, Eric

    2014-01-01

    As a result of the industrial revolution, anthropogenic activities have enhanced there distribution of many toxic heavy metals from the earth's crust to different environmental compartments. Environmental pollution by toxic heavy metals is increasing worldwide, and poses a rising threat to both the environment and to human health.Plants are exposed to heavy metals from various sources: mining and refining of ores, fertilizer and pesticide applications, battery chemicals, disposal of solid wastes(including sewage sludge), irrigation with wastewater, vehicular exhaust emissions and adjacent industrial activity.Heavy metals induce various morphological, physiological, and biochemical dysfunctions in plants, either directly or indirectly, and cause various damaging effects. The most frequently documented and earliest consequence of heavy metal toxicity in plants cells is the overproduction of ROS. Unlike redox-active metals such as iron and copper, heavy metals (e.g, Pb, Cd, Ni, AI, Mn and Zn) cannot generate ROS directly by participating in biological redox reactions such as Haber Weiss/Fenton reactions. However, these metals induce ROS generation via different indirect mechanisms, such as stimulating the activity of NADPH oxidases, displacing essential cations from specific binding sites of enzymes and inhibiting enzymatic activities from their affinity for -SH groups on the enzyme.Under normal conditions, ROS play several essential roles in regulating the expression of different genes. Reactive oxygen species control numerous processes like the cell cycle, plant growth, abiotic stress responses, systemic signalling, programmed cell death, pathogen defence and development. Enhanced generation of these species from heavy metal toxicity deteriorates the intrinsic antioxidant defense system of cells, and causes oxidative stress. Cells with oxidative stress display various chemical,biological and physiological toxic symptoms as a result of the interaction between ROS and

  17. Kinetic and mechanistic studies of reactive intermediates in photochemical and transition metal-assisted oxidation, decarboxylation and alkyl transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Carraher, Jack McCaslin [Iowa State Univ., Ames, IA (United States)

    2014-01-01

    Reactive species like high-valent metal-oxo complexes and carbon and oxygen centered radicals are important intermediates in enzymatic systems, atmospheric chemistry, and industrial processes. Understanding the pathways by which these intermediates form, their relative reactivity, and their fate after reactions is of the utmost importance. Herein are described the mechanistic detail for the generation of several reactive intermediates, synthesis of precursors, characterization of precursors, and methods to direct the chemistry to more desirable outcomes yielding ‘greener’ sources of commodity chemicals and fuels.

  18. Reactive Atom Plasma Processing of Slumped Glass Wedges Project

    Data.gov (United States)

    National Aeronautics and Space Administration — The Reactive Atom Plasma (RAPTM) process will be evaluated as a rapid and practical method for fabricating precision wedges in glass sheets. The glass sheets are to...

  19. Integrated Design and Control of Reactive and Non-Reactive Distillation Processes

    DEFF Research Database (Denmark)

    Mansouri, Seyed Soheil; Sales-Cruz, Mauricio; Huusom, Jakob Kjøbsted

    , an alternative approach is to tackle process design and controllability issues simultaneously, in the early stages of process design. This simultaneous synthesis approach provides optimal/near optimal operation and more efficient control of conventional (non-reactive binary distillation columns) (Hamid et al......., 2010) as well as complex chemical processes; for example, intensified processes such as reactive distillation (Mansouri et al., 2015). Most importantly, it identifies and eliminates potentially promising design alternatives that may have controllability problems later. To date, a number...... of methodologies have been proposed and applied on various problems to address the interactions between process design and control, and they range from optimization-based approaches to model-based methods (Sharifzadeh, 2013). In this work, integrated design and control of non-reactive distillation, ternary...

  20. Systematic Integrated Process Design and Control of Binary Element Reactive Distillation Processes

    DEFF Research Database (Denmark)

    Mansouri, Seyed Soheil; Sales-Cruz, Mauricio; Huusom, Jakob Kjøbsted

    2016-01-01

    In this work, integrated process design and control of reactive distillation processes is considered through a computer-aided framework. First, a set of simple design methods for reactive distillation column that are similar in concept to non-reactive distillation design methods are extended to d...

  1. Systematic Integrated Process Design and Control of Binary Element Reactive Distillation Processes

    DEFF Research Database (Denmark)

    Mansouri, Seyed Soheil; Sales-Cruz, Mauricio; Huusom, Jakob Kjøbsted

    2016-01-01

    In this work, integrated process design and control of reactive distillation processes is considered through a computer-aided framework. First, a set of simple design methods for reactive distillation column that are similar in concept to non-reactive distillation design methods are extended....... It is shown that the same design-control principles that apply to a non-reacting binary system of compounds are also valid for a reactive binary system of elements for distillation columns. Application of this framework shows that designing the reactive distillation process at the maximum driving force...... results in a feasible and reliable design of the process as well as the controller structure....

  2. Voltage equilibration for reactive atomistic simulations of electrochemical processes

    Energy Technology Data Exchange (ETDEWEB)

    Onofrio, Nicolas; Strachan, Alejandro, E-mail: strachan@purdue.edu [School of Materials Engineering and Birck Nanotechnology Center, Purdue University, West Lafayette, Indiana 47906 (United States)

    2015-08-07

    We introduce electrochemical dynamics with implicit degrees of freedom (EChemDID), a model to describe electrochemical driving force in reactive molecular dynamics simulations. The method describes the equilibration of external electrochemical potentials (voltage) within metallic structures and their effect on the self-consistent partial atomic charges used in reactive molecular dynamics. An additional variable assigned to each atom denotes the local potential in its vicinity and we use fictitious, but computationally convenient, dynamics to describe its equilibration within connected metallic structures on-the-fly during the molecular dynamics simulation. This local electrostatic potential is used to dynamically modify the atomic electronegativities used to compute partial atomic changes via charge equilibration. Validation tests show that the method provides an accurate description of the electric fields generated by the applied voltage and the driving force for electrochemical reactions. We demonstrate EChemDID via simulations of the operation of electrochemical metallization cells. The simulations predict the switching of the device between a high-resistance to a low-resistance state as a conductive metallic bridge is formed and resistive currents that can be compared with experimental measurements. In addition to applications in nanoelectronics, EChemDID could be useful to model electrochemical energy conversion devices.

  3. Using the Multipole Resonance Probe to Stabilize the Electron Density During a Reactive Sputter Process

    Science.gov (United States)

    Oberberg, Moritz; Styrnoll, Tim; Ries, Stefan; Bienholz, Stefan; Awakowicz, Peter

    2015-09-01

    Reactive sputter processes are used for the deposition of hard, wear-resistant and non-corrosive ceramic layers such as aluminum oxide (Al2O3) . A well known problem is target poisoning at high reactive gas flows, which results from the reaction of the reactive gas with the metal target. Consequently, the sputter rate decreases and secondary electron emission increases. Both parameters show a non-linear hysteresis behavior as a function of the reactive gas flow and this leads to process instabilities. This work presents a new control method of Al2O3 deposition in a multiple frequency CCP (MFCCP) based on plasma parameters. Until today, process controls use parameters such as spectral line intensities of sputtered metal as an indicator for the sputter rate. A coupling between plasma and substrate is not considered. The control system in this work uses a new plasma diagnostic method: The multipole resonance probe (MRP) measures plasma parameters such as electron density by analyzing a typical resonance frequency of the system response. This concept combines target processes and plasma effects and directly controls the sputter source instead of the resulting target parameters.

  4. Reactivity patterns of transition metal hydrides and alkyls

    Energy Technology Data Exchange (ETDEWEB)

    Jones, W.D. II

    1979-05-01

    The complex PPN/sup +/ CpV(CO)/sub 3/H/sup -/ (Cp=eta/sup 5/-C/sub 5/H/sub 5/ and PPN = (Ph/sub 3/P)/sub 2/) was prepared in 70% yield and its physical properties and chemical reactions investigated. PPN/sup +/ CpV(CO)/sub 3/H/sup -/ reacts with a wide range of organic halides. The organometallic products of these reactions are the vanadium halides PPN/sup +/(CpV(C)/sub 3/X)/sup -/ and in some cases the binuclear bridging hydride PPN/sup +/ (CpV(CO)/sub 3/)/sub 2/H/sup -/. The borohydride salt PPN/sup +/(CpV(CO)/sub 3/BH/sub 4/)/sup -/ has also been prepared. The reaction between CpV(CO)/sub 3/H/sup -/ and organic halides was investigated and compared with halide reductions carried out using tri-n-butyltin hydride. Results demonstrate that in almost all cases, the reduction reaction proceeds via free radical intermediates which are generated in a chain process, and are trapped by hydrogen transfer from CpV(CO)/sub 3/H/sup -/. Sodium amalgam reduction of CpRh(CO)/sub 2/ or a mixture of CpRh(CO)/sub 2/ and CpCo(CO)/sub 2/ affords two new anions, PPN/sup +/ (Cp/sub 2/Rh/sub 3/(CO)/sub 4/)/sup -/ and PPN/sup +/(Cp/sub 2/RhCo(CO)/sub 2/)/sup -/. CpMo(CO)/sub 3/H reacts with CpMo(CO)/sub 3/R (R=CH/sub 3/,C/sub 2/H/sub 5/, CH/sub 2/C/sub 6/H/sub 5/) at 25 to 50/sup 0/C to produce aldehyde RCHO and the dimers (CpMo(CO)/sub 3/)/sub 2/ and (CpMo(CO)/sub 2/)/sub 2/. In general, CpV(CO)/sub 3/H/sup -/ appears to transfer a hydrogen atom to the metal radical anion formed in an electron transfer process, whereas CpMo(CO)/sub 3/H transfers hydride in a 2-electron process to a vacant coordination site. The chemical consequences are that CpV(CO)/sub 3/H/sup -/ generally reacts with metal alkyls to give alkanes via intermediate alkyl hydride species whereas CpMo(CO)/sub 3/H reacts with metal alkyls to produce aldehyde, via an intermediate acyl hydride species.

  5. Reactivity patterns of transition metal hydrides and alkyls

    Energy Technology Data Exchange (ETDEWEB)

    Jones, W.D. II

    1979-05-01

    The complex PPN/sup +/ CpV(CO)/sub 3/H/sup -/ (Cp=eta/sup 5/-C/sub 5/H/sub 5/ and PPN = (Ph/sub 3/P)/sub 2/) was prepared in 70% yield and its physical properties and chemical reactions investigated. PPN/sup +/ CpV(CO)/sub 3/H/sup -/ reacts with a wide range of organic halides. The organometallic products of these reactions are the vanadium halides PPN/sup +/(CpV(C)/sub 3/X)/sup -/ and in some cases the binuclear bridging hydride PPN/sup +/ (CpV(CO)/sub 3/)/sub 2/H/sup -/. The borohydride salt PPN/sup +/(CpV(CO)/sub 3/BH/sub 4/)/sup -/ has also been prepared. The reaction between CpV(CO)/sub 3/H/sup -/ and organic halides was investigated and compared with halide reductions carried out using tri-n-butyltin hydride. Results demonstrate that in almost all cases, the reduction reaction proceeds via free radical intermediates which are generated in a chain process, and are trapped by hydrogen transfer from CpV(CO)/sub 3/H/sup -/. Sodium amalgam reduction of CpRh(CO)/sub 2/ or a mixture of CpRh(CO)/sub 2/ and CpCo(CO)/sub 2/ affords two new anions, PPN/sup +/ (Cp/sub 2/Rh/sub 3/(CO)/sub 4/)/sup -/ and PPN/sup +/(Cp/sub 2/RhCo(CO)/sub 2/)/sup -/. CpMo(CO)/sub 3/H reacts with CpMo(CO)/sub 3/R (R=CH/sub 3/,C/sub 2/H/sub 5/, CH/sub 2/C/sub 6/H/sub 5/) at 25 to 50/sup 0/C to produce aldehyde RCHO and the dimers (CpMo(CO)/sub 3/)/sub 2/ and (CpMo(CO)/sub 2/)/sub 2/. In general, CpV(CO)/sub 3/H/sup -/ appears to transfer a hydrogen atom to the metal radical anion formed in an electron transfer process, whereas CpMo(CO)/sub 3/H transfers hydride in a 2-electron process to a vacant coordination site. The chemical consequences are that CpV(CO)/sub 3/H/sup -/ generally reacts with metal alkyls to give alkanes via intermediate alkyl hydride species whereas CpMo(CO)/sub 3/H reacts with metal alkyls to produce aldehyde, via an intermediate acyl hydride species.

  6. INVESTIGATION ON DURABILITY AND REACTIVITY OF PROMISING METAL OXIDE SORBENTS DURING SULFIDATION AND REGENERATION. QUARTERLY AND FINAL REPORT

    Energy Technology Data Exchange (ETDEWEB)

    K.C. KWON

    1998-08-01

    Hot-gas desulfurization for the integrated gasification combined cycle (IGCC) process has been investigated by many researchers to remove effectively hydrogen sulfide with various metal oxide sorbents at high pressures and high temperatures. Metal oxides such as zinc titanate oxides, zinc ferrite oxide, copper oxide, manganese oxide and calcium oxide, were found to be promising sorbents in comparison with other removal methods such as membrane separations and reactive membrane separations. Some metal oxide sorbents exhibited the quite favorable performance in terms of attrition resistance and sulfur capacity. Experiments on removal reaction of H{sub 2}S from coal gas mixtures with formulated metal oxide sorbents were conducted in a batch reactor or a differential reactor. The objectives of this research project are to formulate promising metal oxide sorbents for removal of sulfur from coal gas mixtures, to find initial reaction kinetics for the metal oxide-hydrogen sulfide heterogeneous reaction system, to obtain effects of hydrogen, nitrogen and moisture on dynamic absorption and equilibrium absorption at various absorption temperatures. Promising durable metal oxide sorbents with high-sulfur-absorbing capacity were formulated by mixing active metal oxide powders with inert metal oxide powders, and calcining these powder mixtures. The Research Triangle Institute (RTI), a sub-contractor of this research project, will also prepare promising metal oxide sorbents for this research project, plan experiments on removal of sulfur compounds from coal gases with metal oxide, and review experimental results.

  7. INVESTIGATION ON DURABILITY AND REACTIVITY OF PROMISING METAL OXIDE SORBENTS DURING SULFIDATION AND REGENERATION. QUARTERLY AND FINAL REPORT

    Energy Technology Data Exchange (ETDEWEB)

    K.C. KWON

    1998-08-01

    Hot-gas desulfurization for the integrated gasification combined cycle (IGCC) process has been investigated by many researchers to remove effectively hydrogen sulfide with various metal oxide sorbents at high pressures and high temperatures. Metal oxides such as zinc titanate oxides, zinc ferrite oxide, copper oxide, manganese oxide and calcium oxide, were found to be promising sorbents in comparison with other removal methods such as membrane separations and reactive membrane separations. Some metal oxide sorbents exhibited the quite favorable performance in terms of attrition resistance and sulfur capacity. Experiments on removal reaction of H{sub 2}S from coal gas mixtures with formulated metal oxide sorbents were conducted in a batch reactor or a differential reactor. The objectives of this research project are to formulate promising metal oxide sorbents for removal of sulfur from coal gas mixtures, to find initial reaction kinetics for the metal oxide-hydrogen sulfide heterogeneous reaction system, to obtain effects of hydrogen, nitrogen and moisture on dynamic absorption and equilibrium absorption at various absorption temperatures. Promising durable metal oxide sorbents with high-sulfur-absorbing capacity were formulated by mixing active metal oxide powders with inert metal oxide powders, and calcining these powder mixtures. The Research Triangle Institute (RTI), a sub-contractor of this research project, will also prepare promising metal oxide sorbents for this research project, plan experiments on removal of sulfur compounds from coal gases with metal oxide, and review experimental results.

  8. Enhanced reactive metal wall for dehalogenation of hydrocarbons

    Science.gov (United States)

    Howson, Paul E.; Mackenzie, Patricia D.; Horney, David P.

    1996-01-01

    A method is provided for remediation of contaminated solutions using a tiered metal wall or column. The tiered metal wall or column has at least three zones with graduated sizes of reducing metal particles. Contaminated solutions pass through the tiered wall or column to dehalogenate contaminant halogenated hydrocarbons.

  9. Enhanced reactive metal wall for dehalogenation of hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Howson, P.E.; Mackenzie, P.D.; Horney, D.P.

    1996-08-06

    A method is provided for remediation of contaminated solutions using a tiered metal wall or column. The tiered metal wall or column has at least three zones with graduated sizes of reducing metal particles. Contaminated solutions pass through the tiered wall or column to dehalogenate contaminant halogenated hydrocarbons. 3 figs.

  10. Reduce Plasticizer Migration by Modification of PVC during Reactive Processing

    Institute of Scientific and Technical Information of China (English)

    XING X S; SCOTT G

    2003-01-01

    Plasticizers in plasticized polyvinyl chloride (PVC) are generally physically added into PVC by compounding so that they can be rapidly leached from PVC articles during service. This results in their migration into the human environment with potentially serious consequences and lower effectiveness of the additives in PVC. Potentially the chemical modification of PVC during processing via reactive processing procedure is one of the most attractive solutions to these problems.In this paper, we will report our work in exploring an environmentally friendly and cost-effective reactive processing approach for chemically binding plasticizer into PVC chains.Our research results indicate that it is possible to reduce the plasticizer migration from a plasticized PVC by chemically binding of a certain plasticizer into PVC chains via reactive processing. Thus, high levels of binding of DBM, a maleate plasticizer, to PVC may be reached in less than 10 min under prevailing reactive processing conditions. The extent of binding of DBM as a function of the loading shows two peaks: one at a relatively low loading (less than 0.12 mol*kg-1 PVC) tends to 100%, the other in the high loading region (more than 1.5 mol*kg-1 PVC) approaches around 50%. The DBM modified PVC polymer exhibits behaviours as a plasticized PVC but its bound plasticising groups would not be leached by solvent extraction.

  11. Reduce Plasticizer Migration by Modification of PVC during Reactive Processing

    Institute of Scientific and Technical Information of China (English)

    XINGXS; SCOTTG

    2003-01-01

    Plasticizers in plasticized polyvinyl chloride (PVC) are generally physically added into PVC by compounding so that they can be rapidly leached from PVC articles during service. This results in their migration into the human environment with potentially serious consequences and lower effectiveness of the additives in PVC. Potentially the chemical modification of PVC during processing via reactive processing procedure is one of the most attractive solutions to these problems. In this paper, we will report our work in exploring an environmentally friendly and cost-effective reactive processing approach for chemically binding plasticizer into PVC chains. Our research results indicate that it is possible to reduce the plasticizer migration from a plasticized PVC by chemically binding of a certain plasticizer into PVC chains via reactive processing. Thus, high levels of binding of DBM,a maleate plasticizer, to PVC may be reached in less than 10 min under prevailing reactive processing conditions. The extent of binding of DBM as a function of the loading shows two peaks: one at a relatively low loading (less than 0.12 mol·kg-1 PVC) tends to 100%, the other in the high loading region (more than 1.5 mol·kg-1 PVC) approaches around 50%. The DBM modified PVC polymer exhibits behaviours as a plasticized PVC but its bound plasticising groups would not be leached by solvent extraction.

  12. Reactivity of Zerovalent Metals in Aquatic Media: Effects of Organic Surface Coatings

    Energy Technology Data Exchange (ETDEWEB)

    Tratnyek, Paul G.; Salter-Blanc, Alexandra; Nurmi, James; Amonette, James E.; Liu, Juan; Wang, Chong M.; Dohnalkova, Alice; Baer, Donald R.

    2011-09-02

    Granular, reactive zerovalent metals (ZVMs)—especially iron (ZVI)—form the basis for model systems that have been used in fundamental and applied studies of a wide variety of environmental processes. This has resulted in notable advances in many areas, including the kinetics and mechanisms of contaminant reduction reactions, theory of filtration and transport of colloids in porous media, and modeling of complex reactive-transport scenarios. Recent emphasis on nano-sized ZVI has created a new opportunity: to advance the understanding of how coatings of organic polyelectrolytes—like natural organic matter (NOM)—influence the reactivity of environmental surfaces. Depending on many factors, organic coatings can be activating or passivating with respect to redox reactions at particle-solution interfaces. In this study, we show the effects of organic coatings on nZVI vary with a number of factors including: (i) time (i.e., “aging” is evident not only in the structure and composition of the nZVI but also in the interactions between nZVI and NOM) and (ii) the type of organic matter (i.e., suspensions of nZVI are stabilized by NOM and the model polyelectrolyte carboxymethylcellulose (CMC), but NOM stimulates redox reactions involving nZVI while CMC inhibits them).

  13. Metals Processing Laboratory User Center (MPLUS)

    Energy Technology Data Exchange (ETDEWEB)

    Mackiewicz-Ludtka, G.; Hayden, H.W. [Oak Ridge National Lab., TN (United States)

    1997-04-01

    The Metals Processing Laboratory User (MPLUS) Center was officially designated as a DOE User Facility in February, 1996. It`s primary purpose is to assist researchers in key U.S. industries, universities, and federal laboratories in improving energy efficiency and enhancing U.S. competitiveness in the world market. The MPLUS Center provides users the unique opportunity to address technology-related issues to solve metals-processing problems from a fully integrated approach. DOE facilitates the process and catalyzes industrial interactions that enables technical synergy and financial leveraging to take place between the industrial sector identifying and prioritizing their technological needs, and MPLUS, which provides access to the technical expertise and specialized facilities to address these needs. MPLUS is designed to provide U.S. industries with access to the specialized technical expertise and equipment needed to solve metals-processing issues that limit the development and implementation of emerging metals-processing technologies. As originated, MPLUS includes the following four primary user centers: Metals Processing, Metals Joining, Metals Characterization, and Metals Process Modeling. These centers are devoted to assisting U.S. industries in adjusting to rapid changes in the marketplace and in improving products and processes. This approach optimizes the complementary strengths of industry and government. Tremendous industrial response, has resulted in MPLUS expanding to meet the ever-growing technical needs and requests initiated by U.S. industry.

  14. BIOMASS REACTIVITY IN GASIFICATION BY THE HYNOL PROCESS

    Science.gov (United States)

    A thermobalance reactor was used to evaluate the reactivity of poplar wood in gasification under the operating conditions specific for the Hynol process where biomass is gasified at 30 atm and 800E C with a hydrogen-rich gas recycled from methane synthesis. The gasification invol...

  15. Improvement of reactivity coefficients of metallic fuel LMFBR by adding moderating material

    Energy Technology Data Exchange (ETDEWEB)

    Tsujimoto, K. E-mail: ktsuji@omega.tokai.jaeri.go.jp; Iwasaki, T.; Hirakawa, N.; Osugi, T.; Okajima, S.; Andoh, M

    2001-06-01

    For a metallic fuel liquid metal fast breeder reactor, we studied a core concept for improving the Doppler coefficient and the sodium void reactivity without much sacrificing the breeding ratio and the burnup reactivity loss. In the concept, several ordinary fuel pins in all fuel assemblies of a core are substituted by pins containing only zirconium hydride (ZrH). A parametric survey for the ZrH fraction from about 1 to about 5% was performed in this study to investigate the reactivity coefficients and the associated demerits in order to search the optimum fraction of ZrH. The metallic fuel core containing about 3% of ZrH showed the good results for all parameters. Following the parametric study, the effect of hydrogenous material in a metallic fuel core was experimentally confirmed. Doppler reactivity, sodium void reactivity and sample reactivity worths of plutonium and B{sub 4}C were measured in a series of critical experiment at FCA of JAERI. The experimental results showed that the hydrogenous material significantly improved the Doppler and the sodium void reactivities. Analysis of experimental results was performed to check the applicability of the present design codes for a fast reactor with hydrogenous materials.

  16. Fundamental reactivity of the Metal-Carbon bond in cyclometalated PNC-complexes

    NARCIS (Netherlands)

    Jongbloed, L.S.

    2016-01-01

    The activation of C-H bonds by transition metals and the reactivity of the corresponding metal-carbon bond are interesting research topics form different point of views. Catalytic C-H bond functionalization has emerged as a highly active research area for the development of green construction of Car

  17. Investigation of Ternary Transition-Metal Nitride Systems by Reactive Cosputtering

    NARCIS (Netherlands)

    Dover, R.B. Van; Hessen, B.; Werder, D.; Chen, C.-H.; Felder, R.J.

    1993-01-01

    A reactive dc cosputtering technique has been used to evaluate compound formation in bimetallic transition-metal nitride systems. A wide range in M-M’ composition can be studied in a single deposition run, and the method is applicable to nonalloying metal combinations. Using this technique, it was f

  18. Fundamental reactivity of the Metal-Carbon bond in cyclometalated PNC-complexes

    NARCIS (Netherlands)

    L.S. Jongbloed

    2016-01-01

    The activation of C-H bonds by transition metals and the reactivity of the corresponding metal-carbon bond are interesting research topics form different point of views. Catalytic C-H bond functionalization has emerged as a highly active research area for the development of green construction of Car

  19. Asymptomatic prospective and retrospective cohorts with metal-on-metal hip arthroplasty indicate acquired lymphocyte reactivity varies with metal ion levels on a group basis.

    Science.gov (United States)

    Hallab, Nadim J; Caicedo, Marco; McAllister, Kyron; Skipor, Anastasia; Amstutz, Harlan; Jacobs, Joshua J

    2013-02-01

    Some tissues from metal-on-metal (MoM) hip arthroplasty revisions have shown evidence of adaptive-immune reactivity (i.e., excessive peri-implant lymphocyte infiltration/activation). We hypothesized that, prior to symptoms, some people with MoM hip arthroplasty will develop quantifiable metal-induced lymphocyte reactivity responses related to peripheral metal ion levels. We tested three cohorts (Group 1: n = 21 prospective longitudinal MoM hip arthroplasty; Group 2: n = 17 retrospective MoM hip arthroplasty; and Group 3: n = 20 controls without implants). We compared implant position, metal-ion release, and immuno-reactivity. MoM cohorts had elevated (p Group 1:1.2 ppb Co, 1.5 ppb Cr; Group 2: 3.4 ppb Co, 5.4 ppb Cr; Group 3: 0.01 ppb Co, 0.1 ppb Cr). However, only after 1-4 years post-op did 56% of Group 1 develop metal-reactivity (vs. 5% pre-op, metal-LTT, SI > 2), compared with 76% of Group 2, and 15% of Group 3 controls (patch testing was a poor diagnostic indicator with only 1/21 Group 1 positive). Higher cup-abduction angles (50° vs. 40°) in Group 1 were associated with higher serum Cr (p Group-1 participants (p Group 1 participants. Our results showed that lymphocyte reactivity to metals can develop within the first 1-4 years after MoM arthroplasty in asymptomatic patients and lags increases in metal ion levels. This increased metal reactivity was more prevalent in those individuals with extreme cup angles and higher amounts of circulating metal. Copyright © 2012 Orthopaedic Research Society.

  20. Ligand Control of the Metal Coordination Sphere: Structures, Reactivity and Catalysis

    Directory of Open Access Journals (Sweden)

    Danopoulos Andreas A.

    2016-03-01

    Full Text Available Two major aspects of coordination/organometallic chemistry are discussed in this article: (i the use of functional chelating ligands to stabilize metal complexes while allowing easy stereodifferentiation within the coordination sphere and (ii the choice of suitable ligands to stabilize challenging ‘underligated’ metal complexes with electronically highly unsaturated metal centres, thus potentially displaying unusual reactivity. In both cases, the relevance to homogeneous catalysis will be discussed.

  1. Reactivity of Metal-Free and Metal-Associated Amyloid-β with Glycosylated Polyphenols and Their Esterified Derivatives.

    Science.gov (United States)

    Korshavn, Kyle J; Jang, Milim; Kwak, Yeon Ju; Kochi, Akiko; Vertuani, Silvia; Bhunia, Anirban; Manfredini, Stefano; Ramamoorthy, Ayyalusamy; Lim, Mi Hee

    2015-12-10

    Both amyloid-β (Aβ) and transition metal ions are shown to be involved in the pathogenesis of Alzheimer's disease (AD), though the importance of their interactions remains unclear. Multifunctional molecules, which can target metal-free and metal-bound Aβ and modulate their reactivity (e.g., Aβ aggregation), have been developed as chemical tools to investigate their function in AD pathology; however, these compounds generally lack specificity or have undesirable chemical and biological properties, reducing their functionality. We have evaluated whether multiple polyphenolic glycosides and their esterified derivatives can serve as specific, multifunctional probes to better understand AD. The ability of these compounds to interact with metal ions and metal-free/-associated Aβ, and further control both metal-free and metal-induced Aβ aggregation was investigated through gel electrophoresis with Western blotting, transmission electron microscopy, UV-Vis spectroscopy, fluorescence spectroscopy, and NMR spectroscopy. We also examined the cytotoxicity of the compounds and their ability to mitigate the toxicity induced by both metal-free and metal-bound Aβ. Of the polyphenols investigated, the natural product (Verbascoside) and its esterified derivative (VPP) regulate the aggregation and cytotoxicity of metal-free and/or metal-associated Aβ to different extents. Our studies indicate Verbascoside represents a promising structure for further multifunctional tool development against both metal-free Aβ and metal-Aβ.

  2. Metallic parts fabrication using the SIS process

    Science.gov (United States)

    Mojdeh, Mehdi

    Since early 1980s, quite a few techniques of Rapid Prototyping (RP), also known as Layered Manufacturing, have been developed. By building three-dimensional parts in a layer-by-layer additive manner, these techniques allow freeform fabrication of parts of complex geometry. Despite recent advances in fabrication of polymer parts, most of the existing rapid prototyping processes are still not capable of fabrication of accurate metallic parts with acceptable mechanical properties. Insufficient dimensional accuracy, limited number of materials, proper mechanical properties, required post machining and lack of repeatability between builds have greatly limited the market penetration of these techniques. This dissertation presents an innovative layered manufacturing technique for fabrication of dense metallic parts called Selective Inhibition Sintering (SIS), developed at the University of Southern California. The SIS-Metal technology adapts RP capabilities and extends them to the field of fabrication of metallic parts for a variety of applications such as tooling and low volume production. Using this process, a metallic part, with varying 3 dimensional geometries, can be automatically constructed from a wide range of materials. SIS-Metal is the only RP process which is suitable for fabrication of dense, complex shaped, accurate objects using a variety of materials. In the SIS-Metal process a metallic part is built layer by layer by deposition for each layer of an inhibitor material which defines the corresponding layer boundary and then filling the voids of the created geometry with metal powder; and compacting the layer formed to reach a high powder density. The resulting green part is then sintered in a furnace to yield the final functional part. In this research different inhibition techniques were explored and a series of single and multi layer parts was fabricated using the most promising inhibition technique, namely, macro-mechanical inhibition. Dimensional

  3. Synthesis of functional nanocrystallites through reactive thermal plasma processing

    Directory of Open Access Journals (Sweden)

    Takamasa Ishigaki and Ji-Guang Li

    2007-01-01

    Full Text Available A method of synthesizing functional nanostructured powders through reactive thermal plasma processing has been developed. The synthesis of nanosized titanium oxide powders was performed by the oxidation of solid and liquid precursors. Quench gases, either injected from the shoulder of the reactor or injected counter to the plasma plume from the bottom of the reactor, were used to vary the quench rate, and therefore the particle size, of the resultant powders. The experimental results are well supported by numerical analysis on the effects of the quench gas on the flow pattern and temperature field of the thermal plasma as well as on the trajectory and temperature history of the particles. The plasma-synthesized TiO2 nanoparticles showed phase preferences different from those synthesized by conventional wet-chemical processes. Nanosized particles of high crystallinity and nonequilibrium chemical composition were formed in one step via reactive thermal plasma processing.

  4. Reactive Bonding Film for Bonding Carbon Foam Through Metal Extrusion

    CERN Document Server

    Chertok, Maxwell; Irving, Michael; Neher, Christian; Tripathi, Mani; Wang, Ruby; Zheng, Gayle

    2016-01-01

    Future tracking detectors, such as those under development for the High Luminosity LHC, will require mechanical structures employing novel materials to reduce mass while providing excellent strength, thermal conductivity, and radiation tolerance. Adhesion methods for such materials are under study at present. This paper demonstrates the use of reactive bonding film as an adhesion method for bonding carbon foam.

  5. Paths of progress in liquid metal processing

    Science.gov (United States)

    McLean, A.; Soda, H.; Sommerville, I. D.

    1995-04-01

    Industry has identified three major issues as being fundamental to future technological developments: process step elimination, product-process integration, and intelligent processing. This article reviews these concepts by discussing recent research at the University of Toronto on plasma processing, netshape casting, and diagnostic sensors for the evaluation of liquid metal quality.

  6. LEACHING OF METALS FROM MINERAL PROCESSING WASTE

    Science.gov (United States)

    The purpose of this project is to test the leaching of Mineral Processing Waste (MPW) contaminated with heavy metals using scientifically defendable leaching tests other than TCLP. Past experience and literature have shown that TCLP underestimates the levels of metals such as oxo...

  7. Reaction mechanisms and microstructures of ceramic-metal composites made by reactive metal penetration

    Energy Technology Data Exchange (ETDEWEB)

    Fahrenholtz, W.F. [Univ. of New Mexico, Albuquerque, NM (United States). Advanced Materials Lab.; Ewsuk, K.G.; Loehman, R.E. [Sandia National Labs., NM (United States)] [and others

    1996-12-31

    Ceramic-metal composites can be made by reactive penetration of molten metals into dense ceramic performs. The metal penetration is driven by a large negative Gibbs energy for reaction, which is different from the more common physical infiltration of porous media. Reactions involving Al can be written generally as (x+2)Al + (3/y)MO{sub y} {yields} Al{sub 2}O{sub 3} + M{sub 3/y}Al{sub x}, where MO{sub y} is an oxide that is wet by molten Al. In low Po{sub 2} atmospheres and at temperature above about 900{degrees}c, molten Al reduces mullite to produce Al{sub 2}O{sub 3} + M{sub 3/y}Al{sub x}, where MO is an oxide that is wet by molten Al. In low Po{sub 2} atmospheres and at temperatures above about 900{degrees}C, molten al reduces mullite to produce Al{sub 2}O{sub 3} and Si. The Al/mullite reaction has a {Delta}G{sub r}{degrees} (1200K) of -1014 kJ/mol and, if the mullite is fully dense, the theoretical volume change on reaction is less than 1%. A microstructure of mutually-interpenetrating metal and ceramic phases generally is obtained. Penetration rate increases with increasing reaction temperature from 900 to 1150{degrees}C, and the reaction layer thickness increases linearly with time. Reaction rate is a maximum at 1150{degrees}C; above that temperature the reaction slows and stops after a relatively short period of linear growth. At 1300{degrees}C and above, no reaction layer is detected by optical microscopy. Observations of the reaction front by TEM show only al and Al{sub 2}O{sub 3} after reaction at 900{degrees}C, but Si is present in increasing amounts as the reaction temperature increases to 1100{degrees}C and above. The kinetic and microstructural data suggest that the deviation from linear growth kinetics at higher reaction temperatures and longer times is due to Si build-up and saturation at the reaction front. The activation energy for short reaction times at 900 to 1150{degrees}C varies from {approximately}90 to {approximately}200 kJ/mole.

  8. Process Improvement of Reactive Dye Synthesis Using Six Sigma Concept

    Science.gov (United States)

    Suwanich, Thanapat; Chutima, Parames

    2017-06-01

    This research focuses on the problem occurred in the reactive dye synthesis process of a global manufacturer in Thailand which producing various chemicals for reactive dye products to supply global industries such as chemicals, textiles and garments. The product named “Reactive Blue Base” is selected in this study because it has highest demand and the current chemical yield shows a high variation, i.e. yield variation of 90.4% - 99.1% (S.D. = 2.405 and Cpk = -0.08) and average yield is 94.5% (lower than the 95% standard set by the company). The Six Sigma concept is applied aiming at increasing yield and reducing variation of this process. This approach is suitable since it provides a systematic guideline with five improvement phases (DMAIC) to effectively tackle the problem and find the appropriate parameter settings of the process. Under the new parameter settings, the process yield variation is reduced to range between 96.5% - 98.5% (S.D. = 0.525 and Cpk = 1.83) and the average yield is increased to 97.5% (higher than the 95% standard set by the company).

  9. Structurally defined allyl compounds of main group metals: coordination and reactivity.

    Science.gov (United States)

    Lichtenberg, Crispin; Okuda, Jun

    2013-05-10

    Organometallic allyl compounds are important as allylation reagents in organic synthesis, as polymerization catalysts, and as volatile metal precursors in material science. Whereas the allyl chemistry of synthetically relevant transition metals such as palladium and of the lanthanoids is well-established, that of main group metals has been lagging behind. Recent progress on allyl complexes of Groups 1, 2, and 12-16 now provides a more complete picture. This is based on a fundamental understanding of metal-allyl bonding interactions in solution and in the solid state. Furthermore, reactivity trends have been rationalized and new types of allyl-specific reactivity patterns have been uncovered. Key features include 1) the exploitation of the different types of metal-allyl bonding (highly ionic to predominantly covalent), 2) the use of synergistic effects in heterobimetallic compounds, and 3) the adjustment of Lewis acidity by variation of the charge of allyl compounds.

  10. INVESTIGATION AND OPTIMIZATION OF REACTIVATION OF UREASE BIOSENSOR FOR HEAVY METALS INHIBITION ANALYSIS

    Directory of Open Access Journals (Sweden)

    S. R.

    2015-12-01

    Full Text Available Research was aimed at the optimization of the urease biosensor for analysis of heavy metals and determining the opportunities of its reactivation. A differential pair of gold interdigitated electrodes deposited on a ceramic substrate was used as the conductometric transducer. As a bioselective membrane served urease, coimmobilized with bovine serum albumin by glutaraldehyde cross-linking on the surface of conductometric transducer. 1.0 mM urea was selected as an optimal substrate concentration for the inhibition analysis of heavy metals. The biosensor was tested for its sensitivity to different heavy metals, the calibration curves were plotted. The proposed biosensor was shown to have high reproducibility of signals prior and after inhibition, the measurement error was less than 3%. It was proved a possibility of reactivation of the bioselective membrane after urease irreversible inhibition by heavy metals, using the ethylenediamine tetraacetic acid solution. The optimum conditions of reactivation, i.e. the dependence of its level on time and concentration of heavy metals, were determined. The additional stage, post-inhibition reactivation, was shown to increase significantly the selectivity of biosensor determination of heavy metals.

  11. Nonferrous Metal Processing Plants - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer includes nonferrous metal processing plants in the United States. The data represent commodities covered by the Minerals Information Team (MIT) of the...

  12. Ferrous Metal Processing Plants - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer includes ferrous metal processing plants in the United States. The data represent commodities covered by the Minerals Information Team (MIT) of the...

  13. Optimization and control of metal forming processes

    NARCIS (Netherlands)

    Havinga, Gosse Tjipke

    2016-01-01

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

  14. Dental metal-induced innate reactivity in keratinocytes

    NARCIS (Netherlands)

    Rachmawati, D.; Buskermolen, J.K.; Scheper, R.J.; Gibbs, S.; von Blomberg, B.M.E.; van Hoogstraten, I.M.W.

    2015-01-01

    Gold, nickel, copper and mercury, i.e. four metals frequently used in dental applications, were explored for their capacity to induce innate immune activation in keratinocytes (KC). Due to their anatomical location the latter epithelial cells are key in primary local irritative responses of skin and

  15. Secondary Aluminum Processing Waste: Salt Cake Characterization and Reactivity

    Science.gov (United States)

    Thirty-nine salt cake samples were collected from 10 SAP facilities across the U.S. The facilities were identified by the Aluminum Association to cover a wide range of processes. Results suggest that while the percent metal leached from the salt cake was relatively low, the leac...

  16. Secondary Aluminum Processing Waste: Salt Cake Characterization and Reactivity

    Science.gov (United States)

    Thirty-nine salt cake samples were collected from 10 SAP facilities across the U.S. The facilities were identified by the Aluminum Association to cover a wide range of processes. Results suggest that while the percent metal leached from the salt cake was relatively low, the leac...

  17. Integrated Process Design and Control of Multi-element Reactive Distillation Processes

    DEFF Research Database (Denmark)

    Mansouri, Seyed Soheil; Sales-Cruz, Mauricio; Huusom, Jakob Kjøbsted

    2016-01-01

    In this work, integrated process design and control of reactive distillation processes involving multi-elements is presented. The reactive distillation column is designed using methods and tools which are similar in concept to non-reactive distillation design methods, such as driving force approach......-state analysis it is shown that it has the least energy consumption and carbon footprint. Next, through analytical and dynamic analysis it is verified that the control structure, disturbance rejection and the controllability at the maximum driving force is the best compared to any other design alternative which...

  18. Recognition- and reactivity-based fluorescent probes for studying transition metal signaling in living systems.

    Science.gov (United States)

    Aron, Allegra T; Ramos-Torres, Karla M; Cotruvo, Joseph A; Chang, Christopher J

    2015-08-18

    Metals are essential for life, playing critical roles in all aspects of the central dogma of biology (e.g., the transcription and translation of nucleic acids and synthesis of proteins). Redox-inactive alkali, alkaline earth, and transition metals such as sodium, potassium, calcium, and zinc are widely recognized as dynamic signals, whereas redox-active transition metals such as copper and iron are traditionally thought of as sequestered by protein ligands, including as static enzyme cofactors, in part because of their potential to trigger oxidative stress and damage via Fenton chemistry. Metals in biology can be broadly categorized into two pools: static and labile. In the former, proteins and other macromolecules tightly bind metals; in the latter, metals are bound relatively weakly to cellular ligands, including proteins and low molecular weight ligands. Fluorescent probes can be useful tools for studying the roles of transition metals in their labile forms. Probes for imaging transition metal dynamics in living systems must meet several stringent criteria. In addition to exhibiting desirable photophysical properties and biocompatibility, they must be selective and show a fluorescence turn-on response to the metal of interest. To meet this challenge, we have pursued two general strategies for metal detection, termed "recognition" and "reactivity". Our design of transition metal probes makes use of a recognition-based approach for copper and nickel and a reactivity-based approach for cobalt and iron. This Account summarizes progress in our laboratory on both the development and application of fluorescent probes to identify and study the signaling roles of transition metals in biology. In conjunction with complementary methods for direct metal detection and genetic and/or pharmacological manipulations, fluorescent probes for transition metals have helped reveal a number of principles underlying transition metal dynamics. In this Account, we give three recent

  19. Unique reactivity of fluorinated molecules with transition metals.

    Science.gov (United States)

    Catalán, Silvia; Munoz, Sócrates B; Fustero, Santos

    2014-01-01

    Organofluorine and organometallic chemistry by themselves constitute two potent areas in organic synthesis. Thus, the combination of both offers many chemical possibilities and represents a powerful tool for the design and development of new synthetic methodologies leading to diverse molecular structures in an efficient manner. Given the importance of the selective introduction of fluorine atoms into organic molecules and the effectiveness of transition metals in C-C and C-heteroatom bond formation, this review represents an interesting read for this aim.

  20. A New Model for Reactive Wetting of Metal/Ceramic System

    Institute of Scientific and Technical Information of China (English)

    Fusheng Pan; Jian Chen; Tianmo Liu; Jing Zhang

    2000-01-01

    @@ A new model has been suggested for illustrating the effects of interfacial reactions on the wettability of metal / ceramic system. It is shown that both the free energy change released by the reaction (△Gr) and the change in the nature of interfaces (△δr) are the important factors affecting reactive wetting of metal / ceramic system, but sometimes either of them will become the decisive one.

  1. Nanoporous Hybrid Electrolytes for High-Energy Batteries Based on Reactive Metal Anodes

    KAUST Repository

    Tu, Zhengyuan

    2017-01-06

    Successful strategies for stabilizing electrodeposition of reactive metals, including lithium, sodium, and aluminum are a requirement for safe, high-energy electrochemical storage technologies that utilize these metals as anodes. Unstable deposition produces high-surface area dendritic structures at the anode/electrolyte interface, which causes premature cell failure by complex physical and chemical processes that have presented formidable barriers to progress. Here, it is reported that hybrid electrolytes created by infusing conventional liquid electrolytes into nanoporous membranes provide exceptional ability to stabilize Li. Electrochemical cells based on γ-Al2O3 ceramics with pore diameters below a cut-off value above 200 nm exhibit long-term stability even at a current density of 3 mA cm−2. The effect is not limited to ceramics; similar large enhancements in stability are observed for polypropylene membranes with less monodisperse pores below 450 nm. These findings are critically assessed using theories for ion rectification and electrodeposition reactions in porous solids and show that the source of stable electrodeposition in nanoporous electrolytes is fundamental.

  2. INDUCTION PLASMA REACTIVE DEPOSITION OF TUNGSTENCARBIDE FROM TUNGSTEN METAL POWDER

    Institute of Scientific and Technical Information of China (English)

    X.L. Jiang; M.I. Boulos

    2001-01-01

    Experimental results are reported on the primary carburization reaction between the tungsten powder and methane in the induction plasma, and the secondary carburization of the deposit on substrate at high temperature. Optical microscopy and scanning electron microscopy were used to examine the microstructures of starting tungsten powder, carburized powder, and deposit. X-ray diffraction analysis, thermal gravimetric analysis and microhardness measurement were used to characterize the structures and properties of the powder and the deposit. It is found that the primary carburization reaction in the induction plasma starts from the surface of tungsten particles when the particles are melted. Tungsten particles are partially carburized inside the reactive plasma. Complete carburization is achieved through the secondary carburization reaction of the deposit on substrate at high temperature.``

  3. Synthesis of ternary metal nitride nanoparticles using mesoporous carbon nitride as reactive template.

    Science.gov (United States)

    Fischer, Anna; Müller, Jens Oliver; Antonietti, Markus; Thomas, Arne

    2008-12-23

    Mesoporous graphitic carbon nitride was used as both a nanoreactor and a reactant for the synthesis of ternary metal nitride nanoparticles. By infiltration of a mixture of two metal precursors into mesoporous carbon nitride, the pores act first as a nanoconfinement, generating amorphous mixed oxide nanoparticles. During heating and decomposition, the carbon nitride second acts as reactant or, more precisely, as a nitrogen source, which converts the preformed mixed oxide nanoparticles into the corresponding nitride (reactive templating). Using this approach, ternary metal nitride particles with diameters smaller 10 nm composed of aluminum gallium nitride (Al-Ga-N) and titanium vanadium nitride (Ti-V-N) were synthesized. Due to the confinement effect of the carbon nitride matrix, the composition of the resulting metal nitride can be easily adjusted by changing the concentration of the preceding precursor solution. Thus, ternary metal nitride nanoparticles with continuously adjustable metal composition can be produced.

  4. Supercritical nitrogen processing for the purification of reactive porous materials.

    Science.gov (United States)

    Stadie, Nicholas P; Callini, Elsa; Mauron, Philippe; Borgschulte, Andreas; Züttel, Andreas

    2015-05-15

    Supercritical fluid extraction and drying methods are well established in numerous applications for the synthesis and processing of porous materials. Herein, nitrogen is presented as a novel supercritical drying fluid for specialized applications such as in the processing of reactive porous materials, where carbon dioxide and other fluids are not appropriate due to their higher chemical reactivity. Nitrogen exhibits similar physical properties in the near-critical region of its phase diagram as compared to carbon dioxide: a widely tunable density up to ~1 g ml(-1), modest critical pressure (3.4 MPa), and small molecular diameter of ~3.6 Å. The key to achieving a high solvation power of nitrogen is to apply a processing temperature in the range of 80-150 K, where the density of nitrogen is an order of magnitude higher than at similar pressures near ambient temperature. The detailed solvation properties of nitrogen, and especially its selectivity, across a wide range of common target species of extraction still require further investigation. Herein we describe a protocol for the supercritical nitrogen processing of porous magnesium borohydride.

  5. Pyrometallurgical process of actinide metal

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Jae Hyung; Kang, Young Ho; Woo, Mun Sik; Hwang, Sung Chan

    1999-06-01

    Major subject on pyrometallurgical partitioning technology is to separate transmutation elements (TRU) from rare earth elements(RE). Distribution coefficients of TRU and RE between molten chloride and liquid cadmium were measured for reductive extraction, and TRU were separated from RE in simplified molten chloride system by electrorefining. And separation efficiency between TRU and RE were estimated by using thermodynamics data. The results indicate that uranium, neptunium and plutonium are easy to separate from RE but some amount of RE accompany americium, and that processes have to be optimized to attain good separation efficiency of TRU. (author)

  6. Homometallic rare-Earth metal phosphinidene clusters: synthesis and reactivity.

    Science.gov (United States)

    Wang, Kai; Luo, Gen; Hong, Jianquan; Zhou, Xigeng; Weng, Linhong; Luo, Yi; Zhang, Lixin

    2014-01-20

    Two new trinuclear μ3 -bridged rare-earth metal phosphinidene complexes, [{L(Ln)(μ-Me)}3 (μ3 -Me)(μ3 -PPh)] (L=[PhC(NC6 H4 iPr2 -2,6)2 ](-) , Ln=Y (2 a), Lu (2 b)), were synthesized through methane elimination of the corresponding carbene precursors with phenylphosphine. Heating a toluene solution of 2 at 120 °C leads to an unprecedented ortho CH bond activation of the PhP ligand to form the bridged phosphinidene/phenyl complexes. Reactions of 2 with ketones, thione, or isothiocyanate show clear phospha-Wittig chemistry, giving the corresponding organic phosphinidenation products and oxide (sulfide) complexes. Reaction of 2 with CS2 leads to the formation of novel trinuclear rare-earth metal thione dianion clusters, for which a possible pathway was determined by DFT calculation. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Group 3 metal stilbene complexes: Synthesis, reactivity, and electronic structure studies

    OpenAIRE

    Huang, W.; Abukhalil, PM; Khan, SI; Diaconescu, PL

    2014-01-01

    Group 3 metal (E)-stilbene complexes supported by a ferrocene diamide ligand were synthesized and characterized. Reactivity studies showed that they behave similar to analogous naphthalene complexes. Experimental and computational results indicated that the double bond was reduced and not a phenyl ring, in contrast to a previously reported uranium (E)-stilbene complex. © the Partner Organisations 2014.

  8. Representing Microbial Processes in Environmental Reactive Transport Models

    Science.gov (United States)

    van Cappellen, P.

    2009-04-01

    Microorganisms play a key role in the biogeochemical functioning of the earth's surface and shallow subsurface. In the context of reactive transport modeling, a major challenge is to derive, parameterize, calibrate and verify mathematical expressions for microbially-mediated reactions in the environmental. This is best achieved by combining field observations, laboratory experiments, theoretical principles and modeling. Here, I will illustrate such an integrated approach for the case of microbial respiration processes in aquatic sediments. Important issues that will be covered include experimental design, model consistency and performance, as well as the bioenergetics and transient behavior of geomicrobial reaction systems.

  9. Study of reactive ion etching for reverse tone nanoimprint process

    Energy Technology Data Exchange (ETDEWEB)

    Tsuji, Y; Yanagisawa, M; Yoshinaga, H; Hiratsuka, K, E-mail: tsuji-yukihiro@sei.co.j [Fiber-optics Core Devices R and D Department, Transmission Devices R and D Laboratories, Sumitomo Electric Industries, LTD. 1, Taya-cho, Sakae-ku, Yokohama, Kanagawa, 244-8588 (Japan)

    2009-11-15

    We have used reverse nanoimprint for fabricating diffraction gratings of distributed feedback laser diodes. Generation of residues in the etching process of resin is a serious issue leading to poor line edge roughness of the grating patterns. We have found that the residues are composed of oxide products from Si-containing resin. We have successfully suppressed the generation of the residues by optimizing oxygen partial pressure of reactive ion etching (RIE). We have also succeeded in effectively removing the residues by utilizing sputtering effect of RIE.

  10. Processing metallic glasses by selective laser melting

    Directory of Open Access Journals (Sweden)

    Simon Pauly

    2013-01-01

    Full Text Available Metallic glasses and their descendants, the so-called bulk metallic glasses (BMGs, can be regarded as frozen liquids with a high resistance to crystallization. The lack of a conventional structure turns them into a material exhibiting near-theoretical strength, low Young's modulus and large elasticity. These unique mechanical properties can be only obtained when the metallic melts are rapidly cooled to bypass the nucleation and growth of crystals. Most of the commonly known and used processing routes, such as casting, melt spinning or gas atomization, have intrinsic limitations regarding the complexity and dimensions of the geometries. Here, it is shown that selective laser melting (SLM, which is usually used to process conventional metallic alloys and polymers, can be applied to implement complex geometries and components from an Fe-base metallic glass. This approach is in principle viable for a large variety of metallic alloys and paves the way for the novel synthesis of materials and the development of parts with advanced functional and structural properties without limitations in size and intricacy.

  11. High metal reactivity and environmental risks at a site contaminated by glass waste.

    Science.gov (United States)

    Augustsson, A; Åström, M; Bergbäck, B; Elert, M; Höglund, L O; Kleja, D B

    2016-07-01

    This study addresses the reactivity and risks of metals (Ba, Cd, Co, Cr, Cu, Ni, Pb, Zn, As and Sb) at a Swedish site with large glass waste deposits. Old glassworks sites typically have high total metal concentrations, but as the metals are mainly bound within the glass waste and considered relatively inert, environmental investigations at these kinds of sites are limited. In this study, soil and landfill samples were subjected to a sequential chemical extraction procedure. Data from batch leaching tests and groundwater upstream and downstream of the waste deposits were also interpreted. The sequential extraction revealed that metals in metals are released from pristine glass and subsequently largely retained in the surrounding soil and/or on secondary mineral coatings on fine glass particles. From the approximately 12,000 m(3) of coarse glass waste at the site, almost 4000 kg of Pb is estimated to have been lost through corrosion, which, however, corresponds to only a small portion of the total amount of Pb in the waste. Metal sorption within the waste deposits or in underlying soil layers is supported by fairly low metal concentrations in groundwater. However, elevated concentrations in downstream groundwater and in leachates of batch leaching tests were observed for several metals, indicating on-going leaching. Taken together, the high metal concentrations in geochemically active forms and the high amounts of as yet uncorroded metal-rich glass, indicate considerable risks to human health and the environment.

  12. A mesocosm study of oxygen and trace metal dynamics in sediment microniches of reactive organic material

    DEFF Research Database (Denmark)

    Letho, Niklas; Larsen, Morten; Zhang, Hao

    2017-01-01

    simultaneous measurements of dissolved O2 and trace metal dynamics around an aggregate of reactive organic matter placed on the SWI of a sediment mesocosm. The aggregate induced a rapid, highly localized, decrease in O2 concentration, resulting in an anoxic feature at the SWI. Co-located with this feature, we...... observed intense Fe and Mn mobilization, removal of Co, Ni and Zn and found evidence for the concurrent release and precipitation of Pb within a small confined volume. We also identified two small microniches in the anoxic sediment below the SWI, defined by elevated trace metal mobilization. Differences...... mobilization at the SWI. By using a combined planar optode-DGT (diffusive gradient in thin-films) sensor we obtained simultaneous measurements of dissolved O2 and trace metal dynamics around an aggregate of reactive organic matter placed on the SWI of a sediment mesocosm. The aggregate induced a rapid, highly...

  13. Effect of metal ions on reactive dye decolorization by laccase from Ganoderma lucidum.

    Science.gov (United States)

    Murugesan, Kumarasamy; Kim, Young-Mo; Jeon, Jong-Rok; Chang, Yoon-Seok

    2009-08-30

    In this work, the influence of different metal ions on laccase activity and laccase-catalyzed dye decolorization was investigated under in vitro conditions using crude laccase obtained from a white rot fungus Ganoderma lucidum. Laccase activity was enhanced by metal ions such as Ca(2+), Co(2+), Cu(2+) and Zn(2+) at low concentrations (1mM). Increasing the concentration of metal ions except that of Cu(2+) and Zn(2+) up to 5mM and above decreased the enzyme activity. Among several heavy metals, Fe(2+) highly inhibited the enzyme activity. Effect of metal ions was tested on decolorization of two reactive dyes, namely Remazol black-B (RB-5) and Remazol brilliant blue R (RBBR) at a concentration of 50 mg l(-1). The presence of heavy metals generally did not exert much influence on the decolorization except Fe(2+). Cu(2+) and Cr(6+) enhanced the decolorization of both dyes. In the presence of 1mM Cu(2+), 94% of RB-5 and 35.5% of RBBR were decolorized during 1h incubation. G. lucidum laccase was able to tolerate mixture of several metal ions. Treatment of simulated reactive dye effluent by laccase showed that the redox mediator system is necessary for effluent decolorization. Syringaldehyde, a natural redox mediator, was very effective than the synthetic mediator 1-hydroxybenzotriazole (HBT). The initial rate of effluent decolorization in presence of syringaldehyde (0.0831 h(-1)) was 5.6 times higher than HBT (0.0152 h(-1)). Although the rate of decolorization was markedly decreased in the effluent containing mixed metal ions, presence of syringaldehyde showed effective decolorization. This study indicates that G. lucidum laccase and natural redox mediator system could be a potential candidate for color removal from reactive dye effluent.

  14. Liquid Metal Infiltration Processing of Metallic Composites: A Critical Review

    Science.gov (United States)

    Sree Manu, K. M.; Ajay Raag, L.; Rajan, T. P. D.; Gupta, Manoj; Pai, B. C.

    2016-10-01

    Metal matrix composites (MMC) are one of the advanced materials widely used for aerospace, automotive, defense, and general engineering applications. MMC can be tailored to have superior properties such as enhanced high-temperature performance, high specific strength and stiffness, increased wear resistance, better thermal and mechanical fatigue, and creep resistance than those of unreinforced alloys. To fabricate such composites with ideal properties, the processing technique has to ensure high volume fraction of reinforcement incorporation, uniform distribution of the reinforcement, and acceptable adhesion between the matrix and the reinforcing phase without unwanted interfacial reactions which degrades the mechanical properties. A number of processing techniques such as stir casting/vortex method, powder metallurgy, infiltration, casting etc. have been developed to synthesize MMC employing a variety of alloy and the reinforcement's combinations. Among these, infiltration process is widely used for making MMC with high volume fraction of reinforcements and offers many more advantages compared to other conventional manufacturing processes. The present paper critically reviews the various infiltration techniques used for making the MMC, their process parameters, characteristics, and selected studies carried out worldwide and by authors on the development of metal ceramic composites by squeeze infiltration process.

  15. Adsorption and Reactive Desorption on Metal-Organic Frameworks: A Direct Strategy for Lactic Acid Recovery.

    Science.gov (United States)

    Stassin, Timothée; Reinsch, Helge; Van de Voorde, Ben; Wuttke, Stefan; Medina, Dana D; Stock, Norbert; Bein, Thomas; Ameloot, Rob; De Vos, Dirk

    2017-02-08

    Biomass-derived lactic acid (LA) is an important platform chemical towards the sustainable production of numerous materials. However, the fermentation process currently in use is limited by the difficult recovery of the LA product from the fermentation broth and results in the generation of stoichiometric amounts of gypsum waste. Herein, we show that metal-organic frameworks (MOFs) of the UiO-66(Zr) type are effective adsorbents for the separation of LA from aqueous (buffer) solutions. These frameworks based on zirconium clusters and terephthalic acid derivatives display a tremendous uptake (up to 42 wt %) and a high affinity for LA. The latter can further be tuned by changing the hydrogen-bonding properties of the functional groups present on the organic ligand. A Rietveld refinement disclosed the specific interaction of LA with the clusters of UiO-66(Zr) and a preferential adsorption on open zirconium sites. Taking advantage of the catalytic activity of UiO-66(Zr), desorption of LA was performed in alcohols to recover up to 73 % as ester. Applied to the recovery of LA, adsorption and reactive desorption offer a direct and gypsum-free strategy as an alternative for the current multi-step process. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Changes in the chemical reactivity of metals exposed to an inert gas glow discharge

    Energy Technology Data Exchange (ETDEWEB)

    Klemperer, D.F.; Williams, D.J. (Bristol Univ. (UK). Dept. of Physical Chemistry)

    1983-05-01

    From time to time the literature mentions curious effects on the chemical reactivity of metals due to inert gas ion bombardment: reactivity in corrosive environments is variously said to be inhibited or enhanced. Although there is no obvious explanation for such effects, some possible mechanisms have been suggested. Some simple experiments have been carried out to demonstrate that reactivity effects really do exist and to test such mechanisms. The results are qualitative because a glow discharge was used to implant the rare gas ions. Evaporated films of aluminium and nickel become amorphous after bombardment with xenon ions and the films resisted gaseous and liquid corrosion. On the other hand, aluminium foil bombarded with xenon ions in a Penning pump arrangement was attacked more heavily than unbombarded aluminium. Passivation is attributed to the known lack of reactivity of amorphous metals. Glassy materials appear to lack the normal routes of attack between their subsurface regions and the attacking medium. On the other hand, when a metal surface is heavily ion bombarded the surface is probably damaged to such an extent that the attacking medium gains physical access to the interior and corrosion proceeds rapidly.

  17. INVESTIGATION OF THE METAL MELTING PROCESS

    Directory of Open Access Journals (Sweden)

    V. I. Timoshpolskij

    2006-01-01

    Full Text Available The nonlinear mathematical model of calculation of temperature fields in the process of metal melting is formulated and solved using the method of equivalent source taking into account nonlinearity of thermophysical properties of material and variable terms of heat exchange.

  18. Reactive oxygen species-related activities of nano-iron metal and nano-iron oxides

    Directory of Open Access Journals (Sweden)

    Haohao Wu

    2014-03-01

    Full Text Available Nano-iron metal and nano-iron oxides are among the most widely used engineered and naturally occurring nanostructures, and the increasing incidence of biological exposure to these nanostructures has raised concerns about their biotoxicity. Reactive oxygen species (ROS-induced oxidative stress is one of the most accepted toxic mechanisms and, in the past decades, considerable efforts have been made to investigate the ROS-related activities of iron nanostructures. In this review, we summarize activities of nano-iron metal and nano-iron oxides in ROS-related redox processes, addressing in detail the known homogeneous and heterogeneous redox mechanisms involved in these processes, intrinsic ROS-related properties of iron nanostructures (chemical composition, particle size, and crystalline phase, and ROS-related bio-microenvironmental factors, including physiological pH and buffers, biogenic reducing agents, and other organic substances.

  19. Exploring the reactivity of flavonoid compounds with metal-associated amyloid-β species.

    Science.gov (United States)

    He, Xiaoming; Park, Hyun Min; Hyung, Suk-Joon; DeToma, Alaina S; Kim, Cheal; Ruotolo, Brandon T; Lim, Mi Hee

    2012-06-01

    Metal ions associated with amyloid-β (Aβ) peptides have been suggested to be involved in the development of Alzheimer's disease (AD), but this remains unclear and controversial. Some attempts to rationally design or select small molecules with structural moieties for metal chelation and Aβ interaction (i.e., bifunctionality) have been made to gain a better understanding of the hypothesis. In order to contribute to these efforts, four synthetic flavonoid derivatives FL1-FL4 were rationally selected according to the principles of bifunctionality and their abilities to chelate metal ions, interact with Aβ, inhibit metal-induced Aβ aggregation, scavenge radicals, and regulate the formation of reactive oxygen species (ROS) were studied using physical methods and biological assays. The compounds FL1-FL3 were able to chelate metal ions, but showed limited solubility in aqueous buffered solutions. In the case of FL4, which was most compatible with aqueous conditions, its binding affinities for Cu(2+) and Zn(2+) (nM and μM, respectively) were obtained through solution speciation studies. The direct interaction between FL4 and Aβ monomer was weak, which was monitored by NMR spectroscopy and mass spectrometry. Employing FL1-FL4, no noticeable inhibitory effect on metal-mediated Aβ aggregation was observed. Among FL1-FL4, FL3, having 3-OH, 4-oxo, and 4'-N(CH(3))(2) groups, exhibited similar antioxidant activity to the vitamin E analogue, Trolox, and ca. 60% reduction in the amount of hydrogen peroxide (H(2)O(2)) generated by Cu(2+)-Aβ in the presence of dioxygen (O(2)) and a reducing agent. Overall, the studies here suggest that although four flavonoid molecules were selected based on expected bifunctionality, their properties and metal-Aβ reactivity were varied depending on the structure differences, demonstrating that bifunctionality must be well tuned to afford desirable reactivity.

  20. In situ silica-EPDM nanocomposites obtained via reactive processing

    NARCIS (Netherlands)

    Miloskovska, Elena; Hristova-Bogaerds, Denka; van Duin, Martin; de With, Gijsbertus

    2015-01-01

    In situ rubber nanocomposites prepared via reactive batch mixing and via reactive extrusion were studied. Materials produced via reactive batch mixing showed a significantly higher silica content for a similar reaction time as compared to previously prepared in situ nanocomposites using a diffusion

  1. Nitrous oxide production from reactive nitrification intermediates: a concerted action of biological and chemical processes

    Science.gov (United States)

    Brüggemann, Nicolas; Heil, Jannis; Liu, Shurong; Wei, Jing; Vereecken, Harry

    2017-04-01

    This contribution tries to open up a new perspective on biogeochemical N2O production processes, taking the term bio-geo-chemistry literally. What if a major part of N2O is produced from reactive intermediates of microbiological N turnover processes ("bio…") leaking out of the involved microorganisms into the soil ("…geo…") and then reacting chemically ("…chemistry") with the surrounding matrix? There are at least two major reactive N intermediates that might play a significant role in these coupled biological-chemical reactions, i.e. hydroxylamine (NH2OH) and nitrite (NO2-), both of which are produced during nitrification under oxic conditions, while NO2- is also produced during denitrification under anoxic conditions. Furthermore, NH2OH is assumed to be also a potential intermediate of DNRA and/or anammox. First, this contribution will summarize information about several chemical reactions involving NH2OH and NO2- leading to the formation of N2O. These abiotic reactions are: reactions of NO2- with reduced metal cations, nitrosation reactions of NO2- and soil organic matter (SOM), the reaction between NO2- and NH2OH, and the oxidation of NH2OH by oxidized metal ions. While these reactions can occur over a broad range of soil characteristics, they are ignored in most current N trace gas studies in favor of biological processes only. Disentangling microbiological from purely chemical N2O production is further complicated by the fact that the chemically formed N2O is either undiscernible from N2O produced during nitrification, or shows an intermediate 15N site preference between that of N2O from nitrification and denitrification, respectively. Results from experiments with live and sterilized soil samples, with artificial soil mixtures and with phenolic lignin decomposition model compounds will be presented that demonstrate the potential contribution of these abiotic processes to soil N trace gas emissions, given a substantial leakage rate of these reactive

  2. Perinatal Factors, Parenting Behavior, and Reactive Aggression: Does Cortisol Reactivity Mediate This Developmental Risk Process?

    Science.gov (United States)

    Ryan, Stacy R.; Schechter, Julia C.; Brennan, Patricia A.

    2012-01-01

    Little is known about the mechanisms of action that link perinatal risk and the development of aggressive behavior. The aim of this study was to examine whether perinatal risk and parenting interacted to specifically predict reactive aggression, as opposed to general aggressive behavior, and to examine cortisol reactivity as a mediator of this…

  3. Low Temperature Reactive Sputtering of Thin Aluminum Nitride Films on Metallic Nanocomposites.

    Science.gov (United States)

    Ramadan, Khaled Sayed Elbadawi; Evoy, Stephane

    2015-01-01

    Piezoelectric aluminum nitride thin films were deposited on aluminum-molybdenum (AlMo) metallic nanocomposites using reactive DC sputtering at room temperature. The effect of sputtering parameters on film properties was assessed. A comparative study between AlN grown on AlMo and pure aluminum showed an equivalent (002) crystallographic texture. The piezoelectric coefficients were measured to be 0.5±0.1 C m(-2) and 0.9±0.1 C m(-2), for AlN deposited on Al/0.32Mo and pure Al, respectively. Films grown onto Al/0.32Mo however featured improved surface roughness. Roughness values were measured to be 1.3nm and 5.4 nm for AlN films grown on AlMo and on Al, respectively. In turn, the dielectric constant was measured to be 8.9±0.7 for AlN deposited on Al/0.32Mo seed layer, and 8.7±0.7 for AlN deposited on aluminum; thus, equivalent within experimental error. Compatibility of this room temperature process with the lift-off patterning of the deposited AlN is also reported.

  4. C-H bond activation by metal-superoxo species: what drives high reactivity?

    Science.gov (United States)

    Ansari, Azaj; Jayapal, Prabha; Rajaraman, Gopalan

    2015-01-01

    Metal-superoxo species are ubiquitous in metalloenzymes and bioinorganic chemistry and are known for their high reactivity and their ability to activate inert C-H bonds. The comparative oxidative abilities of M-O2(.-) species (M = Cr(III), Mn(III), Fe(III), and Cu(II)) towards C-H bond activation reaction are presented. These superoxo species generated by oxygen activation are found to be aggressive oxidants compared to their high-valent metal-oxo counterparts generated by O⋅⋅⋅O bond cleavage. Our calculations illustrate the superior oxidative abilities of Fe(III)- and Mn(III)-superoxo species compared to the others and suggest that the reactivity may be correlated to the magnetic exchange parameter.

  5. Th1 type lymphocyte reactivity to metals in patients with total hip arthroplasty

    Directory of Open Access Journals (Sweden)

    Finnegan Alison

    2008-02-01

    Full Text Available Abstract Background All prostheses with metallic components release metal debris that can potentially activate the immune system. However, implant-related metal hyper-reactivity has not been well characterized. In this study, we hypothesized that adaptive immunity reaction(s, particularly T-helper type 1 (Th1 responses, will be dominant in any metal-reactivity responses of patients with total joint replacements (TJAs. We tested this hypothesis by evaluating lymphocyte reactivity to metal "ions" in subjects with and without total hip replacements, using proliferation assays and cytokine analysis. Methods Lymphocytes from young healthy individuals without an implant or a history of metal allergy (Group 1: n = 8 were used to assess lymphocyte responses to metal challenge agents. In addition, individuals (Group 2: n = 15 with well functioning total hip arthroplasties (average Harris Hip Score = 91, average time in-situ 158 months were studied. Age matched controls with no implants were also used for comparison (Group 3, n = 8, 4 male, 4 female average age 70, range 49–80. Group 1 subjects' lymphocyte proliferation response to Aluminum+3, Cobalt+2, Chromium+3, Copper+2, Iron+3, Molybdenum+5, Manganeese+2, Nickel+2, Vanadium+3 and Sodium+2 chloride solutions at a variety of concentrations (0.0, 0.05, 0.1, 0.5, 1.0 and 10.0 mM was studied to establish toxicity thresholds. Mononuclear cells from Group 2 and 3 subjects were challenged with 0.1 mM CrCl3, 0.1 mM NiCl2, 0.1 mM CoCl2 and approx. 0.001 mM titanium and the reactions measured with proliferation assays and cytokine analysis to determine T-cell subtype prominence. Results Primary lymphocytes from patients with well functioning total hip replacements demonstrated a higher incidence and greater magnitude of reactivity to chromium than young healthy controls (p 2 fold stimulation index response, p 10 mM. The differential secretion of signature T-cell subsets' cytokines (Th1 and Th2 lymphocytes

  6. Reactive Molecular Dynamics Investigations of Alkoxysilane Sol-Gel and Surface Coating Processes

    Science.gov (United States)

    Deetz, Joshua David

    The ability to generate nanostructured materials with tailored morphology or chemistry is of great technological interest. One proven method of generating metal-oxide materials, and chemically modifying metal-oxide surfaces is through the reactions of molecular building blocks known as alkoxysilanes. Alkoxysilanes are a class of chemicals which contain one or more organic alkoxy groups bonded to silicon atoms. Alkoxysilane (Si-O-R) chemical groups can undergo reactions to form bridges (Si-O-M) with metal oxides. Due to their ability to "attach" to metal-oxides through condensation reactions, alkoxysilanes have a number of interesting applications, such as: the generation of synthetic siloxane materials through the sol-gel process, and the formation of functionalized surface coatings on metal-oxide surfaces. Despite widespread study of sol-gel and surface coatings processes, it is difficult to predict the morphology of the final products due to the large number of process variables involved, such as precursor molecule structure, solvent effects, solution composition, temperature, and pH. To determine the influence of these variables on the products of sol-gel and coatings processes reactive molecular dynamics simulations are used. A reactive force field was used (ReaxFF) to allow the chemical bonds in simulation to dynamically form and break. The force field parameters were optimized using a parallel optimization scheme with a combination of experimental information, and density functional theory calculations. Polycondensation of alkoxysilanes in mixtures of alcohol and water were studied. Steric effects were observed to influence the rates of hydrolysis and condensation in solutions containing different precursor monomers. By restricting the access of nucleophiles to the central silicon atom, the nucleation rate of siloxanes can be controlled. The influence of solution precursor, water, and methanol composition on reaction rates was explored. It was determined that

  7. Metal-organic frameworks reactivate deceased diatoms to be efficient CO(2) absorbents.

    Science.gov (United States)

    Liu, Dingxin; Gu, Jiajun; Liu, Qinglei; Tan, Yongwen; Li, Zhuo; Zhang, Wang; Su, Yishi; Li, Wuxia; Cui, Ajuan; Gu, Changzhi; Zhang, Di

    2014-02-26

    Diatomite combined with certain metal-organic frameworks (MOFs) is shown to be an effective CO2 absorbent, although diatomite alone is regarded as inert with respect to CO2 absorption. This finding opens the prospect of reactivating millions of tons of diatomite for CO2 absorption. It also shows for the first time that diatom frustules can act as CO2 buffers, an important link in a successive biological CO2 concentration mechanism chain that impacts on global warming.

  8. 自反应喷射成形过程中复合粉金属成分的氧化问题探讨%Discussion on Oxidation of Metallic Components in Composite Powders During Self-reactive Spray Forming Process

    Institute of Scientific and Technical Information of China (English)

    刘宏伟; 马世宁; 孙晓峰; 王建江

    2011-01-01

    During forming Ti(C, N)-TiB2 by self-reactive spray, metallic components are easy to be oxidized ,which make the preforms contain the undesirable phase TiO2. To dissolve the problems, the rule of the metallic oxidation of the composite powders was studied by synthetic thermal analyzer, and the influences of 5wt% additive of A1 on the role of metallic oxidation and the structure and properties of the spray-formed preforms were discussed. The results show that during self-reactive forming process, the oxidation of the metallic components in the Ti-BaC-C system accords with parabola-linearity rule. After adding 5wt% A1 into the spraying system, the oxidation rule of the metallic components changes into linearity-parabola because the compact oxide film of A12O3 forms on the surface by the selective oxidation of Al and effectively restrains the oxidation of Ti. The relative density, hardness, flexural strength and fracture toughness of the preforms increases from 97.2%, 17.3 GPa, 387 MPa, 6.0 MPa. m1/2, to 97.7%, 20.6 GPa, 425 MPa, 7.3 MPa. m1/2, respectively.%针对利用Ti-BC-C体系复合粉制备Ti(C,N)-TiB陶瓷坯件时,复合粉中金属组元易被氧化,使喷射沉积坯件内含有有害相TiO的问题,利用综合热分析仪研究分析了该复合粉中金属组元Ti的氧化规律,探讨了向喷射体系中加入5wt%Al对复合粉氧化规律及喷射沉积坯件组织结构的影响.结果表明:在自反应喷射成形过程中,喷射体系中金属组元Ti的氧化机理遵从抛物线一线性氧化规律;复合粉体系中引入活性组元Al后,由于A1的选择氧化,在金属表面形成具有保护性作用的致密氧化膜A1O,有效抑制了Ti的氧化;金属的氧化机理转变为Ti-Al二元金属的线性-抛物线规律;喷射沉积坯件的致密度、硬度、弯曲强度和断裂韧性等性能也由97.2%、17.3GPa、387MPa、6.0MPa·m分别提高到97.7%、20.6 GPa、425 MPa、7.3 MPa·in.

  9. An evaluation of sodium void reactivity for metal fuel FBR cores

    Energy Technology Data Exchange (ETDEWEB)

    Ohta, Hirokazu; Yokoo, Takeshi [Central Research Inst. of Electric Power Industry, Komae, Tokyo (Japan). Komae Research Lab

    2000-07-01

    The sodium void reactivity in metal fuel FBR cores has been evaluated by a detailed method which takes into account the neutron streaming effects in the fuel subassemblies and the neutron transport corrections in whole-core systems. The neutron streaming effects caused by the heterogeneity of the fuel element structure or the coolant paths were evaluated on the basis of Benoist's anisotropic diffusion coefficient. We clarified that the sodium void reactivity is worth less than $8, even in the 1,000 MWe or 1,500 MWe-class large-scale cores. Further, we also found that, in the case of 1,500 MWe metal fuel FBRs recycling a few percent of minor actinide elements (MA), the sodium void reactivity does not exceed $10 with a suitable design that eliminates the upper and lower axial blankets. These results show that these metal fuel FBRs satisfy the safety criterion ($8-10) for avoiding the prompt criticality in the HCDA events. However, MA enrichment should be controlled to less than about two per cent, when the axial blanket is loaded to gain higher breeding performance. (author)

  10. The Role of Reactive Oxygen Species (ROS in the Biological Activities of Metallic Nanoparticles

    Directory of Open Access Journals (Sweden)

    Ahmed Abdal Dayem

    2017-01-01

    Full Text Available Nanoparticles (NPs possess unique physical and chemical properties that make them appropriate for various applications. The structural alteration of metallic NPs leads to different biological functions, specifically resulting in different potentials for the generation of reactive oxygen species (ROS. The amount of ROS produced by metallic NPs correlates with particle size, shape, surface area, and chemistry. ROS possess multiple functions in cellular biology, with ROS generation a key factor in metallic NP-induced toxicity, as well as modulation of cellular signaling involved in cell death, proliferation, and differentiation. In this review, we briefly explained NP classes and their biomedical applications and describe the sources and roles of ROS in NP-related biological functions in vitro and in vivo. Furthermore, we also described the roles of metal NP-induced ROS generation in stem cell biology. Although the roles of ROS in metallic NP-related biological functions requires further investigation, modulation and characterization of metallic NP-induced ROS production are promising in the application of metallic NPs in the areas of regenerative medicine and medical devices.

  11. Uncoupling of reactive oxygen species accumulation and defence signalling in the metal hyperaccumulator plant Noccaea caerulescens.

    Science.gov (United States)

    Fones, Helen N; Eyles, Chris J; Bennett, Mark H; Smith, J Andrew C; Preston, Gail M

    2013-09-01

    The metal hyperaccumulator plant Noccaea caerulescens is protected from disease by the accumulation of high concentrations of metals in its aerial tissues, which are toxic to many pathogens. As these metals can lead to the production of damaging reactive oxygen species (ROS), metal hyperaccumulator plants have developed highly effective ROS tolerance mechanisms, which might quench ROS-based signals. We therefore investigated whether metal accumulation alters defence signalling via ROS in this plant. We studied the effect of zinc (Zn) accumulation by N. caerulescens on pathogen-induced ROS production, salicylic acid accumulation and downstream defence responses, such as callose deposition and pathogenesis-related (PR) gene expression, to the bacterial pathogen Pseudomonas syringae pv. maculicola. The accumulation of Zn caused increased superoxide production in N. caerulescens, but inoculation with P. syringae did not elicit the defensive oxidative burst typical of most plants. Defences dependent on signalling through ROS (callose and PR gene expression) were also modified or absent in N. caerulescens, whereas salicylic acid production in response to infection was retained. These observations suggest that metal hyperaccumulation is incompatible with defence signalling through ROS and that, as metal hyperaccumulation became effective as a form of elemental defence, normal defence responses became progressively uncoupled from ROS signalling in N. caerulescens. © 2013 The Authors. New Phytologist © 2013 New Phytologist Trust.

  12. Solar Convective Furnace for Metals Processing

    Science.gov (United States)

    Patidar, Deepesh; Tiwari, Sheetanshu; Sharma, Piyush; Pardeshi, Ravindra; Chandra, Laltu; Shekhar, Rajiv

    2015-11-01

    Metals processing operations, primarily soaking, heat treatment, and melting of metals are energy-intensive processes using fossil fuels, either directly or indirectly as electricity, to operate furnaces at high temperatures. Use of concentrated solar energy as a source of heat could be a viable "green" option for industrial heat treatment furnaces. This paper introduces the concept of a solar convective furnace which utilizes hot air generated by an open volumetric air receiver (OVAR)-based solar tower technology. The potential for heating air above 1000°C exists. Air temperatures of 700°C have already been achieved in a 1.5-MWe volumetric air receiver demonstration plant. Efforts to retrofit an industrial aluminium soaking furnace for integration with a solar tower system are briefly described. The design and performance of an OVAR has been discussed. A strategy for designing a 1/15th-scale model of an industrial aluminium soaking furnace has been presented. Preliminary flow and thermal simulation results suggest the presence of recirculating flow in existing furnaces that could possibly result in non-uniform heating of the slabs. The multifarious uses of concentrated solar energy, for example in smelting, metals processing, and even fuel production, should enable it to overcome its cost disadvantage with respect to solar photovoltaics.

  13. Reactive oxygen species (ROS: Beneficial companions of plants’ developmental processes

    Directory of Open Access Journals (Sweden)

    Rachana Singh

    2016-09-01

    Full Text Available Reactive oxygen species (ROS are continuously generated inevitably in the redox reactions of plants, including respiration and photosynthesis. In earlier studies, ROS were considered as toxic by-products of aerobic pathways of the metabolism. But in recent years, concept about ROS has changed because they also participate in developmental processes of plants by acting as signaling molecules. In plants, ROS regulate many developmental processes such as cell proliferation and differentiation, programmed cell death, seed germination, gravitropism, root hair growth and pollen tube development, senescence, etc. Despite much progress, a comprehensive update of advances in the understanding of the mechanisms evoked by ROS that mediate in cell proliferation and development are fragmentry and the matter of ROS perception and the signaling cascade remains open. Therefore, keeping in view the above facts, an attempt has been made in this article to summarize the recent findings regarding updates made in the regulatory action of ROS at various plant developmental stages, which are still not well known.

  14. Reactive Oxygen Species (ROS): Beneficial Companions of Plants’ Developmental Processes

    Science.gov (United States)

    Singh, Rachana; Singh, Samiksha; Parihar, Parul; Mishra, Rohit K.; Tripathi, Durgesh K.; Singh, Vijay P.; Chauhan, Devendra K.; Prasad, Sheo M.

    2016-01-01

    Reactive oxygen species (ROS) are generated inevitably in the redox reactions of plants, including respiration and photosynthesis. In earlier studies, ROS were considered as toxic by-products of aerobic pathways of the metabolism. But in recent years, concept about ROS has changed because they also participate in developmental processes of plants by acting as signaling molecules. In plants, ROS regulate many developmental processes such as cell proliferation and differentiation, programmed cell death, seed germination, gravitropism, root hair growth and pollen tube development, senescence, etc. Despite much progress, a comprehensive update of advances in the understanding of the mechanisms evoked by ROS that mediate in cell proliferation and development are fragmentry and the matter of ROS perception and the signaling cascade remains open. Therefore, keeping in view the above facts, an attempt has been made in this article to summarize the recent findings regarding updates made in the regulatory action of ROS at various plant developmental stages, which are still not well-known. PMID:27729914

  15. Failure Prediction in Bulk Metal Forming Process

    Directory of Open Access Journals (Sweden)

    Ameen Topa

    2014-01-01

    Full Text Available An important concern in metal forming is whether the desired deformation can be accomplished without defects in the final product. Various ductile fracture criteria have been developed and experimentally verified for a limited number of cases of metal forming processes. These criteria are highly dependent on the geometry of the workpiece and cannot be utilized for complicated shapes without experimental verification. However, experimental work is a resource hungry process. This paper proposes the ability of finite element analysis (FEA software such as LS-DYNA to pinpoint the crack-like flaws in bulk metal forming products. Two different approaches named as arbitrary Lagrangian-Eulerian (ALE and smooth particle hydrodynamics (SPH formulations were adopted. The results of the simulations agree well with the experimental work and a comparison between the two formulations has been carried out. Both approximation methods successfully predicted the flow of workpiece material (plastic deformation. However ALE method was able to pinpoint the location of the flaws.

  16. A cross-reactive sensor array for the fluorescence qualitative analysis of heavy metal ions.

    Science.gov (United States)

    Kang, Huaizhi; Lin, Liping; Rong, Mingcong; Chen, Xi

    2014-11-01

    A cross-reactive sensor array using mercaptopropionic acid modified cadmium telluride (CdTe), glutathione modified CdTe, poly(methacrylic acid) modified silver nanoclusters, bovine serum albumin modified gold nanoclusters, rhodamine derivative and calcein blue as fluorescent indicators has been designed for the detection of seven heavy metal ions (Ag(+), Hg(2+), Pb(2+), Cu(2+), Cr(3+), Mn(2+) and Cd(2+)). The discriminatory capacity of the sensor array to different heavy metal ions in different pH solutions has been tested and the results have been analyzed with linear discriminant analysis. Results showed that the sensor array could be used to qualitatively analyze the selected heavy metal ions. The array performance was also evaluated in the identification of known and unknown samples and the preliminary results suggested the promising practicability of the designed sensor assay.

  17. Reliable processing of graphene using metal etchmasks

    Directory of Open Access Journals (Sweden)

    Peltekis Nikos

    2011-01-01

    Full Text Available Abstract Graphene exhibits exciting properties which make it an appealing candidate for use in electronic devices. Reliable processes for device fabrication are crucial prerequisites for this. We developed a large area of CVD synthesis and transfer of graphene films. With patterning of these graphene layers using standard photoresist masks, we are able to produce arrays of gated graphene devices with four point contacts. The etching and lift off process poses problems because of delamination and contamination due to polymer residues when using standard resists. We introduce a metal etch mask which minimises these problems. The high quality of graphene is shown by Raman and XPS spectroscopy as well as electrical measurements. The process is of high value for applications, as it improves the processability of graphene using high-throughput lithography and etching techniques.

  18. Simulation of reactive processes related to biodegradation in aquifers. 1. Structure of the three-dimensional reactive transport model

    Science.gov (United States)

    Schäfer, Dirk; Schäfer, Wolfgang; Kinzelbach, Wolfgang

    1998-05-01

    The reactive transport model TBC (transport, biochemistry, and chemistry) numerically solves the equations for reactive transport in three-dimensional saturated groundwater flow. A finite element approximation and a standard Galerkin method are used. Solute transport is coupled to microbially mediated organic carbon degradation. Microbial growth is assumed to follow Monod-type kinetics. Substrate consumption and release of metabolic products is coupled to microbial growth via yield coefficients and stoichiometric relations. Additionally, the effects of microbial activity on selected inorganic chemical species in the aquifer can be considered. TBC allows the user to specify a wide range of possible biochemical and chemical reactions in the input file. This makes TBC a powerful and flexible simulation tool. It was developed to simulate reactive processes related to in situ bioremediation, but further fields of application are laboratory column studies on redox processes coupled to organic carbon degradation, field cases of intrinsic biodegradation, and early diagenetic processes in sediments.

  19. Reactivity of Metal Oxide Sorbents for Removal of H{sub 2}S

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, K.C.; Crowe, E.R. [Chemical Engineering Dept., School of Engineering and Architecture, Tuskegee Univ., AL (United States)

    1996-12-31

    Removal of hydrogen sulfide contained in hot coal gases produced from integrated gasification combined cycle power generation systems is required to protect downstream combustion turbines from being corroded with sulfur compounds. Removal of sulfur compounds from hot coal gas products is investigated by using various metal oxide sorbents and membrane separation methods. The main requirements of these metal oxide sorbents are durability and high sulfur loading capacity during absorption-regeneration cycles. In this research, durable metal oxide sorbents were formulated. Reactivity of the formulated metal oxide sorbents with simulated coal gas mixtures was examined to search for an ideal sorbent formulation with a high-sulfur loading capacity suitable for removal of hydrogen sulfide from coal gases. The main objectives of this research are to formulate durable metal oxide sorbents with high-sulfur loading capacity by a physical mixing method, to investigate reaction kinetics on the removal of sulfur compounds from coal gases at high temperature and pressure, to study reaction kinetics on the regeneration of sulfided sorbents, to identify effects of hydrogen partial pressures and moisture on equilibrium/dynamic absorption of hydrogen sulfide into formulated metal oxide sorbents as well as initial reaction rates of H{sub 2}S with formulated metal oxide sorbents, and to evaluate intraparticular diffusivity of H{sub 2}S into formulated sorbents at various reaction conditions. The metal oxide sorbents such as TU-1, TU-19, TU-24, TU-25 and TU-28 were formulated with zinc oxide powder as an active sorbent ingredient, bentonite as a binding material and titanium oxide as a supporting metal oxide.

  20. ICM METALLICITY EVOLUTION: EFFECTS OF DYNAMICAL PROCESSES

    Directory of Open Access Journals (Sweden)

    S. Cora

    2009-01-01

    Full Text Available We present a study on the origin of the metallicity evolution of the intracluster medium (ICM by applying a semi-analytic model of galaxy formation to N-Body/SPH non-radiative cosmological simulations of clusters of galaxies. The results obtained for a set of clusters with virial masses of - 1:5 - 1015 h-1M contribute to the theoretical interpretation of recent observational X-ray data, which indicate a decrease of the average iron content of the intracluster gas with increasing redshift, z. We nd that this evolution is mainly due to a progressive increase of the iron content within 15 per cent of the virial radius as a result of dynamical processes. The clusters have been considerably enriched by z - 1 with very low contribution from recent star formation. Low entropy gas that has been enriched at high z sink to the cluster centre contributing to the evolution of the metallicity pro les.

  1. Second sphere coordination of hybrid metal-organic materials: solid state reactivity.

    Science.gov (United States)

    Guo, Fang; Martí-Rujas, Javier

    2016-09-21

    When compared to other hybrid metal organic materials such as metal-organic frameworks, hydrogen bonded materials self-assembled by metals and organic molecules using second sphere interactions have been poorly investigated. Consequently, their solid-sate properties are also scarce. In this perspective, earlier research mainly on host-guest chemistry and its evolution towards more extended structures by applying crystal engineering principles using second sphere coordination is described. Crystal-to-crystal guest exchange reactions, permanently porous hybrid metal organic materials, mechanochemical reactivity, thermally induced phase transformations as well as some examples of functional technological applications using second sphere adducts such as gas adsorption, separation and non-linear optical phenomena are also reported. Although some tutorial reviews on second sphere adducts have been conducted mainly in the solution state focusing on metal based anion receptors, to the best of our knowledge, an overview on relevant works that focus on the solid-state properties has not been carried out. The aim of this article is to highlight from some of the early fundamental work to the latest reports on hybrid metal-organic materials self-assembled via second sphere interactions with a focus on solid-state chemistry.

  2. Influences of Mn(II) and V(IV) on Bacterial Surface Chemistry and Metal Reactivity

    Science.gov (United States)

    French, S.; Fakra, S.; Glasauer, S.

    2009-05-01

    Microorganisms in terrestrial and marine environments are typically bathed in solutions that contain a range of metal ions, toxic and beneficial. Bacteria such as Shewanella putrefaciens CN32 are metabolically versatile in their respiration, and the reductive dissolution of widely dispersed metals such as Fe(III), Mn(IV), or V(V) can present unique challenges if nearby bodies of water are used for irrigation or drinking. In redox transition zones, dissimilatory metal reduction (DMR) by bacteria can lead to generation of high concentrations of soluble metals. It has been shown that metals will associate with negatively charged bacterial membranes, and the mechanisms of metal reduction are well defined for many species of bacteria. The interaction of metals with the cell wall during DMR is, however, not well documented; very little is known about the interaction of respired transition metals with membrane lipids. Furthermore, bacterial surfaces tend to change in response to their immediate environments. Variations in conditions such as oxygen or metal presence may affect surface component composition, including availability of metal reactive sites. Our research seeks to characterize the biochemical nature of metal-membrane interactions, as well as identify the unique changes at the cell surface that arise as a result of metal presence in their environments. We have utilized scanning transmission X-ray microscopy (STXM) to examine the dynamics of soluble Mn(II) and V(IV) interactions with purified bacterial membranes rather than whole cells. This prevents intracellular interferences, and allows for near edge X-ray absorption fine structure (NEXAFS) spectroscopic analyses of cell surface and surface-associated components. NEXAFS spectra for carbon, nitrogen, and oxygen edges indicate that Mn(II) and V(IV) induce biological modifications of the cell membrane in both aerobic and anaerobic conditions. These changes depend not only on the metal, but also on the presence of

  3. Structure-Reactivity Relationships in Multi-Component Transition Metal Oxide Catalysts FINAL Report

    Energy Technology Data Exchange (ETDEWEB)

    Altman, Eric I. [Yale Univ., New Haven, CT (United States)

    2015-10-06

    The focus of the project was on developing an atomic-level understanding of how transition metal oxide catalysts function. Over the course of several renewals the specific emphases shifted from understanding how local structure and oxidation state affect how molecules adsorb and react on the surfaces of binary oxide crystals to more complex systems where interactions between different transition metal oxide cations in an oxide catalyst can affect reactivity, and finally to the impact of cluster size on oxide stability and reactivity. Hallmarks of the work were the use of epitaxial growth methods to create surfaces relevant to catalysis yet tractable for fundamental surface science approaches, and the use of scanning tunneling microscopy to follow structural changes induced by reactions and to pinpoint adsorption sites. Key early findings included the identification of oxidation and reduction mechanisms on a tungsten oxide catalyst surface that determine the sites available for reaction, identification of C-O bond cleavage as the rate limiting step in alcohol dehydration reactions on the tungsten oxide surface, and demonstration that reduction does not change the favored reaction pathway but rather eases C-O bond cleavage and thus reduces the reaction barrier. Subsequently, a new reconstruction on the anatase phase of TiO2 relevant to catalysis was discovered and shown to create sites with distinct reactivity compared to other TiO2 surfaces. Building on this work on anatase, the mechanism by which TiO2 enhances the reactivity of vanadium oxide layers was characterized and it was found that the TiO2 substrate can force thin vanadia layers to adopt structures they would not ordinarily form in the bulk which in turn creates differences in reactivity between supported layers and bulk samples. From there, the work progressed to studying well-defined ternary oxides where synergistic effects between the two cations can induce

  4. Governing processes for reactive nitrogen compounds in the European atmosphere

    Science.gov (United States)

    Hertel, O.; Skjøth, C. A.; Reis, S.; Bleeker, A.; Harrison, R. M.; Cape, J. N.; Fowler, D.; Skiba, U.; Simpson, D.; Jickells, T.; Kulmala, M.; Gyldenkærne, S.; Sørensen, L. L.; Erisman, J. W.; Sutton, M. A.

    2012-12-01

    Reactive nitrogen (Nr) compounds have different fates in the atmosphere due to differences in the governing processes of physical transport, deposition and chemical transformation. Nr compounds addressed here include reduced nitrogen (NHx: ammonia (NH3) and its reaction product ammonium (NH4+)), oxidized nitrogen (NOy: nitrogen monoxide (NO) + nitrogen dioxide (NO2) and their reaction products) as well as organic nitrogen compounds (organic N). Pollution abatement strategies need to take into account the differences in the governing processes of these compounds when assessing their impact on ecosystem services, biodiversity, human health and climate. NOx (NO + NO2) emitted from traffic affects human health in urban areas where the presence of buildings increases the residence time in streets. In urban areas this leads to enhanced exposure of the population to NOx concentrations. NOx emissions generally have little impact on nearby ecosystems because of the small dry deposition rates of NOx. These compounds need to be converted into nitric acid (HNO3) before removal through deposition is efficient. HNO3 sticks quickly to any surface and is thereby either dry deposited or incorporated into aerosols as nitrate (NO3-). In contrast to NOx compounds, NH3 has potentially high impacts on ecosystems near the main agricultural sources of NH3 because of its large ground-level concentrations along with large dry deposition rates. Aerosol phase NH4+ and NO3- contribute significantly to background PM2.5 and PM10 (mass of aerosols with an aerodynamic diameter of less than 2.5 and 10 μm, respectively) with an impact on radiation balance as well as potentially on human health. Little is known quantitatively and qualitatively about organic N in the atmosphere, other than that it contributes a significant fraction of wet-deposited N, and is present in both gaseous and particulate forms. Further studies are needed to characterise the sources, air chemistry and

  5. Effect of thermal processing on T cell reactivity of shellfish allergens - Discordance with IgE reactivity

    Science.gov (United States)

    Abramovitch, Jodie B.; Lopata, Andreas L.; O’Hehir, Robyn E.

    2017-01-01

    Crustacean allergy is a major cause of food-induced anaphylaxis. We showed previously that heating increases IgE reactivity of crustacean allergens. Here we investigate the effects of thermal processing of crustacean extracts on cellular immune reactivity. Raw and cooked black tiger prawn, banana prawn, mud crab and blue swimmer crab extracts were prepared and IgE reactivity assessed by ELISA. Mass spectrometry revealed a mix of several allergens in the raw mud crab extract but predominant heat-stable tropomyosin in the cooked extract. PBMC from crustacean-allergic and non-atopic control subjects were cultured with the crab and prawn extracts and proliferation of lymphocyte subsets was analysed by CFSE labelling and flow cytometry. Effector responses were assessed by intracellular IL-4 and IFN-γ, and regulatory T (CD4+CD25+CD127loFoxp3+) cell proportions in cultures were also compared by flow cytometry. For each crustacean species, the cooked extract had greater IgE reactivity than the raw (mud crab pcrustacean-stimulated PBMC cultures, dividing CD4+ and CD56+ lymphocytes showed higher IL-4+/IFN-γ+ ratios for crustacean-allergic subjects than for non-atopics (pcrustacean extracts, but decreased induction of Tregs. In contrast, IgE reactivity of cooked extracts was increased markedly. These novel findings have important implications for improved diagnostics, managing crustacean allergy and development of future therapeutics. Assessment of individual allergen T cell reactivity is required. PMID:28273149

  6. Manufacturing processes of cellular metals. Part II. Solid route, metals deposition, other processes; Procesos de fabricacion de metales celulares. Parte II: Via solida, deposicion de metales otros procesos

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez, P.; Cruz, L. J.; Coleto, J.

    2009-07-01

    At the first part of this paper review a description about cellular metal processes by liquid route, was made. In this second part, solid processes and metals deposition are described. In similar way, the different kind of processes in each case are reviewed; making a short description about the main parameters involved and the advantages and drawbacks in each of them. (Author) 147 refs.

  7. An evaluation of the reactivity of synthetic and natural apatites in the presence of aqueous metals.

    Science.gov (United States)

    Dybowska, Agnieszka; Manning, David A C; Collins, Matthew J; Wess, Timothy; Woodgate, Stephen; Valsami-Jones, Eugenia

    2009-04-01

    Metal removal from contaminated effluents was examined following reaction with natural apatites of biological and geological origin or a synthetic hydroxylapatite (HAP). Mammalian meat and bone meal (MBM), a by-product from meat industry, was the biological apatite source. The effect of incineration on metal removal capacity of MBM and HAP was also examined. The reactivity of apatites for all tested metals (Pb, Cd, Cu and Zn) followed the general order: synthetic > biological > mineral. For all apatites tested, Pb was removed best and preferentially from multi-metal solutions. MBM and HAP (0.5 g solid) removed Pb completely from both highly concentrated single metal solutions (50 ml, 1000 mg/L Pb) and from multi-metal solutions (50 ml) with 100 mg/L each of Cd, Cu and Zn in addition to Pb. The incineration of MBM (725 degrees C and 850 degrees C) reduced significantly its capacity for removal of Zn (by 47%, from 56 mg/g to 9 mg/g) and Cd (by 38%, from 53 mg/g to 13 mg/g) in particular and to a lesser extent for Cu (by 14%, from 61 mg/g to 46 mg/g) while the removal of Pb was not affected (100 mg/g). The same pattern was observed for incinerated HAP. SEM and XRD analysis indicated that HAP reacted with the metals by precipitation of pure metal phosphates--Pb hydroxylapatite, Zn phosphate (hopeite), a Cd phosphate (identified only by ED-SEM) and Cu phosphate (libenthenite).

  8. Application of the Condensed Fukui Function to Predict Reactivity in Core–Shell Transition Metal Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Allison, Thomas C.; Tong, Yu ye J.

    2013-07-01

    Chemical reactivity descriptors are a powerful means for understanding reactivity in a wide variety of chemical compounds. These descriptors, rooted in density functional theory, have found broad application in organic chemical reactions, but have not been as widely applied for other classes of chemical species such as nanoparticles, which are the subject of this article. Specifically, we explore application of the Fukui function, the global hardness and softness, the local softness, and the dual descriptor to pure metallic and core–shell nanoparticles, with and without a CO molecule bound to the surface. We find that the Fukui function is useful in predicting and interpreting chemical reactivity, and that it correlates well with the results of the popular d-band center method. Differences in the Fukui function before and after bonding of a CO molecule to the surface of a nanoparticle reveal interesting information about the reactivity of the nanoparticle surface. The change in the Fukui function when an electric field is applied to the molecule is also considered. Though the results are generally good, some of the limitations of this approach become clear.

  9. Simulations of Metal Cu in Heating Process

    Institute of Scientific and Technical Information of China (English)

    ZHANG, Tao(张弢); WU, Ai-Ling(吴爱玲); GUAN, Li(管立); QI, Yuan-Hua(齐元华)

    2004-01-01

    Based on the Finnis-Sinsclair (FS) many-body potential model, the melting process of a system, which consists of 500 Cu atoms, controlled by period boundary condition has been simulated. The means of pair correlation function, mean square displacement and Honeycutt-Anderson bonded pair have been used to characterize the melting behavior of Cu at different heating rates. The simulation indicates that melting point of metal Cu is 1444 K during a continuous heating process, and the calculated diffusion constant at the melting point is 4.31×10-9 m2/s. These results are better than those from the EAM method, showing that the FS potential model works well in some disordered systems.

  10. Drop Dynamics and Speciation in Isolation of Metals from Liquid Wastes by Reactive Scavenging

    Energy Technology Data Exchange (ETDEWEB)

    Arne J. Pearlstein; Alexander Scheeline

    2002-08-30

    Computational and experimental studies of the motion and dynamics of liquid drops in gas flows were conducted with relevance to reactive scavenging of metals from atomized liquid waste. Navier-Stoke's computations of deformable drops revealed a range of conditions from which prolate drops are expected, and showed how frajectiones of deformable drops undergoing deceleration can be computed. Experimental work focused on development of emission fluorescence, and scattering diagnostics. The instrument developed was used to image drop shapes, soot, and nonaxisymmetric departures from steady flow in a 22kw combustor

  11. A simple reactivity feedback model accounting for radial core expansion effects in the liquid metal fast reactor

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Young Min; Lee, Yong Bum; Chang, Won Pyo; Haha, Do Hee [KAERI, Taejon (Korea, Republic of)

    2002-10-01

    The radial core expansion due to the structure temperature rise is one of major negative reactivity insertion mechanisms in metallic fueled reactor. Thermal expansion is a result of both the laws of nature and the particular core design and it causes negative reactivity feedback by the combination of increased core volume captures and increased core surface leakage. The simple radial core expansion reactivity feedback model developed for the SSC-K code was evaluated by the code-to-code comparison analysis. From the comparison results, it can be stated that the radial core expansion reactivity feedback model employed into the SSC-K code may be reasonably accurate in the UTOP analysis.

  12. Governing processes for reactive nitrogen compounds in the European atmosphere

    Directory of Open Access Journals (Sweden)

    O. Hertel

    2012-12-01

    Full Text Available Reactive nitrogen (Nr compounds have different fates in the atmosphere due to differences in the governing processes of physical transport, deposition and chemical transformation. Nr compounds addressed here include reduced nitrogen (NHx: ammonia (NH3 and its reaction product ammonium (NH4+, oxidized nitrogen (NOy: nitrogen monoxide (NO + nitrogen dioxide (NO2 and their reaction products as well as organic nitrogen compounds (organic N. Pollution abatement strategies need to take into account the differences in the governing processes of these compounds when assessing their impact on ecosystem services, biodiversity, human health and climate. NOx (NO + NO2 emitted from traffic affects human health in urban areas where the presence of buildings increases the residence time in streets. In urban areas this leads to enhanced exposure of the population to NOx concentrations. NOx emissions generally have little impact on nearby ecosystems because of the small dry deposition rates of NOx. These compounds need to be converted into nitric acid (HNO3 before removal through deposition is efficient. HNO3 sticks quickly to any surface and is thereby either dry deposited or incorporated into aerosols as nitrate (NO3. In contrast to NOx compounds, NH3 has potentially high impacts on ecosystems near the main agricultural sources of NH3 because of its large ground-level concentrations along with large dry deposition rates. Aerosol phase NH4+ and NO3 contribute significantly to background PM2.5 and PM10 (mass of aerosols with an aerodynamic diameter of less than 2.5 and 10 μm, respectively with an impact on radiation balance as well as potentially on human

  13. Emerging technologies in extraction and processing of metals

    Science.gov (United States)

    Reddy, Ramana G.

    2003-04-01

    The growing need to conserve energy and materials and prevent environmental pollution led to an increased demand for better understanding of potential as well as existing processes. In this context, thermodynamic and transport modeling of materials and processes provides a rapid and cost-effective means of conducting and minimizing the complexity of experimental investigations and developing innovative and environmentally friendly metallurgical processes. This presentation concentrates on some fundamentals on new technologies as extractive metallurgy of copper, lead, aluminum, and other nonferrous metals and processing of nanocomposites. The newer routes of copper smelting and modeling of impurities in copper and lead slags and mattes are reviewed. The copper smelting capacity increased by a factor of 10 during the last three decades, the smelting rate increased by a factor of 6, and the process fuel equivalent decreased by a factor of 2. The a priori prediction, with no adjustable parameters, of impurity capacities of S and As in copper slags and S in lead slags, based on the Reddy-Blander model, is reviewed. Excellent agreement between the model-predicted capacities data and laboratory experimental and industrial data was observed. The model is an invaluable tool for optimization of process parameters in the efficient removal of impurities from the nonferrous-metals smelting and refining processes. A new in-situ processing technology for the production of a lightweight alloy matrix with ceramic particle reinforcements such as SiC in aluminum alloy matrix composites by bubbling reactive gas is reviewed. Thermal plasma processing of a nanoscale aluminum alloy matrix with TiC and TiN composites is discussed. The in-situ formed reinforcements are thermodynamically stable, and the composite particles are of uniform size. The optimum process parameters for the production of composite powders by thermal plasma are discussed. A low-temperature aluminum production and

  14. Process for fabrication of metal oxide films

    Energy Technology Data Exchange (ETDEWEB)

    Tracy, C.E.; Benson, D.; Svensson, S.

    1990-07-17

    This invention is comprised of a method of fabricating metal oxide films from a plurality of reactants by inducing a reaction by plasma deposition among the reactants. The plasma reaction is effective for consolidating the reactants and producing thin films of metal oxides, e.g. electro-optically active transition metal oxides, at a high deposition rate. The presence of hydrogen during the plasma reaction enhances the deposition rate of the metal oxide. Various types of metal oxide films can be produced.

  15. Trends in low-temperature water–gas shift reactivity on transition metals

    DEFF Research Database (Denmark)

    Schumacher, Nana Maria Pii; Boisen, Astrid; Dahl, Søren;

    2005-01-01

    Low-temperature water–gas shift reactivity trends on transition metals were investigated with the use of a microkinetic model based on a redox mechanism. It is established that the adsorption energies for carbon monoxide and oxygen can describe to a large extent changes in the remaining activation...... and adsorption energies through linear correlations. In comparisons with experimental data it is found that the model predicts well the order of catalytic activities for transition metals, although it fails to quantitatively describe the experimental data. This discrepancy could be due to the assumption...... that the redox mechanism dominates and to the neglect of adsorbate interactions, which play an important role at high coverages. The model predicts that the activity of copper can be improved by increasing the strengths with which carbon monoxide and oxygen are bonded to the surface, thus suggesting possible...

  16. Investigation of Reactivity Feedback Mechanism of Axial and Radial Expansion Effect of Metal-Fueled Sodium-Cooled Fast Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Seong, Seung-Hwan; Choi, Chi-Woong; Jeong, Tae-Kyung; Ha, Gi-Seok [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2015-05-15

    The major inherent reactivity feedback models for a ceramic fuel used in a conventional light water reactor are Doppler feedback and moderator feedback. The metal fuel has these two reactivity feedback mechanisms previously mentioned. In addition, the metal fuel has two more reactivity feedback models related to the thermal expansion phenomena of the metal fuel. Since the metal fuel has a good capability to expand according to the temperature changes of the core, two more feedback mechanisms exist. These additional two feedback mechanism are important to the inherent safety of metal fuel and can make metal-fueled SFR safer than oxide-fueled SFR. These phenomena have already been applied to safety analysis on design extended condition. In this study, the effect of these characteristics on power control capability was examined through a simple load change operation. The axial expansion mechanism is induced from the change of the fuel temperature according to the change of the power level of PGSFR. When the power increases, the fuel temperatures in the metal fuel will increase and then the reactivity will decrease due to the axial elongation of the metal fuel. To evaluate the expansion effect, 2 cases were simulated with the same scenario by using MMS-LMR code developed at KAERI. The first simulation was to analyze the change of the reactor power according to the change of BOP power without the reactivity feedback model of the axial and radial expansion of the core during the power transient event. That is to say, the core had only two reactivity feedback mechanism of Doppler and coolant temperature.

  17. Laser Processing of Metals and Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Singaravelu, Senthilraja [Old Dominion Univ., Norfolk, VA (United States)

    2012-05-01

    A laser offers a unique set of opportunities for precise delivery of high quality coherent energy. This energy can be tailored to alter the properties of material allowing a very flexible adjustment of the interaction that can lead to melting, vaporization, or just surface modification. Nowadays laser systems can be found in nearly all branches of research and industry for numerous applications. Sufficient evidence exists in the literature to suggest that further advancements in the field of laser material processing will rely significantly on the development of new process schemes. As a result they can be applied in various applications starting from fundamental research on systems, materials and processes performed on a scientific and technical basis for the industrial needs. The interaction of intense laser radiation with solid surfaces has extensively been studied for many years, in part, for development of possible applications. In this thesis, I present several applications of laser processing of metals and polymers including polishing niobium surface, producing a superconducting phase niobium nitride and depositing thin films of niobium nitride and organic material (cyclic olefin copolymer). The treated materials were examined by scanning electron microscopy (SEM), electron probe microanalysis (EPMA), atomic force microscopy (AFM), high resolution optical microscopy, surface profilometry, Fourier transform infrared spectroscopy (FTIR) and x-ray diffraction (XRD). Power spectral density (PSD) spectra computed from AFM data gives further insight into the effect of laser melting on the topography of the treated niobium.

  18. Noble Metal/Ceramic Composites in Flame Processes

    DEFF Research Database (Denmark)

    Schultz, Heiko; Madler, Lutz; Strobel, Reto

    Noble metals on metal oxides play a major role in the performance of electrodes, catalysts and many other applications. Today, impregnation of noble metals on metal oxides is done in the wet phase involving multiple steps. The physicochemical nature of the support, the precursor and the reaction...... conditions influence the resulting noble metal particles size in those systems [1]. For every specific application the particle size and the metal/metal oxide interaction affect the performance of these nano-composite materials [2]. Recently, aerosol processes have been successfully used to produce platinum......-7] with metal particles smaller than 7 nm on the metal oxide [3-7]. This makes them attractive for reactions with mass transfer limitation and for high temperature applications. An intimate contact of the two particles was observed in HRTEM images [3-5,7]. For a specific metal oxide support the metal particle...

  19. Catalytic extraction processing of contaminated scrap metal

    Energy Technology Data Exchange (ETDEWEB)

    Griffin, T.P.; Johnston, J.E.; Payea, B.M. [Molten Metal Technology, Inc., Waltham, MA (United States)] [and others

    1995-10-01

    The U.S. Department of Energy issued a Planned Research and Development Announcement (PRDA) in 1993, with the objective of identifying unique technologies which could be applied to the most hazardous waste streams at DOE sites. The combination of radioactive contamination with additional contamination by hazardous constituents such as those identified by the Resource Conservation and Recovery Act (RCRA) pose an especially challenging problem. Traditional remediation technologies are increasingly becoming less acceptable to stakeholders and regulators because of the risks they pose to public health and safety. Desirable recycling technologies were described by the DOE as: (1) easily installed, operated, and maintained; (2) exhibiting superior environmental performance; (3) protective of worker and public health and safety; (4) readily acceptable to a wide spectrum of evaluators; and (5) economically feasible. Molten Metal Technology, Inc. (MMT) was awarded a contract as a result of the PRDA initiative to demonstrate the applicability of Catalytic Extraction Processing (CEP), MMT`s proprietary elemental recycling technology, to DOE`s inventory of low level mixed waste. This includes DOE`s inventory of radioactively- and RCRA-contaminated scrap metal and other waste forms expected to be generated by the decontamination and decommissioning (D&D) of DOE sites.

  20. REACTIVE MINERALS IN AQUIFERS: FORMATION PROCESSES AND QUANTITATIVE ANALYSIS

    Science.gov (United States)

    The presentation will focus on the occurrence, form, and characterization of reactive iron minerals in aquifers and soils. The potential for abiotic reductive transformations of contaminants at the mineral-water interface will be discussed along with available tools for site min...

  1. Ultrathin magnesia films as support for molecules and metal clusters: Tuning reactivity by thickness and composition

    Energy Technology Data Exchange (ETDEWEB)

    Vaida, Mihai E.; Bernhardt, Thorsten M. [Institute of Surface Chemistry and Catalysis, University of Ulm (Germany); Barth, Clemens [CINAM-CNRS, Marseille (France); Esch, Friedrich; Heiz, Ueli [Department of Chemistry, Technical University of Munich, Garching (Germany); Landman, Uzi [School of Physics, Georgia Institute of Technology, Atlanta, Georgia (United States)

    2010-05-15

    Ultrathin metal oxide films have attracted considerable interest in recent years as versatile substrate for the design of nanocatalytic model systems. In particular, it has been proposed theoretically and confirmed experimentally that the electronic structure of adsorbates can be influenced by the layer thickness and the stoichiometry, i.e., the type and number of defects, of the oxide film. This has important consequences on the chemical reactivity of the oxide surface itself and of oxide supported metal clusters. It also opens new possibilities to influence and to control chemical reactions occurring at the surface of these systems. The present feature focuses on very recent experiments that illustrate the effects of a proper adjustment of layer thickness and composition of ultrathin MgO(100) films on chemical transformations. On the magnesia surface itself, the photodissociation dynamics of methyl iodide molecules is investigated via femtosecond-laser pump-probe mass spectrometry. Furthermore, the catalytic oxidation of carbon monoxide at mass-selected Au{sub 20} clusters deposited on magnesia is explored through temperature programmed reaction measurements. In the latter case, detailed first principles calculations are able to correlate the experimentally observed reactivity with structural dimensionality changes that are induced by the changing thickness and composition of the magnesia support. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  2. Statistical model for combustion of high-metal magnesium-based hydro-reactive fuel

    Institute of Scientific and Technical Information of China (English)

    Hu Jian-Xin; Han Chao; Xia Zhi-Xun; Huang Li-Ya; Huang Xu

    2012-01-01

    We investigate experimentally and analytically the combustion behavior of a high-metal magnesium-based hydro-reactive fuel under high temperature gaseous atmosphere.The fuel studied in this paper contains 73% magnesium powders.An experimental system is designed and experimeuts are carried out in both argon and water vapor atmospheres.It is found that the burning surface temperature of the fuel is higher in water vapor than that in argon and both of them are higher than the melting point of magnesium,which indicates the molten state of magnesium particles in the burning surface of the fuel.Based on physical considerations and experimental results,a mathematical one-dimensional model is formulated to describe the combustion behavior of the high-metal magnesium-based hydro-reactive fuel.The model enables the evaluation of the burning surface temperature,the burning rate and the flame standoff distance each as a function of chamber pressure and water vapor concentration.The results predicted by the model show that the burning rate and the surface temperature increase when the chamber pressure and the water vapor concentration increase,which are in agreement with the observed experimental trends.

  3. Process for removing technetium from iron and other metals

    Science.gov (United States)

    Leitnaker, James M.; Trowbridge, Lee D.

    1999-01-01

    A process for removing technetium from iron and other metals comprises the steps of converting the molten, alloyed technetium to a sulfide dissolved in manganese sulfide, and removing the sulfide from the molten metal as a slag.

  4. Impact of interactions between metal oxides to oxidative reactivity of manganese dioxide.

    Science.gov (United States)

    Taujale, Saru; Zhang, Huichun

    2012-03-01

    Manganese oxides typically exist as mixtures with other metal oxides in soil-water environments; however, information is only available on their redox activity as single oxides. To bridge this gap, we examined three binary oxide mixtures containing MnO(2) and a secondary metal oxide (Al(2)O(3), SiO(2) or TiO(2)). The goal was to understand how these secondary oxides affect the oxidative reactivity of MnO(2). SEM images suggest significant heteroaggregation between Al(2)O(3) and MnO(2) and to a lesser extent between SiO(2)/TiO(2) and MnO(2). Using triclosan and chlorophene as probe compounds, pseudofirst-order kinetic results showed that Al(2)O(3) had the strongest inhibitory effect on MnO(2) reactivity, followed by SiO(2) and then TiO(2). Al(3+) ion or soluble SiO(2) had comparable inhibitory effects as Al(2)O(3) or SiO(2), indicating the dominant inhibitory mechanism was surface complexation/precipitation of Al/Si species on MnO(2) surfaces. TiO(2) inhibited MnO(2) reactivity only when a limited amount of triclosan was present. Due to strong adsorption and slow desorption of triclosan by TiO(2), precursor-complex formation between triclosan and MnO(2) was much slower and likely became the new rate-limiting step (as opposed to electron transfer in all other cases). These mechanisms can also explain the observed adsorption behavior of triclosan by the binary oxide mixtures and single oxides.

  5. Possible Roles of Plant Sulfurtransferases in Detoxification of Cyanide, Reactive Oxygen Species, Selected Heavy Metals and Arsenate

    Directory of Open Access Journals (Sweden)

    Parvin Most

    2015-01-01

    Full Text Available Plants and animals have evolved various potential mechanisms to surmount the adverse effects of heavy metal toxicity. Plants possess low molecular weight compounds containing sulfhydryl groups (-SH that actively react with toxic metals. For instance, glutathione (γ-Glu-Cys-Gly is a sulfur-containing tripeptide thiol and a substrate of cysteine-rich phytochelatins (γ-Glu-Cys2–11-Gly (PCs. Phytochelatins react with heavy metal ions by glutathione S-transferase in the cytosol and afterwards they are sequestered into the vacuole for degradation. Furthermore, heavy metals induce reactive oxygen species (ROS, which directly or indirectly influence metabolic processes. Reduced glutathione (GSH attributes as an antioxidant and participates to control ROS during stress. Maintenance of the GSH/GSSG ratio is important for cellular redox balance, which is crucial for the survival of the plants. In this context, sulfurtransferases (Str, also called rhodaneses, comprise a group of enzymes widely distributed in all phyla, paving the way for the transfer of a sulfur atom from suitable sulfur donors to nucleophilic sulfur acceptors, at least in vitro. The best characterized in vitro reaction is the transfer of a sulfane sulfur atom from thiosulfate to cyanide, leading to the formation of sulfite and thiocyanate. Plants as well as other organisms have multi-protein families (MPF of Str. Despite the presence of Str activities in many living organisms, their physiological role has not been clarified unambiguously. In mammals, these proteins are involved in the elimination of cyanide released from cyanogenic compounds. However, their ubiquity suggests additional physiological functions. Furthermore, it is speculated that a member of the Str family acts as arsenate reductase (AR and is involved in arsenate detoxification. In summary, the role of Str in detoxification processes is still not well understood but seems to be a major function in the organism.

  6. FEM Analysis on Electromagnetic Processing of Thin Metal Sheets

    Directory of Open Access Journals (Sweden)

    PASCA Sorin

    2014-10-01

    Full Text Available Based on finite element analysis, this paper investigates a possible new technology for electromagnetic processing of thin metal sheets, in order to improve the productivity, especially on automated manufacturing lines. This technology consists of induction heating process followed by magnetoforming process, both applied to metal sheet, using the same tool coil for both processes.

  7. Process for the enhanced capture of heavy metal emissions

    Science.gov (United States)

    Biswas, Pratim; Wu, Chang-Yu

    2001-01-01

    This invention is directed to a process for forming a sorbent-metal complex. The process includes oxidizing a sorbent precursor and contacting the sorbent precursor with a metallic species. The process further includes chemically reacting the sorbent precursor and the metallic species, thereby forming a sorbent-metal complex. In one particular aspect of the invention, at least a portion of the sorbent precursor is transformed into sorbent particles during the oxidation step. These sorbent particles then are contacted with the metallic species and chemically reacted with the metallic species, thereby forming a sorbent-metal complex. Another aspect of the invention is directed to a process for forming a sorbent metal complex in a combustion system. The process includes introducing a sorbent precursor into a combustion system and subjecting the sorbent precursor to an elevated temperature sufficient to oxidize the sorbent precursor and transform the sorbent precursor into sorbent particles. The process further includes contacting the sorbent particles with a metallic species and exposing the sorbent particles and the metallic species to a complex-forming temperature whereby the metallic species reacts with the sorbent particles thereby forming a sorbent-metal complex under UV irradiation.

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

    Science.gov (United States)

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

    2012-06-27

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

  9. Formation of Metal Selenide and Metal-Selenium Nanoparticles using Distinct Reactivity between Selenium and Noble Metals.

    Science.gov (United States)

    Park, Se Ho; Choi, Ji Yong; Lee, Young Hwan; Park, Joon T; Song, Hyunjoon

    2015-07-01

    Small Se nanoparticles with a diameter of ≈20 nm were generated by the reduction of selenium chloride with NaBH4 at -10 °C. The reaction with Ag at 60 °C yielded stable Ag2 Se nanoparticles, which subsequently were transformed into M-Se nanoparticles (M=Cd, Zn, Pb) through cation exchange reactions with corresponding ions. The reaction with Pt formed Pt layers that were evenly coated on the surface of the Se nanoparticles, and the dissolution of the Se cores with hydrazine generated uniform Pt hollow nanoparticles. The reaction with Au generated tiny Au clusters on the Se surface, and eventually formed acorn-shaped Au-Se nanoparticles through heat treatment. These results indicate that small Se nanoparticles with diameters of ≈20 nm can be used as a versatile platform for the synthesis of metal selenide and metal-selenium hybrid nanoparticles with complex structures.

  10. Monitoring metal-fill in a lost foam casting process.

    Science.gov (United States)

    Abdelrahman, Mohamed; Arulanantham, Jeanison Pradeep; Dinwiddie, Ralph; Walford, Graham; Vondra, Fred

    2006-10-01

    The lost foam casting (LFC) process is emerging as a reliable casting method. The metal-fill profile in LFC plays an important role among several factors that affect casting quality. The metal-fill profile is in turn affected by several factors. Several casting defects may result due to an improper metal-fill process. Hence, it becomes essential to characterize and control, if possible, the metal-fill process in LFC. This research presents instrumentation and a technique to monitor and characterize the metal-fill process. The characterization included the determination of the position of the metal front and the profile in which the metal fills up the foam pattern. The instrumentation included capacitive sensors. Each sensor is comprised of two electrodes whose capacitive coupling changes as the metal fills the foam pattern. Foundry tests were conducted to obtain the sensors' responses to the metal fill. Two such sensors were used in the foundry tests. Data representing the responses of these sensors during the metal-fill process were collected using a data acquisition system. A number of finite element electrostatic simulations were carried out to study the metal-fill process under conditions similar to those experienced in foundry tests. An artificial neural network was trained using the simulation data as inputs and the corresponding metal-fill profiles as outputs. The neural network was then used to infer the profile of the metal-fill during foundry tests. The results were verified by comparing the metal-fill profile inferred from the neural network to the actual metal-fill profile captured by an infrared camera used during the foundry tests. The match up between the inferred profiles and the infrared camera measurements was satisfactory, indicating that the developed technique provides a reliable and cost effective method to monitor the metal-fill profile in LFC.

  11. Theta frontoparietal connectivity associated with proactive and reactive cognitive control processes.

    Science.gov (United States)

    Cooper, Patrick S; Wong, Aaron S W; Fulham, W Ross; Thienel, Renate; Mansfield, Elise; Michie, Patricia T; Karayanidis, Frini

    2015-03-01

    Cognitive control involves both proactive and reactive processes. Paradigms that rely on reactive control have shown that frontoparietal oscillatory synchronization in the theta frequency band is associated with interference control. This study examines whether proactive control is also associated with connectivity in the same frontoparietal theta network or involves a distinct neural signature. A task-switching paradigm was used to differentiate between proactive and reactive control processes, involved in preparing to switch or repeat a task and resolving post-target interference, respectively. We confirm that reactive control is associated with frontoparietal theta connectivity. Importantly, we show that proactive control is also associated with theta band oscillatory synchronization but in a different frontoparietal network. These findings support the existence of distinct proactive and reactive cognitive control processes that activate different theta frontoparietal oscillatory networks.

  12. Pervious concrete reactive barrier for removal of heavy metals from acid mine drainage - column study.

    Science.gov (United States)

    Shabalala, Ayanda N; Ekolu, Stephen O; Diop, Souleymane; Solomon, Fitsum

    2017-02-05

    This paper presents a column study conducted to investigate the potential use of pervious concrete as a reactive barrier for treatment of water impacted by mine waste. The study was done using acid mine drainage (AMD) collected from a gold mine (WZ) and a coalfield (TDB). Pervious concrete mixtures consisting of Portland cement CEM I 52.5R with or without 30% fly ash (FA) were prepared at a water-cementitious ratio of 0.27 then used to make cubes which were employed in the reactor columns. It was found that the removal efficiency levels of Al, Fe, Mn, Co and Ni were 75%, 98%, 99%, 94% and 95% for WZ; 87%, 96%, 99%, 98% and 90% for TDB, respectively. The high rate of acid reduction and metal removal by pervious concrete is attributed to dissolution of portlandite which is a typical constituent of concrete. The dominant reaction product in all four columns was gypsum, which also contributed to some removal of sulphate from AMD. Formation of gypsum, goethite, and Glauber's salt were identified. Precipitation of metal hydroxides seems to be the dominant metal removal mechanism. Use of pervious concrete offers a promising alternative treatment method for polluted or acidic mine water. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Structural Integrity of Single - Molecules on Metal Surfaces with Different Reactivity

    Science.gov (United States)

    Fahrendorf, Sarah; Matthes, Frank; Bürgler, Daniel E.; Schneider, Claus M.; Atodiresei, Nicolae; Caciuc, Vasile; Blügel, Stefan; Besson, Claire; Kögerler, Paul

    2014-07-01

    Magnetic molecules are auspicious candidates to act as functional units in molecular spintronics. Integrating molecules into a device environment providing mechanical support and electrical contacts requires their deposition as intact entities onto substrates. Thermal sublimation is a very clean deposition process that, however, thermally decomposes molecules of insufficient stability leading to the deposition of molecular fragments. Here, we show that the molecule-surface interaction of chemisorbed molecules affects the intramolecular bonding and can lead depending on the surface reactivity to either molecular decomposition or enhanced stability. We study the integrity of single bis(phthalocyaninato)-neodymium(III) molecules (NdPc2) deposited by sublimation on differently reactive surfaces, namely Au(111), Cu(100), and two atomic layers of Fe on W(110), on the single molecular level by scanning tunneling microscopy (STM) and spectroscopy. We find a strongly substrate-dependent tendency of the NdPc2 molecules to decompose into two Pc molecules. Surprisingly, the most reactive Fe/W(110) surface shows the lowest molecular decomposition probability, whereas there are no intact NdPc2 molecules at all on the least reactive Au(111) surface. We attribute these findings to substrate-dependent partial charge transfer from the substrate to the Pc ligands of the molecule, which strengthens the intramolecular bonding mediated predominantly by electrostatic interaction.

  14. Reactivity of the Bacteria-Water Interface: Linking Nutrient Availability to Bacteria-Metal Interactions

    Science.gov (United States)

    Fowle, D. A.; Daughney, C. J.; Riley, J. L.

    2002-12-01

    Identifying and quantifying the controls on metal mobilities in geologic systems is critical in order to understand processes such as global element cycling, metal transport in near-surface water-rock systems, sedimentary diagenesis, and mineral formation. Bacteria are ubiquitous in near-surface water-rock systems, and numerous laboratory and field studies have demonstrated that bacteria can facilitate the formation and dissolution of minerals, and enhance or inhibit contaminant transport. However, despite the growing evidence that bacteria play a key role in many geologic processes in low temperature systems, our understanding of the influence of the local nutrient dynamics of the system of interest on bacteria-metal interactions is limited. Here we present data demonstrating the effectiveness of coupling laboratory experiments with geochemical modeling to isolate the effect of nutrient availability on bacterially mediated proton and metal adsorption reactions. Experimental studies of metal-bacteria interactions were conducted in batch reactors as a function of pH, and solid-solute interactions after growth in a variety of defined and undefined media. Media nutrient composition (C,N,P) was quantified before and after harvesting the cells. Surface complexation models (SCM) for the adsorption reactions were developed by combining sorption data with the results of acid-base titrations, and in some cases zeta potential titrations of the bacterial surface. Our results indicate a clear change in both buffering potential and metal binding capacity of the cell walls of Bacillus subtilis as a function of initial media conditions. Combining current studies with our past studies on the effects of growth phase and others work on temperature dependence on metal adsorption we hope to develop a holistic surface complexation model for quantifying bacterial effects on metal mass transfer in many geologic systems.

  15. Neurophysiological evidence of an association between cognitive control and defensive reactivity processes in young children.

    Science.gov (United States)

    Lo, Sharon L; Schroder, Hans S; Moran, Tim P; Durbin, C Emily; Moser, Jason S

    2015-10-01

    Interactions between cognitive control and affective processes, such as defensive reactivity, are intimately involved in healthy and unhealthy human development. However, cognitive control and defensive reactivity processes are often studied in isolation and rarely examined in early childhood. To address these gaps, we examined the relationships between multiple neurophysiological measures of cognitive control and defensive reactivity in young children. Specifically, we assessed two event-related potentials thought to index cognitive control processes--the error-related negativity (ERN) and error positivity (Pe)--measured across two tasks, and two markers of defensive reactivity processes--startle reflex and resting parietal asymmetry--in a sample of 3- to 7-year old children. Results revealed that measures of cognitive control and defensive reactivity were related such that evidence of poor cognitive control (smaller ERN) was associated with high defensive reactivity (larger startle and greater right relative to left parietal activity). The strength of associations between the ERN and measures of defensive reactivity did not vary by age, providing evidence that poor cognitive control relates to greater defensive reactivity across early childhood years. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

  16. Alterations of TH1/TH2 reactivity by heavy metals: possible consequences include induction of autoimmune diseases.

    Science.gov (United States)

    Hemdan, Nasr Y A; Emmrich, Frank; Faber, Sonya; Lehmann, Joerg; Sack, Ulrich

    2007-08-01

    Heavy metal pollution still represents a primary concern regarding human health. Recently, it become evident that the contribution of heavy metals extends far beyond their accepted role in allergic diseases, and that they may play a more extensive role in a variety of other diseases. Several lines of evidence indicate that heavy metals have a key role in the induction or exacerbation of several autoimmune diseases (AD). Moreover, the association between exposure to heavy metals and the signs of autoimmunity are supported by some studies. The mechanisms by which heavy metals induce the development of AD are not yet fully understood. Our objective here is to highlight the association of exposure to some heavy metals and AD. In addition, we present recent results showing the possible alterations in Th1/Th2 reactivity by some heavy metals, which may constitute the trigger for the incidence of autoimmunity in susceptible individuals.

  17. The Modeling and Simulation of Reactive Distillation for the Esterification Process

    Institute of Scientific and Technical Information of China (English)

    朱建华; 沈复

    2003-01-01

    In this paper,a generalized model of the reactive distillation processes was developed via rate-based approach. The homotopy-continuation method was employed to solve the complicated nonlinear model equations efficiently. The simulation on the reactive distillation processes was carried out with the profiles of stage temperature,composition and flow rate for both vapor and liquid phases obtained. Based on careful analysis of the simulation results, the pitfalls in experimental design were detected. Finally, a software package for the simulation of reactive distillation processes was developed.

  18. Does cardiovascular reactivity during speech reflect self-construction processes?

    Science.gov (United States)

    Lyons, A C; Spicer, J; Tuffin, K; Chamberlain, K

    2000-11-01

    Abstract Substantial empirical research has been undertaken on cardiovascular reactivity (CVR). however interpretation of this research is hampered by a lack of theoretical frameworks. This paper develops a framework initially stimulated by evidence demonstrating that the cardiovascular system increases in activity during communication, and that the extent of this activation depends upon numerous and diverse psychosocial factors. We attempt to account for this phenomenon using merit post-structuralist ideas concerning the constructive nature of language and its centrality to an individual's sense of self. Our theoretical framework proposes that the CVR exhibited during language use is explicable in terms of self-construction - From this analysis we hypothesised that CVR would differ across conversations about private self. public self and non-self topics, and that these differences would depend upon people's speaking histories. We found that the blood pressure and heart rate of 102 women was most reactive when they talked in a laboratory with a stranger about aspects of their private self, and least reactive during non-self talk, whilst their heart rate was most reactive during talk about their public self. Overall the results highlight the inextricable link between our inherent socialness and our cardiovascular systems. SUMMARY The explanatory scheme outlined here is an attempt to provide a social reconceptualisation of a phenomenon that is typically interpreted in individualistic psychophysiological terms, and which is consistent with the notion that repeated exposure to situations which provoke large haemodynamic changes may lead to CHD disease progression. The explanation draws heavily on post-structuralist ideas regarding language, and the social constructionist notion that engaging in language use is central to constructing and maintaining a sense of self. This sense of self is a central theoretical entity in our everyday lives, produced and maintained in our

  19. Process to separate alkali metal salts from alkali metal reacted hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard; Alvare, Javier; Larsen, Dennis; Killpack, Jeff

    2017-06-27

    A process to facilitate gravimetric separation of alkali metal salts, such as alkali metal sulfides and polysulfides, from alkali metal reacted hydrocarbons. The disclosed process is part of a method of upgrading a hydrocarbon feedstock by removing heteroatoms and/or one or more heavy metals from the hydrocarbon feedstock composition. This method reacts the oil feedstock with an alkali metal and an upgradant hydrocarbon. The alkali metal reacts with a portion of the heteroatoms and/or one or more heavy metals to form an inorganic phase containing alkali metal salts and reduced heavy metals, and an upgraded hydrocarbon feedstock. The inorganic phase may be gravimetrically separated from the upgraded hydrocarbon feedstock after mixing at a temperature between about 350.degree. C. to 400.degree. C. for a time period between about 15 minutes and 2 hours.

  20. Simulation on flow process of filtered molten metals

    Institute of Scientific and Technical Information of China (English)

    房文斌; 耿耀宏; 魏尊杰; 安阁英; 叶荣茂

    2002-01-01

    Filtration and flow process of molten metals was analyzed by water simulation experiments. Fluid dynamic phenomena of molten metal cells through a foam ceramic filter was described and calculated by ERGOR equation as well. The results show that the filter is most useful for stable molten metals and the filtered flow is laminar, so that inclusions can be removed more effectively.

  1. Molecular weight and chemical reactivity of dissolved trace metals (Cd, Cu, Ni) in surface waters from the Mississippi River to Gulf of Mexico

    Science.gov (United States)

    Wen, Liang-Saw; Santschi, Peter H.; Warnken, Kent W.; Davison, William; Zhang, Hao; Li, Hsiu-Ping; Jiann, Kuo-Tung

    2011-05-01

    It is generally assumed that estuarine mixing is continuous for metals from terrestrial sources, gradually decreasing towards the open ocean endmember. Here we show that, chemical reactivity, determined by ion exchange method, and molecular weight distributions, obtained using cross-flow ultrafiltration, of dissolved Cd, Cu, and Ni in the surface waters of the Gulf of Mexico varied systematically across the estuarine mixing zone of the Mississippi River. Most size or chemical affinity fractions of dissolved metals (warm core ring in the Gulf of Mexico. Dissolved Cd was mostly present as a truly dissolved (behavior between Cu and the other two metals might indicate differences in the biopolymeric nature of the metal-organic chelates. In particular, the anionic-organic Cd fractions accounted for just 3 ± 1%, on average. However, for Cu, it was 24 ± 4%, and for Ni, it was 9 ± 6%. The fractions of the total dissolved metal fractions that were "inert" averaged 31 ± 10% for Cu and 29 ± 12% for Ni. Small but noticeable amounts (6 ± 3%) of dissolved inert Cd fractions were also present. Apparent non-local transport processes, likely associated with cross-shelf sediment resuspension processes, could have been responsible for the relatively high concentrations of 'inert' and 'anionic' metal fractions in high salinity coastal waters, and accounting for the persistence of metals bound to humic substances in the Gulf of Mexico.

  2. Quantum and classical dynamics of reactive scattering of H2 from metal surfaces.

    Science.gov (United States)

    Kroes, Geert-Jan; Díaz, Cristina

    2016-06-27

    We review the state-of-the art in dynamics calculations on the reactive scattering of H2 from metal surfaces, which is an important model system of an elementary reaction that is relevant to heterogeneous catalysis. In many applications, quantum dynamics and classical trajectory calculations are performed within the Born-Oppenheimer static surface model. However, ab initio molecular dynamics (AIMD) is finding increased use in applications aimed at modeling the effect of surface phonons on the dynamics. Molecular dynamics with electronic friction has been used to model the effect of electron-hole pair excitation. Most applications are still based on potential energy surfaces (PESs) or forces computed with density functional theory (DFT), using a density functional within the generalized gradient approximation to the exchange-correlation energy. A new development is the use of a semi-empirical version of DFT (the specific reaction parameter (SRP) approach to DFT). We also discuss the accurate methods that have become available to represent electronic structure data for the molecule-surface interaction in global PESs. It has now become possible to describe highly activated H2 + metal surface reactions with chemical accuracy using the SRP-DFT approach, as has been shown for H2 + Cu(111) and Cu(100). However, chemical accuracy with SRP-DFT has yet to be demonstrated for weakly activated systems like H2 + Ru(0001) and non-activated systems like H2 + Pd(111), for which SRP DFs are not yet available. There is now considerable evidence that electron-hole pair (ehp) excitation does not need to be modeled to achieve the (chemically) accurate calculation of dissociative chemisorption and scattering probabilities. Dynamics calculations show that phonons can be safely neglected in the chemically accurate calculation of sticking probabilities on cold metal surfaces for activated systems, and in the calculation of a number of other observables. However, there is now sufficient

  3. Ozonation of reactive dye, Procion red MX-5B catalyzed by metal ions.

    Science.gov (United States)

    Pachhade, K; Sandhya, S; Swaminathan, K

    2009-08-15

    Ozonation of aqueous solution of Procion red MX-5B, a commercial azo reactive dye was investigated. The effect of various experimental variables on decolorization and degradation of the dye has been studied. Color removal was faster than organic removal. Dye mineralization was evident by the generation of sulphate, chloride, nitrate, oxalic and acetic acid during ozonation. The decolorization and organic removal followed pseudo-first-order kinetics. Among the metal ions studied, manganese catalyzed ozonation showed better decolorization and organic removal. Fourier transform infrared (FTIR) spectroscopy results indicated the disappearance of bands for aromatics and appearance of bands due to carboxylic acids in the ozonated samples. Acetyl benzoic acid, diethyl phthalate and phthalic anhydride were identified as intermediates by gas chromatography mass spectra (GC/MS). Based on these findings a tentative pathway for the degradation MX-5B was postulated.

  4. Fundamental study of an industrial reactive HPPMS (Cr,Al)N process

    Science.gov (United States)

    Bobzin, K.; Brögelmann, T.; Kruppe, N. C.; Engels, M.; von Keudell, A.; Hecimovic, A.; Ludwig, A.; Grochla, D.; Banko, L.

    2017-07-01

    In this work, a fundamental investigation of an industrial (Cr,Al)N reactive high power pulsed magnetron sputtering (HPPMS) process is presented. The results will be used to improve the coating development for the addressed application, which is the tool coating for plastics processing industry. Substrate-oriented plasma diagnostics and deposition of the (Cr,Al)N coatings were performed for a variation of the HPPMS pulse frequency with values from f = 300 Hz to f = 2000 Hz at constant average power P = 2.5 kW and pulse length ton = 40 μs. The plasma was investigated using an oscilloscope, an intensified charge coupled device camera, phase-resolved optical emission spectroscopy, and an energy-dispersive mass spectrometer. The coating properties were determined by means of scanning electron microscopy, glow discharge optical emission spectroscopy, cantilever stress sensors, nanoindentation, and synchrotron X-ray diffraction. Regarding the plasma properties, it was found that the average energy within the plasma is nearly constant for the frequency variation. In contrast, the metal to gas ion flux ratio is changed from JM/JG = 0.51 to JM/JG = 0.10 for increasing frequency. Regarding the coating properties, a structure refinement as well as lower residual stresses, higher universal hardness, and a changing crystal orientation from (111) to (200) were observed at higher frequencies. By correlating the plasma and coating properties, it can be concluded that the change in the gas ion to metal ion flux ratio results in a competitive crystal growth of the film, which results in changing coating properties.

  5. Sequential biphotonic processes: photochemical reactivity of phthalocyanine radicals

    Energy Technology Data Exchange (ETDEWEB)

    Van Vlierberge, B.; Ferraudi, G.

    1987-01-28

    Results of a study of the photochemistry of Rh(III), Al(III), and Zn(II) phthalocyanine cation radicals are reported here. The radicals were generated in a flash photolysis apparatus, which employs two flash-lamp-pump dye lasers. This excitation of the metallophthalocyanines at wavelengths of the phthalocyanine's Q band produced the long-lived triplet state. Irradiation of the phthalocyanine radicals led to rapid (t less than 1 ..mu..s) decomposition of these species followed by a partial recovery of the radical concentration. The dependence of radical yield on medium conditions was noted, and this dependence was probably attributable to an increase in the yield of the reactive excited state and/or a decrease in the rate of excited-state relaxation in changing from protic to aprotic media or replacing D/sub 2/O by H/sub 2/O. 10 references, 3 figures, 2 tables.

  6. Numerical Controlled Rolling Process of Thick Metal Plate

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Thick metal plate rolling process has become more and more important in building a flat roof of drilling on the bottom at sea. This is because not only the product quality requirement higher and higher but also the marketing competition. To improve the process of thick metal plate rolling and to increase productivity a numerical controlled rolling process is developed, which include the process planning, the mathematical model establishment and the numerical control system development. The process is for ...

  7. Process for simultaneously processing of used metal and/or metal scrap and scrap containing halogenated hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Dapper, G.; Kirchner, W.; Sloterdijk, W.; Verbraak, C.A.

    1982-03-02

    A process is presened for reducing environmental pollution resulting from disposal of waste containing halogenated hydrocarbons by simultaneous treatment with used metal and/or metal scrap at elevated temperatures. The halogenated hydrocarbons are pyrolyzed and the resulting hydrogen halide containing gas is brought into contact with the used metal and/or metal scrap at elevated temperatures so as to form metal halogenides that are volatile under the conditions applied. The volatile metal halogenides are largely separated from the gaseous mixture formed, and at least part of the remaining gaseous mixture and/or hydrocarbon residue is used as fuel to maintain the required temperature. The waste feed compositions and process conditions can be chosen to effect separation between various metals by selective halogenation and condensation, and substantially all of the hydrogen halide can be tied up and recovered as metal halogenides.

  8. Co-gasification of tire and biomass for enhancement of tire-char reactivity in CO2 gasification process.

    Science.gov (United States)

    Lahijani, Pooya; Zainal, Zainal Alimuddin; Mohamed, Abdul Rahman; Mohammadi, Maedeh

    2013-06-01

    In this investigation, palm empty fruit bunch (EFB) and almond shell (AS) were implemented as two natural catalysts rich in alkali metals, especially potassium, to enhance the reactivity of tire-char through co-gasification process. Co-gasification experiments were conducted at several blending ratios using isothermal Thermogravimetric analysis (TGA) under CO2. The pronounced effect of inherent alkali content of biomass-chars on promoting the reactivity of tire-char was proven when acid-treated biomass-chars did not exert any catalytic effect on improving the reactivity of tire-char in co-gasification experiments. In kinetic studies of the co-gasified samples in chemically-controlled regime, modified random pore model (M-RPM) was adopted to describe the reactive behavior of the tire-char/biomass-char blends. By virtue of the catalytic effect of biomass, the activation energy for tire-char gasification was lowered from 250 kJ/mol in pure form 203 to 187 kJ/mol for AS-char and EFB-char co-gasified samples, respectively.

  9. A reactive distillation process for the treatment of LiCl-KCl eutectic waste salt containing rare earth chlorides

    Science.gov (United States)

    Eun, H. C.; Choi, J. H.; Kim, N. Y.; Lee, T. K.; Han, S. Y.; Lee, K. R.; Park, H. S.; Ahn, D. H.

    2016-11-01

    The pyrochemical process, which recovers useful resources (U/TRU metals) from used nuclear fuel using an electrochemical method, generates LiCl-KCl eutectic waste salt containing radioactive rare earth chlorides (RECl3). It is necessary to develop a simple process for the treatment of LiCl-KCl eutectic waste salt in a hot-cell facility. For this reason, a reactive distillation process using a chemical agent was achieved as a method to separate rare earths from the LiCl-KCl waste salt. Before conducting the reactive distillation, thermodynamic equilibrium behaviors of the reactions between rare earth (Nd, La, Ce, Pr) chlorides and the chemical agent (K2CO3) were predicted using software. The addition of the chemical agent was determined to separate the rare earth chlorides into an oxide form using these equilibrium results. In the reactive distillation test, the rare earth chlorides in LiCl-KCl eutectic salt were decontaminated at a decontamination factor (DF) of more than 5000, and were mainly converted into oxide (Nd2O3, CeO2, La2O3, Pr2O3) or oxychloride (LaOCl, PrOCl) forms. The LiCl-KCl was purified into a form with a very low concentration (<1 ppm) for the rare earth chlorides.

  10. Studies in reactive extrusion processing of biodegradable polymeric materials

    Science.gov (United States)

    Balakrishnan, Sunder

    Various reaction chemistries such as Polymerization, Polymer cross-linking and Reactive grafting were investigated in twin-screw extruders. Poly (1,4-dioxan-2-one) (PPDX) was manufactured in melt by the continuous polymerization of 1,4-dioxan-2-one (PDX) monomer in a twin-screw extruder using Aluminum tri-sec butoxide (ATSB) initiator. Good and accurate control over molecular weight was obtained by controlling the ratio of monomer to initiator. A screw configuration consisting of only conveying elements was used for the polymerization. The polymerization reaction was characterized by a monomer-polymer dynamic equilibrium, above the melting temperature of the polymer, limiting the equilibrium conversion to 78-percent. Near complete (˜100-percent) conversion was obtained on co-polymerizing PDX monomer with a few mol-percent (around 8-percent) Caprolactone (CL) monomer in a twin-screw extruder using ATSB initiator. The co-polymers exhibited improved thermal stability with reduction in glass transition temperature. The extruder was modeled as an Axial Dispersed Plug Flow Reactor for the polymerization of CL monomer using Residence Time Distribution (RTD) Analysis. The model provided a good fit to the experimental RTD and conversion data. Aliphatic and aliphatic-aromatic co-polyesters, namely Polycaprolactone (PCL) and Poly butylenes (adipate-co-terephthalate) (Ecoflex) were cross-linked in a twin-screw extruder using radical initiator to form micro-gel reinforced biodegradable polyesters. Cross-linked Ecoflex was further extrusion blended with talc to form blends suitable to be blown into films. A screw configuration consisting of conveying and kneading elements was found to be effective in dispersion of the talc particles (5--10 microns) in the polyester matrix. While the rates of crystallization increased for the talc filled polyester blends, overall crystallinity reduced. Mechanical, tear and puncture properties of films made using the talc filled polyester blends

  11. Evaluation of single and multilayered reactive zones for heavy metals removal from stormwater.

    Science.gov (United States)

    Pawluk, Katarzyna; Fronczyk, Joanna

    2015-01-01

    In this paper, the ability of granular activated carbon (GAC), silica spongolite (SS) and zeolite (Z) to remove heavy metals from aqueous solutions has been investigated through column tests. The breakthrough times for a mobile tracer that does not sorb to the material for SS, GAC and layered SS, Z and GAC were as follows: 2.54×10(4) s, 2.38×10(4) s and 3.02×10(4) s. The breakthrough time (tbR) for Ni was in the range from tbR=1.70×10(6) s for SS, through tbR=3.98×10(5) s for the layered bed, to tbR=8.75×10(5) s for GAC. The breakthrough time for Cd was in the range from tbR=1.83×10(5) s for GAC to tbR=1.30×10(6) s for SS, Z, GAC. During the experiment, the concentration of Cd, Cu, Pb and Zn in the solution from a column filled with construction aggregate and the concentration of Pb, and Cu in a filtrate from the column filled with several materials was close to zero. The reduction in metal ions removal was due to high pH values of the solution (above 8.00). In addition, during the testing period, an increase in Cd and Zn concentrations in the filtrate from the column filled with the layered bed was observed, but at the end of the experiment the concentrations did not reach the maximum values. The test results suggest that the multilayered permeable reactive barrier is the most effective technology for long time effective removal of heavy metals.

  12. The existence of a double S-shaped process curve during reactive magnetron sputtering

    Science.gov (United States)

    Schelfhout, R.; Strijckmans, K.; Depla, D.

    2016-09-01

    The four dimensional parameter space (discharge voltage and current and reactive gas flow and pressure) related to a reactive Ar/O2 DC magnetron discharge with an aluminum target and constant pumping speed was acquired by measuring current-voltage characteristics at different oxygen flows. The projection onto the pressure-flow plane allows us to study the well-known S-shaped process curve. This experimental procedure guarantees no time dependent effects on the result. The obtained process curve appears not to be unique but rather two significantly different S-shaped curves are noticed which depend on the history of the steady state target condition. As such, this result has not only an important impact on the fundamental description of the reactive sputtering process but it can also have its consequences on typical feedback control systems for the operation in the transition regime of the hysteresis during reactive magnetron sputtering.

  13. Metal-ligand binding affinity vs reactivity: qualitative studies in Rh(I)-catalyzed asymmetric ring-opening reactions.

    Science.gov (United States)

    Tsui, Gavin Chit; Dougan, Patrick; Lautens, Mark

    2013-06-01

    Rh(I)-catalyzed asymmetric ring opening (ARO) of oxabenzonorbornadiene is used as a model system to qualitatively study reactions involving multiple metal-ligand interactions. The key feature of this approach is the use of product ee as an indicator to quickly gain important information such as the relative ligand binding affinity and relative reactivity of catalysts.

  14. Trace metal pyritization variability in response to mangrove soil aerobic and anaerobic oxidation processes.

    Science.gov (United States)

    Machado, W; Borrelli, N L; Ferreira, T O; Marques, A G B; Osterrieth, M; Guizan, C

    2014-02-15

    The degree of iron pyritization (DOP) and degree of trace metal pyritization (DTMP) were evaluated in mangrove soil profiles from an estuarine area located in Rio de Janeiro (SE Brazil). The soil pH was negatively correlated with redox potential (Eh) and positively correlated with DOP and DTMP of some elements (Mn, Cu and Pb), suggesting that pyrite oxidation generated acidity and can affect the importance of pyrite as a trace metal-binding phase, mainly in response to spatial variability in tidal flooding. Besides these aerobic oxidation effects, results from a sequential extraction analyses of reactive phases evidenced that Mn oxidized phase consumption in reaction with pyrite can be also important to determine the pyritization of trace elements. Cumulative effects of these aerobic and anaerobic oxidation processes were evidenced as factors affecting the capacity of mangrove soils to act as a sink for trace metals through pyritization processes.

  15. Understanding metallic bonding: Structure, process and interaction by Rasch analysis

    Science.gov (United States)

    Cheng, Maurice M. W.; Oon, Pey-Tee

    2016-08-01

    This paper reports the results of a survey of 3006 Year 10-12 students on their understandings of metallic bonding. The instrument was developed based on Chi's ontological categories of scientific concepts and students' understanding of metallic bonding as reported in the literature. The instrument has two parts. Part one probed into students' understanding of metallic bonding as (a) a submicro structure of metals, (b) a process in which individual metal atoms lose their outermost shell electrons to form a 'sea of electrons' and octet metal cations or (c) an all-directional electrostatic force between delocalized electrons and metal cations, that is, an interaction. Part two assessed students' explanation of malleability of metals, for example (a) as a submicro structural rearrangement of metal atoms/cations or (b) based on all-directional electrostatic force. The instrument was validated by the Rasch Model. Psychometric assessment showed that the instrument possessed reasonably good properties of measurement. Results revealed that it was reliable and valid for measuring students' understanding of metallic bonding. Analysis revealed that the structure, process and interaction understandings were unidimensional and in an increasing order of difficulty. Implications for the teaching of metallic bonding, particular through the use of diagrams, critiques and model-based learning, are discussed.

  16. Planning of Sheet Metal Drawing Processes Based on Information Strategies

    Directory of Open Access Journals (Sweden)

    José Roberto Marty Delgado

    2011-10-01

    Full Text Available Sheet metal forming processes represent an important group of manufacturing processes for dissimilar applications. The development of numerical simulation methods has created new possibilities in important industrial aspects with regard to optimization and integration CAPP system in sheet metal drawing processes. The result of the processes depends on a large number of parameters and their interdependence hence, knowledge and experience of the designer are critical. The present work deals with the elements to be considered in the integral design, planning and optimization sheet metal drawing processes under a set of criteria and as such the possibilities that this task offers in the decision making, preparation along with the analysis and synthesis of engineering systems. In addition a methodology for integration design and process planning of sheet metal forming process analysis is summarized.

  17. Improving the relationship between soil characteristics and metal bioavailability by using reactive fractions of soil parameters in calcareous soils.

    Science.gov (United States)

    de Santiago-Martín, Ana; van Oort, Folkert; González, Concepción; Quintana, José R; Lafuente, Antonio L; Lamy, Isabelle

    2015-01-01

    The contribution of the nature instead of the total content of soil parameters relevant to metal bioavailability in lettuce was tested using a series of low-polluted Mediterranean agricultural calcareous soils offering natural gradients in the content and composition of carbonate, organic, and oxide fractions. Two datasets were compared by canonical ordination based on redundancy analysis: total concentrations (TC dataset) of main soil parameters (constituents, phases, or elements) involved in metal retention and bioavailability; and chemically defined reactive fractions of these parameters (RF dataset). The metal bioavailability patterns were satisfactorily explained only when the RF dataset was used, and the results showed that the proportion of crystalline Fe oxides, dissolved organic C, diethylene-triamine-pentaacetic acid (DTPA)-extractable Cu and Zn, and a labile organic pool accounted for 76% of the variance. In addition, 2 multipollution scenarios by metal spiking were tested that showed better relationships with the RF dataset than with the TC dataset (up to 17% more) and new reactive fractions involved. For Mediterranean calcareous soils, the use of reactive pools of soil parameters rather than their total contents improved the relationships between soil constituents and metal bioavailability. Such pool determinations should be systematically included in studies dealing with bioavailability or risk assessment.

  18. Reactive-Separator Process Unit for Lunar Regolith Project

    Data.gov (United States)

    National Aeronautics and Space Administration — NASA's plans for a lunar habitation outpost call out for process technologies to separate hydrogen sulfide and sulfur dioxide gases from regolith product gas...

  19. Thermochemistry and Dynamics of Reactive Species: Nitrogen-rich Compounds, Metals and SiC Clusters in Free and Solvated Environment

    Science.gov (United States)

    2005-10-31

    of Reactive Species : Nitrogen-rich F49620-02-1-0371 Compounds, Metals and SiC clusters in Free and Solvated Environments Sb. GRANT NUMBER 5c. PROGRAM...F49620-02-1-0371 Thermochemistry and Dynamics of Reactive Species : Nitrogen-rich Compounds, Metals, and SiC clusters in Free and Solvated Environments...research program remain the same as before: obtaining fundamental thermochemical and dynamical data on reactive species Status of Effort This report

  20. Chemical reactivity evaluation: The CCPS program. [CCPS (Center for Chemical Process Safety)

    Energy Technology Data Exchange (ETDEWEB)

    West, A.S. (American Institute of Chemical Engineers, New York, NY (United States))

    1993-01-01

    A summary is presented of the chemical reactivity evaluation aspects of the soon to be published [open quotes]Guidelines for Chemical Reactivity Evaluation and Application to Process Design[close quotes] developed under the sponsorship of the Center for Chemical Process Safety. Emphasis is placed on strategies for thermochemical evaluation of industrial chemical substances. Certain structural entities, for example, high degrees of unsaturation and nitrogen-halogen linkages, will likely identify hazardous reactive chemicals. The effects of impurities in the chemicals, as well as, for example, incidental contact with water and air (oxygen), must also be considered in the evaluation of potential reactivity hazards, representing undesired reactions. Various test methods are indicated briefly along with the rationale for use of specific methods in hazard evaluation. 30 refs., 1 fig., 9 tabs.

  1. In vitro reactivity to implant metals demonstrates a person-dependent association with both T-cell and B-cell activation.

    Science.gov (United States)

    Hallab, Nadim James; Caicedo, Marco; Epstein, Rachel; McAllister, Kyron; Jacobs, Joshua J

    2010-02-01

    Hypersensitivity to metallic implants remains relatively unpredictable and poorly understood. We initially hypothesized that metal-induced lymphocyte proliferation responses to soluble metal challenge (ions) are mediated exclusively by early T-cell activation (not B-cells), typical of a delayed-type-hypersensitivity response. We tested this by comparing proliferation (6 days) of primary lymphocytes with early T-cell and B-cell activation (48 h) in three groups of subjects likely to demonstrate elevated metal reactivity: group 1 (n = 12) history of metal sensitivity with no implant; group 2a (n = 6) well performing metal-on-metal THRs, and group 2b (n = 20) subjects with poorly performing metal-on-polymer total joint arthroplasties (TJA). Group 1 showed 100% (12/12) metal reactivity (stimulation index > 2) to Ni. Groups 2a and 2b were 83% (5/6) and 75% (15/22) metal reactive (to Co, Cr, or Ni), respectively. Of the n = 32 metal-reactive subjects to Co, Cr, or Ni (SI > 2), n = 22/32 demonstrated >2-fold elevations in % of T-cell or B-cell activation (CD25+, CD69+) to metal challenge when compared with untreated control. 18/22 metal-activated subjects demonstrated an exclusively T-cell or B-cell activation response to metal challenge, where 6/18 demonstrated exclusively B-cell activation and 12/18 demonstrated a T-cell only response, as measured by surface activation markers CD25+ and CD69+. However, there was no direct correlation (R(2) metal reactivity than did subject-dependent results of flow-cytometry analysis of T-cell or B-cell activation. The high incidence of lymphocyte reactivity and activation indicate that more complex than initially hypothesized immune responses may contribute to the etiology of debris-induced osteolysis in metal-sensitive individuals.

  2. Nuclear fuel materials processing in reactive gas plasma

    Energy Technology Data Exchange (ETDEWEB)

    Min, Jin Young; Yang, Myung Seung; Seo, Yong Dae; Kim Yong Soo [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    2000-07-01

    DUPIC fuel cycle development project in KAERI of Korea was initiated in 1991 and has advanced in relevant technologies for last 10 years. The project includes five different topics such as nuclear fuel manufacturing, compatibility evaluation, performance evaluation, manufacturing facility management, and safeguards. The contents and results of DUPIC R and D up to now are as follow: - the basic foundation was established for the critically required pelletizing technology and powder treatment technology for DUPIC. - development of DUPIC process line and deployment of 20 each process equipment and examination instruments in DFDF. - powder and pellet characterization study was done at PIEF based on the simfuel study results, and 30 DUPIC pellets were successfully produced. - the manufactured pellets were used for sample fuel rods irradiated in July,2000 in HANARO research reactor in KAERI and have been under post irradiation examination. (Hong, J. S.)

  3. Changes in attentional processing and affective reactivity in pregnancy and postpartum

    Directory of Open Access Journals (Sweden)

    Gollan JK

    2014-11-01

    Full Text Available Jackie K Gollan, Laina Rosebrock, Denada Hoxha, Katherine L Wisner Asher Center for the Study and Treatment of Depressive Disorders, Department of Psychiatry and Behavioral Sciences, Northwestern University Feinberg School of Medicine, Chicago, IL, USA Abstract: The aim of this review is to provide an overview of the research in attentional processing and affective reactivity in pregnancy and postpartum to inform future research. Numerous changes occur in attentional processing and affective reactivity across the childbearing period. This review focuses on the definition and methods of measuring attentional processing and affective reactivity. We discuss research studies that have examined the changes in these two processes during the perinatal phases of pregnancy and postpartum, with and without depression and anxiety. We evaluate the importance of using multiple levels of measurement, including physiological and neuroimaging techniques, to study these processes via implicit and explicit tasks. Research that has identified regions of brain activation using functional magnetic resonance imaging as well as other physiological assessments is integrated into the discussion. The importance of using sophisticated methodological techniques in future studies, such as multiple mediation models, for the purpose of elucidating mechanisms of change during these processes in pregnancy and postpartum is emphasized. We conclude with a discussion of the effect of these processes on maternal psychological functioning and infant outcomes. These processes support a strategy for individualizing treatment for pregnant and postpartum women suffering from depression and anxiety. Keywords: attentional processing, emotion, affective reactivity, depression, pregnancy, postpartum

  4. Mechanical Properties, Purifying Techniques and Processing Methods of Metal Yttrium

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The mechanical properties of metal yttrium such as strength, plasticity, hardness and elasticity were introduced. The purifying techniques of yttrium were discussed in detail. The processing methods for metal yttrium including extruding, forging, rolling, wiredrawing and welding were also introduced. Finally, the potential use of yttrium and its alloys were prospected.

  5. Non-noble metal based catalysts for aqueous phase processing

    NARCIS (Netherlands)

    van Haasterecht, T.

    2015-01-01

    This thesis concerns the evaluation of the potential of supported non-noble metal catalysts in aqueous phase processes for the production hydrogen and oxygenates. The aim of this thesis is to investigate how different factors, especially the nature of the metal, additives and reaction conditions, de

  6. Non-noble metal based catalysts for aqueous phase processing

    NARCIS (Netherlands)

    van Haasterecht, T.

    2015-01-01

    This thesis concerns the evaluation of the potential of supported non-noble metal catalysts in aqueous phase processes for the production hydrogen and oxygenates. The aim of this thesis is to investigate how different factors, especially the nature of the metal, additives and reaction conditions,

  7. A metamodel based optimisation algorithm for metal forming processes

    NARCIS (Netherlands)

    Bonte, M.H.A.; Boogaard, van den A.H.; Huetink, J.; Banabic, Dorel

    2007-01-01

    Cost saving and product improvement have always been important goals in the metal forming industry. To achieve these goals, metal forming processes need to be optimised. During the last decades, simulation software based on the Finite Element Method (FEM) has significantly contributed to designing f

  8. Fabrication of metal suspending nanostructures by nanoimprint lithography (NIL) and isotropic reactive ion. etching (RIE)

    Institute of Scientific and Technical Information of China (English)

    XIE GuoYong; ZHANG Jin; ZHANG YongYi; ZHANG YingYing; ZHU Tao; LIU ZhongFan

    2009-01-01

    We report herein e rational approach for fabricating metal suspending nanostructures by nanoimprint lithography (NIL) and isotropic reactive ion etching (RIE). The approach comprises three principal steps:(1) mold fabrication, (2) structure replication by NIL, and (3) suspending nanostructures creation by isotropic RIE. Using this approach, suspending nanostructures with Au, Au/Ti or Ti/Au bilayers, and Au/TilAu sandwiched structures are demonstrated. For Au nanostructures, straight suspending nanostructurea can be obtained when the thickness of Au film is up to 50 nm for nano-bridge and 90 nm for nano-finger patterns. When the thickness of Au is below 50 nm for nano-bridge and 90 nm for nano-finger, the Au suspending nanostructures bend upward as a result of the mismatch of thermal expansion between the thin Au films and Si substrate. This leads to residual stresses in the thin Au films. For Au/Ti or Ti/Au bilayers nanostructures, the cantilevers bend toward Au film, since Au has a larger thermal expansion coefficient than that of Ti. While in the case of sandwich structures, straight suspending nanostructures are obtained, this may be due to the balance of residual stress between the thin films.

  9. A Mechanistic Reliability Assessment of RVACS and Metal Fuel Inherent Reactivity Feedbacks

    Energy Technology Data Exchange (ETDEWEB)

    Grabaskas, David; Brunett, Acacia J.; Passerini, Stefano; Grelle, Austin

    2017-09-24

    GE Hitachi Nuclear Energy (GEH) and Argonne National Laboratory (Argonne) participated in a two year collaboration to modernize and update the probabilistic risk assessment (PRA) for the PRISM sodium fast reactor. At a high level, the primary outcome of the project was the development of a next-generation PRA that is intended to enable risk-informed prioritization of safety- and reliability-focused research and development. A central Argonne task during this project was a reliability assessment of passive safety systems, which included the Reactor Vessel Auxiliary Cooling System (RVACS) and the inherent reactivity feedbacks of the metal fuel core. Both systems were examined utilizing a methodology derived from the Reliability Method for Passive Safety Functions (RMPS), with an emphasis on developing success criteria based on mechanistic system modeling while also maintaining consistency with the Fuel Damage Categories (FDCs) of the mechanistic source term assessment. This paper provides an overview of the reliability analyses of both systems, including highlights of the FMEAs, the construction of best-estimate models, uncertain parameter screening and propagation, and the quantification of system failure probability. In particular, special focus is given to the methodologies to perform the analysis of uncertainty propagation and the determination of the likelihood of violating FDC limits. Additionally, important lessons learned are also reviewed, such as optimal sampling methodologies for the discovery of low likelihood failure events and strategies for the combined treatment of aleatory and epistemic uncertainties.

  10. Novel process integration for biodiesel blend in membrane reactive divided wall (MRDW column

    Directory of Open Access Journals (Sweden)

    Sakhre Vandana

    2016-03-01

    Full Text Available The paper proposes a novel process integration for biodiesel blend in the Membrane assisted Reactive Divided Wall Distillation (MRDW column. Biodiesel is a green fuel and grade of biodiesel blend is B20 (% which consist of 20% biodiesel and rest 80% commercial diesel. Instead of commercial diesel, Tertiary Amyl Ethyl Ether (TAEE was used as an environment friendly fuel for blending biodiesel. Biodiesel and TAEE were synthesized in a pilot scale reactive distillation column. Dual reactive distillation and MRDW were simulated using aspen plus. B20 (% limit calculation was performed using feed flow rates of both TAEE and biodiesel. MRDW was compared with dual reactive distillation column and it was observed that MRDW is comparatively cost effective and suitable in terms of improved heat integration and flow pattern.

  11. Development of Modeling Methods and Tools for Predicting Coupled Reactive Transport Processes in Porous Media at Multiple Scales

    Energy Technology Data Exchange (ETDEWEB)

    Clement, T Prabhakar; Barnett, Mark O; Zheng, Chunmiao; Jones, Norman L

    2010-05-05

    DE-FG02-06ER64213: Development of Modeling Methods and Tools for Predicting Coupled Reactive Transport Processes in Porous Media at Multiple Scales Investigators: T. Prabhakar Clement (PD/PI) and Mark O. Barnett (Auburn), Chunmiao Zheng (Univ. of Alabama), and Norman L. Jones (BYU). The objective of this project was to develop scalable modeling approaches for predicting the reactive transport of metal contaminants. We studied two contaminants, a radioactive cation [U(VI)] and a metal(loid) oxyanion system [As(III/V)], and investigated their interactions with two types of subsurface materials, iron and manganese oxyhydroxides. We also developed modeling methods for describing the experimental results. Overall, the project supported 25 researchers at three universities. Produced 15 journal articles, 3 book chapters, 6 PhD dissertations and 6 MS theses. Three key journal articles are: 1) Jeppu et al., A scalable surface complexation modeling framework for predicting arsenate adsorption on goethite-coated sands, Environ. Eng. Sci., 27(2): 147-158, 2010. 2) Loganathan et al., Scaling of adsorption reactions: U(VI) experiments and modeling, Applied Geochemistry, 24 (11), 2051-2060, 2009. 3) Phillippi, et al., Theoretical solid/solution ratio effects on adsorption and transport: uranium (VI) and carbonate, Soil Sci. Soci. of America, 71:329-335, 2007

  12. Tuning the reactivity of an actor ligand for tandem CO2 and C-H activations: from spectator metals to metal-free.

    Science.gov (United States)

    Annibale, Vincent T; Dalessandro, Daniel A; Song, Datong

    2013-10-30

    The 4,5-diazafluorenide ligand (L(-)) serves as an actor ligand in the formal insertion of CO2 into a C-H bond remote from the metal center. With the Ru(II) complex of L(-) as the starting point, Rh(III), Rh(I), and Cu(I) were used as spectator metal centers to tune the reactivity of the actor ligand toward CO2. In the case of Rh(III)-diazafluorenide a room temperature reversible activation of CO2 was observed, similar to the isoelectronic Ru(II) analogue. In the case of Rh(I)- and Cu(I)-diazafluorenide CO2 is trapped by the formation of dinuclear carboxylate complexes and diazafluorene (LH). The spectator metal center could even be replaced entirely with an organic group allowing for the first metal-free reversible tandem CO2 and C-H activation.

  13. Catalytic reactive distillation process development for 1,1 diethoxy butane production from renewable sources.

    Science.gov (United States)

    Agirre, I; Barrio, V L; Güemez, B; Cambra, J F; Arias, P L

    2011-01-01

    Some acetals can be produced from renewable resources (bioalcohols) and seem to be good candidates for different applications such as oxygenated diesel additives. In the present case the production of 1,1 diethoxy butane from bioethanol and butanal is presented. Butanal can be obtained from biobutanol following a partial oxidation or a dehydrogenation process. In this paper innovative process development about the synthesis of the mentioned acetal including catalytic reactive distillation experimental and simulation results will be presented and discussed. Katapak SP modules containing Amberlyst 47 resin were used as structured catalytic packings. This reactive system allowed reaching higher conversions than the equilibrium ones at the same temperatures. All the experimental data gathered allowed to tune a simulation model for the reactive distillation operation which showed a fairly good behavior in order to perform initial 1,1 diethoxy butane production process design studies.

  14. An analysis of reactivity prediction during the reactor start-up process

    Energy Technology Data Exchange (ETDEWEB)

    Bajgl, Josef [CEZ a.s., Dukovany (Czech Republic); Krysl, Vaclav; Svarny, Jiri [SKODA JS a.s., Plzen (Czech Republic)

    2015-09-15

    The different VVER-440 core fuel loadings subcriticality evaluations are performed during the start-up process by boron dilution or control assembly withdrawn by macrocode MOBY-DICK calculations. The dynamic reactivity and quasicritical reactivity are compared and sensitivity of reactivity prediction at the low boundary of start-up interval (ρ = -0,01) has been provided on the basis of different modelling of ionization chamber (IC) response calculation. Special attention is paid to the impact of power distribution and spontaneous fission distribution form factor on IC response correction during control assembly movement. Precision and robustness of different corrections of IC signal processing in real core start-up processed IC signals was evaluated.

  15. Transport phenomena of reactive fluid flow in heterogeneous combustion processes.

    Science.gov (United States)

    Hung, W. S. Y.; Chen, C. S.; Haviland, J. K.

    1972-01-01

    A previously developed computer program was used to model two transient hybrid combustion processes involving tubes of solid Plexiglas. In the first study, representing combustion of a hybrid rocket, the oxidizing gas was oxygen, and calculations were continued sufficiently long to obtain steady-state values. Systematic variations were made in reaction rate constant, mass flow rate, and pressure, alternatively using constant and temperature dependent regression rate models for the fuel surface. Consistent results were obtained, as is evidenced by the values for the mass function of the reaction product and the flame temperature, for which plots are supplied. In the second study, fire initiation in a duct was studied, with an air mixture as the oxidizing gas. It was demonstrated that a satisfactory flame spread mechanism could be reproduced on the computer. In both of the above applications, the general, transient, two-dimensional conservation equations were represented, together with chemical reactions, solid-fuel interface conditions, and heat conduction in the solid fuel.

  16. A bioseparation process for removing heavy metals from waste ...

    African Journals Online (AJOL)

    A bioseparation process for removing heavy metals from waste water using biosorbents. ... In recent years, many low cost sorbents such as algae, fungi bacteria and ... In this comprehensive review, the emphasis is on outlining the occurrences ...

  17. High-rate squeezing process of bulk metallic glasses

    Science.gov (United States)

    Fan, Jitang

    2017-03-01

    High-rate squeezing process of bulk metallic glasses from a cylinder into an intact sheet achieved by impact loading is investigated. Such a large deformation is caused by plastic flow, accompanied with geometrical confinement, shear banding/slipping, thermo softening, melting and joining. Temperature rise during the high-rate squeezing process makes a main effect. The inherent mechanisms are illustrated. Like high-pressure torsion (HPT), equal channel angular pressing (ECAP) and surface mechanical attrition treatments (SMAT) for refining grain of metals, High-Rate Squeezing (HRS), as a multiple-functions technique, not only creates a new road of processing metallic glasses and other metallic alloys for developing advanced materials, but also directs a novel technology of processing, grain refining, coating, welding and so on for treating materials.

  18. Fiber Metal Laminates Made by the VARTM Process

    Science.gov (United States)

    Jensen, Brian J.; Cano, Roberto J.; Hales, Stephen J.; Alexa, Joel A.; Weiser, Erik S.; Loos, Alfred; Johnson, W.S.

    2009-01-01

    Fiber metal laminates (FMLs) are multi-component materials utilizing metals, fibers and matrix resins. Tailoring their properties is readily achievable by varying one or more of these components. Established FMLs like GLARE utilize aluminum foils, glass fibers and epoxy matrices and are manufactured using an autoclave. Two new processes for manufacturing FMLs using vacuum assisted resin transfer molding (VARTM) have been developed at the NASA Langley Research Center (LaRC). A description of these processes and the resulting FMLs are presented.

  19. Reactive processing of ceramic binding systems for refractory castables

    Science.gov (United States)

    Ye, Guotian

    The general applied objective of this project is to develop hydratable alumina-bonded castables of properties comparable to the high-temperature fired basic bricks. This work is focused on improving the sintering of the ceramic binding systems at relatively low temperatures (˜1300°C) through incorporation of ultrafine powders. Ultrafine magnesium aluminate spinel powders were synthesized using already known and original methods. Combustible ingredients were incorporated to prevent the direct contacts of the precursor particles during drying and the combustibles leave a continuous pore network when they burn off during calcination at 700-800°C. Mechanical activation of the spinel precursor prepared using a heterogeneous sol-gel process decreased the activation energy for spinel formation from 688 kJ/mol to 468 kJ/mol, and lowered the incipient temperature of spinel formation from 900°C to 800°C, and the temperature of complete spinellization from >1280°C to 900°C. A new method for preparing homogeneous spine] precursor was presented and completely crystallized spinel with specific surface area of 105 m2/g, and crystallite size of 13 nm was formed from the precursor after calcination at 900°C. This work established the influence of ultrafine-sized powders on the sintering and strength development of multi-sized systems rich in large particles at relatively low temperatures, with emphasis on the temperatures around 1280°C. It was found that the relationship between the strength and linear shrinkage for the powder compacts consisting of uniform particle size distribution does not apply to the binding systems with wide particle size distributions (90 nm--90 mum). The addition of the ultrafine powders (≤0.5 mum median) up to 10% had no significant influence on strength in two-component binding systems after firing at 1280°C and 1450°C. However, the ultrafine powders increased the strength of three-component binding systems presumably because the addition of

  20. Reactivity of biogenic manganese oxide for metal sequestration and photochemistry: Computational solid state physics study

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, K.D.; Sposito, G.

    2010-02-01

    Many microbes, including both bacteria and fungi, produce manganese (Mn) oxides by oxidizing soluble Mn(II) to form insoluble Mn(IV) oxide minerals, a kinetically much faster process than abiotic oxidation. These biogenic Mn oxides drive the Mn cycle, coupling it with diverse biogeochemical cycles and determining the bioavailability of environmental contaminants, mainly through strong adsorption and redox reactions. This mini review introduces recent findings based on quantum mechanical density functional theory that reveal the detailed mechanisms of toxic metal adsorption at Mn oxide surfaces and the remarkable role of Mn vacancies in the photochemistry of these minerals.

  1. Column Testing and 1D Reactive Transport Modeling to Evaluate Uranium Plume Persistence Processes

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Raymond H. [Navarro Research and Engineering, Inc.; Morrison, Stan [Navarro Research and Engineering, Inc.; Morris, Sarah [Navarro Research and Engineering, Inc.; Tigar, Aaron [Navarro Research and Engineering, Inc.; Dam, William [U.S. Department of Energy, Office of Legacy Management; Dayvault, Jalena [U.S. Department of Energy, Office of Legacy Management

    2016-04-26

    Motivation for Study: Natural flushing of contaminants at various U.S. Department of Energy Office of Legacy Management sites is not proceeding as quickly as predicted (plume persistence) Objectives: Help determine natural flushing rates using column tests. Use 1D reactive transport modeling to better understand the major processes that are creating plume persistence Approach: Core samples from under a former mill tailings area Tailings have been removed. Column leaching using lab-prepared water similar to nearby Gunnison River water. 1D reactive transport modeling to evaluate processes

  2. Analysis of a reactive extraction process for biodiesel production using a lipase immobilized on magnetic nanostructures.

    Science.gov (United States)

    Dussan, K J; Cardona, C A; Giraldo, O H; Gutiérrez, L F; Pérez, V H

    2010-12-01

    Magnetic nanoparticles were prepared by coprecipitating Fe(2+) and Fe(3+) ions in a sodium hydroxide solution and used as support for lipase. The lipase-coated particles were applied in a reactive extraction process that allowed separation of the products formed during transesterification. Kinetics data for triolein and ethanol consumption during biodiesel (ethyl oleate) synthesis together with a thermodynamic phase equilibrium model (liquid-liquid) were used for simulation of batch and continuous processes. The analysis demonstrated the possibility of applying this biocatalytic system in the reactive zone using external magnetic fields. This approach implies new advantages in efficient location and use of lipases in column reactors for producing biodiesel.

  3. Study of the reactivity effect of bubble collapse in molten liquid metal cooled reactors

    Energy Technology Data Exchange (ETDEWEB)

    Munno, F.J.; Sheaks, O.J.

    1977-08-01

    The reactivity effect of void collapse on a Core Disruptive Accident in a sodium free fast reactor core was studied. A two-dimensional transport theory computer code was employed to obtain a reactivity model which incorporated random distributions of voids in spatial location and bubble size. This model was implemented into VENUS-II and several excursions were investigated for the purpose of assessing the effect of bubble collapse reactivity on excursion energy. In addition, comparisons were made between the VENUS-II results obtained using the transport reactivity model and those obtained using a reactivity model developed from the Behrens' formulation of the leakage effects due to the presence of bubbles. The results indicate that excursion energy is sensitive to the shape of the reactivity versus void fraction function and that reactivity models based strictly on leakage effects are probably conservative compared to models which include both self-multiplication and leakage.

  4. Sol-gel processing with inorganic metal salt precursors

    Science.gov (United States)

    Hu, Zhong-Cheng

    2004-10-19

    Methods for sol-gel processing that generally involve mixing together an inorganic metal salt, water, and a water miscible alcohol or other organic solvent, at room temperature with a macromolecular dispersant material, such as hydroxypropyl cellulose (HPC) added. The resulting homogenous solution is incubated at a desired temperature and time to result in a desired product. The methods enable production of high quality sols and gels at lower temperatures than standard methods. The methods enable production of nanosize sols from inorganic metal salts. The methods offer sol-gel processing from inorganic metal salts.

  5. Oxidation does not (always) kill reactivity of transition metals: solution-phase conversion of nanoscale transition metal oxides to phosphides and sulfides.

    Science.gov (United States)

    Muthuswamy, Elayaraja; Brock, Stephanie L

    2010-11-17

    Unexpected reactivity on the part of oxide nanoparticles that enables their transformation into phosphides or sulfides by solution-phase reaction with trioctylphosphine (TOP) or sulfur, respectively, at temperatures of ≤370 °C is reported. Impressively, single-phase phosphide products are produced, in some cases with controlled anisotropy and narrow polydispersity. The generality of the approach is demonstrated for Ni, Fe, and Co, and while manganese oxides are not sufficiently reactive toward TOP to form phosphides, they do yield MnS upon reaction with sulfur. The reactivity can be attributed to the small size of the precursor particles, since attempts to convert bulk oxides or even particles with sizes approaching 50 nm were unsuccessful. Overall, the use of oxide nanoparticles, which are easily accessed via reaction of inexpensive salts with air, in lieu of organometallic reagents (e.g., metal carbonyls), which may or may not be transformed into metal nanoparticles, greatly simplifies the production of nanoscale phosphides and sulfides. The precursor nanoparticles can easily be produced in large quantities and stored in the solid state without concern that "oxidation" will limit their reactivity.

  6. Removal of heavy metals by hybrid electrocoagulation and microfiltration processes.

    Science.gov (United States)

    Keerthi; Vinduja, V; Balasubramanian, N

    2013-01-01

    This study is based on the investigation of the performance of electrocoagulation (EC), followed by the microfiltration process for heavy metal removal in synthetic model waste water containing Zn2+, Ni2+ and Cd2+ ions. Effects of initial concentration, current density and pH on metal removal were analysed to optimize the EC process. The optimized EC process was then integrated with dead-end microfiltration (MF) and was found that the hybrid process was capable of 99% removal of heavy metals. The cake layer formed over the membrane by the hybrid process was analysed through scanning electron microscope-energy-dispersive X-ray spectroscopy. The particle size analysis of the sludge formed during EC was done to investigate the fouling caused during the process.

  7. Metal cutting analogy for establishing Friction Stir Welding process parameters

    Science.gov (United States)

    Stafford, Sylvester Allen

    A friction stir weld (FSW) is a solid state joining operation whose processing parameters are currently determined by lengthy trial and error methods. To implement FSWing rapidly in various applications will require an approach for predicting process parameters based on the physics of the process. Based on hot working conditions for metals, a kinematic model has been proposed for calculating the shear strain and shear strain rates during the FSW process, validation of the proposed model with direct measuring is difficult however. Since the shear strain and shear strain rates predicted for the FSW process, are similar to those predicted in metal cutting, validation of the FSW algorithms with microstructural studies of metal chips may be possible leading to the ability to predict FSW processing parameters.

  8. Ceramic/metal nanocomposites by lyophilization: Processing and HRTEM study

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez-Gonzalez, C.F. [Centro de Investigacion en Nanomateriales y Nanotecnologia (CINN), Consejo Superior de Investigaciones Cientificas - CSIC - Universidad de Oviedo - UO - Principado de Asturias - PA, Parque Tecnologico de Asturias, 33428 Llanera (Spain); Agouram, S. [Department of Applied Physics and Electromagnetism, Universitat de Valencia, 46100 Burjassot (Spain); Torrecillas, R. [Centro de Investigacion en Nanomateriales y Nanotecnologia (CINN), Consejo Superior de Investigaciones Cientificas - CSIC - Universidad de Oviedo -UO - Principado de Asturias- PA, Parque Tecnologico de Asturias, 33428 Llanera (Spain); Moya, J.S. [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Cientificas (ICMM-CSIC), Cantoblanco, 28049 Madrid (Spain); Lopez-Esteban, S., E-mail: s.lopez@cinn.es [Centro de Investigacion en Nanomateriales y Nanotecnologia (CINN), Consejo Superior de Investigaciones Cientificas - CSIC - Universidad de Oviedo - UO - Principado de Asturias - PA, Parque Tecnologico de Asturias, 33428 Llanera (Spain)

    2012-02-15

    Highlights: Black-Right-Pointing-Pointer A cryogenic route has been used to obtain ceramic/metal nanostructured powders. Black-Right-Pointing-Pointer The powders present good homogeneity and dispersion of metal. Black-Right-Pointing-Pointer The metal nanoparticle size distributions are centred in 17-35 nm. Black-Right-Pointing-Pointer Both phases, ceramic and metal, present a high degree of crystallinity. Black-Right-Pointing-Pointer Good metal/ceramic interfaces due to epitaxial growth, studied by HRTEM. -- Abstract: This work describes a wet-processing route based on spray-freezing and subsequent lyophilization designed to obtain nanostructured ceramic/metal powders. Starting from the ceramic powder and the corresponding metal salt, a water-based suspension is sprayed on liquid nitrogen. The frozen powders are subsequently freeze-dried, calcined and reduced. The material was analyzed using X-ray diffraction analysis at all stages. High resolution transmission electron microscopy studies showed a uniform distribution of metal nanoparticles on the ceramic grain surfaces, good interfaces and high crystallinity, with an average metal particle size in the nanometric range.

  9. Color removal from acid and reactive dye solutions by electrocoagulation and electrocoagulation/adsorption processes.

    Science.gov (United States)

    Bellebia, S; Kacha, S; Bouberka, Z; Bouyakoub, A Z; Derriche, Z

    2009-04-01

    In this study, electrocoagulation of Marine Blue Erionyl MR (acid dye) and electrocoagulation followed by adsorption of Brilliant Blue Levafix E-BRA (reactive dye) from aqueous solutions were investigated, using aluminum electrodes and granular activated carbon (GAC). In the electrocoagulation and adsorption of dyestuff solutions, the effects of current density, loading charge, pH, conductivity, stirring velocity, contact time, and GAC concentration were examined. The optimum conditions for the electrocoagulation process were identified as loading charges 7.46 and 1.49 F/m3, for a maximum abatement of 200 mg/L reactive and acid dye, respectively. The residual reactive dye concentration was completely removed with 700 mg/L GAC. The results of this investigation provide important data for the development of a combined process to remove significant concentrations of recalcitrant dyes from water, using moderate activated carbon energy and aluminum consumption, and thereby lowering the cost of treatment.

  10. PP-EPDM thermoplastic vulcanisates (TPVs by electron induced reactive processing

    Directory of Open Access Journals (Sweden)

    2009-11-01

    Full Text Available Reactive processing combines melt mixing process and chemical reaction simultaneously. TPVs are produced by such reactive processing. Polymer modification with high energy electrons is based on generation of excited atoms or molecules and ions for subsequent molecular changes via radical induced chemical reactions. In the present study, electron induced reactive processing is used for the development of TPVs. A 1.5 MeV electron accelerator was directly coupled to an internal mixer in order to induce chemical reactions by energy input via high energy electrons under dynamic conditions of melt mixing of polypropylene (PP and ethylene propylene diene monomer rubber (EPDM. The influence of absorbed dose (25 to 100 kGy as well as electron energy (1.5 and 0.6 MeV and electron treatment time (15 to 60 s have been studied. Increased values of both tensile strength and elongation at break of the TPVs indicate in-situ compatibilisation of PP and EPDM as well as cross-linking in the EPDM phase upon electron induced reactive processing. Dynamic mechanical analyses showed a decrease in value of glass transition temperature peak of EPDM in tangent delta curve with increasing dose. This also indicates higher degree of cross-linking in EPDM phase, which is further supported by a gel content that is higher than the EPDM content itself in the blend.

  11. Metal Enrichment Processes in the Intra-Cluster Medium

    CERN Document Server

    Schindler, S; Domainko, W; Mair, M; Van Kampen, E; Kronberger, T; Kimeswenger, S; Ruffert, M; Mangete, O E; Breitschwerdt, D

    2005-01-01

    We present numerical simulations of galaxy clusters which include interaction processes between the galaxies and the intra-cluster gas. The considered interaction processes are galactic winds and ram-pressure stripping, which both transfer metal-enriched interstellar medium into the intra-cluster gas and hence increase its metallicity. We investigate the efficiency and time evolution of the interaction processes by simulated metallicity maps, which are directly comparable to those obtained from X-ray observations. We find that ram-pressure stripping is more efficient than quiet (i.e. non-starburst driven) galactic winds in the redshift interval between 1 and 0. The expelled metals are not mixed immediately with the intra-cluster gas, but inhomogeneities are visible in the metallicity maps. Even stripes of higher metallicity that a single galaxy has left behind can be seen. The spatial distribution of the metals transported by ram-pressure stripping and by galactic winds are very different for massive clusters...

  12. Generation and Characteristics of IV-VI transition Metal Nitride and Carbide Nanoparticles using a Reactive Mesoporous Carbon Nitride

    KAUST Repository

    Alhajri, Nawal Saad

    2016-02-22

    Interstitial nitrides and carbides of early transition metals in groups IV–VI exhibit platinum-like electronic structures, which make them promising candidates to replace noble metals in various catalytic reactions. Herein, we present the preparation and characterization of nano-sized transition metal nitries and carbides of groups IV–VI (Ti, V, Nb, Ta, Cr, Mo, and W) using mesoporous graphitic carbon nitride (mpg-C3N4), which not only provides confined spaces for restricting primary particle size but also acts as a chemical source of nitrogen and carbon. We studied the reactivity of the metals with the template under N2 flow at 1023 K while keeping the weight ratio of metal to template constant at unity. The produced nanoparticles were characterized by powder X-ray diffraction, CHN elemental analysis, nitrogen sorption, X-ray photoelectron spectroscopy, and transmission electron microscopy. The results show that Ti, V, Nb, Ta, and Cr form nitride phases with face centered cubic structure, whereas Mo and W forme carbides with hexagonal structures. The tendency to form nitride or carbide obeys the free formation energy of the transition metal nitrides and carbides. This method offers the potential to prepare the desired size, shape and phase of transition metal nitrides and carbides that are suitable for a specific reaction, which is the chief objective of materials chemistry.

  13. Synthesis and Processing of Ultra-High Temperature Metal Carbide and Metal Diboride Nanocomposite Materials

    Science.gov (United States)

    2008-04-15

    Synthesis and Processing of Ultra-High Temperature Metal Carbide and Metal Diboride Nanocomposite Materials Final Performance Report Contract Number...sintered commercially-available powders. Each project is summarized below: Synthesis : Zirconium diboride and a zirconium diboride/tantalum diboride...mixture were synthesized by solution-based processing. Zirconium n-propoxide was refluxed with 2,4-pentanedione to form zirconium diketonate . This compound

  14. Synthesis and Reactivity of Metal Complexes in Trigonal N,O,O,O-Environments

    OpenAIRE

    Adelhardt, Mario Erwin

    2016-01-01

    High-valent iron complexes, for instance stabilized by multiple bonded oxo, nitrido, or imido ligands, have been identified as reactive intermediates in biological as well as technical systems. Although numerous synthetic model complexes have been synthesized and characterized in the past four decades, they often lack the high reactivity of their parental compounds. One strategy to enhance the reactivity of, for example, Fe(IV) oxo complexes is to enforce a trigonal coordination geometry ar...

  15. Efficient integration of stiff kinetics with phase change detection for reactive reservoir processes

    DEFF Research Database (Denmark)

    Kristensen, Morten Rode; Gerritsen, Margot G.; Thomsen, Per Grove;

    2007-01-01

    We propose the use of implicit one-step Explicit Singly Diagonal Implicit Runge-Kutta (ESDIRK) methods for integration of the stiff kinetics in reactive, compositional and thermal processes that are solved using operator-splitting type approaches. To facilitate the algorithmic development we...

  16. Biodiesel production from integration between reaction and separation system: reactive distillation process.

    Science.gov (United States)

    da Silva, Nívea de Lima; Santander, Carlos Mario Garcia; Batistella, César Benedito; Filho, Rubens Maciel; Maciel, Maria Regina Wolf

    2010-05-01

    Biodiesel is a clean burning fuel derived from a renewable feedstock such as vegetable oil or animal fat. It is biodegradable, non-inflammable, non-toxic, and produces lesser carbon monoxide, sulfur dioxide, and unburned hydrocarbons than petroleum-based fuel. The purpose of the present work is to present an efficient process using reactive distillation columns applied to biodiesel production. Reactive distillation is the simultaneous implementation of reaction and separation within a single unit of column. Nowadays, it is appropriately called "Intensified Process". This combined operation is especially suited for the chemical reaction limited by equilibrium constraints, since one or more of the products of the reaction are continuously separated from the reactants. This work presents the biodiesel production from soybean oil and bioethanol by reactive distillation. Different variables affect the conventional biodiesel production process such as: catalyst concentration, reaction temperature, level of agitation, ethanol/soybean oil molar ratio, reaction time, and raw material type. In this study, the experimental design was used to optimize the following process variables: the catalyst concentration (from 0.5 wt.% to 1.5 wt.%), the ethanol/soybean oil molar ratio (from 3:1 to 9:1). The reactive column reflux rate was 83 ml/min, and the reaction time was 6 min.

  17. Octanol-solubility of dissolved and particulate trace metals in contaminated rivers: implications for metal reactivity and availability.

    Science.gov (United States)

    Turner, Andrew; Mawji, Edward

    2005-05-01

    The lipid-like, amphiphilic solvent, n-octanol, has been used to determine a hydrophobic fraction of dissolved and particulate trace metals (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) in contaminated rivers. In a sample from the River Clyde, southwest Scotland, octanol-solubility was detected for all dissolved metals except Co, with conditional octanol-water partition coefficients, D(ow), ranging from about 0.2 (Al and Cu) to 1.25 (Pb). In a sample taken from the River Mersey, northwest England, octanol-solubility was detected for dissolved Al and Pb, but only after sample aliquots had been spiked with individual ionic metal standards and equilibrated. Spiking of the River Clyde sample revealed competition among different metals for hydrophobic ligands. Metal displacement from hydrophobic complexes was generally most significant following the addition of ionic Al or Pb, although the addition of either of these metals had little effect on the octanol-solubility of the other. In both river water samples hydrophobic metals were detected on the suspended particles retained by filtration following their extraction in n-octanol. In general, particulate Cu and Zn (up to 40%) were most available, and Al, Co and Pb most resistant (metal to octanol-soluble dissolved metal were in the range 10(3.3)-10(5.3)mlg(-1). The presence of hydrophobic dissolved and particulate metal species has implications for our understanding of the biogeochemical behaviour of metals in aquatic environments. Specifically, such species are predicted to exhibit characteristics of non-polar organic contaminants, including the potential to penetrate the lipid bilayer. Current strategies for assessing the bioavailability and toxicity of dissolved and particulate trace metals in natural waters may, therefore, require revision.

  18. Predictive Modeling of Metal-Catalyzed Polyolefin Processes

    OpenAIRE

    Khare, Neeraj Prasad

    2003-01-01

    This dissertation describes the essential modeling components and techniques for building comprehensive polymer process models for metal-catalyzed polyolefin processes. The significance of this work is that it presents a comprehensive approach to polymer process modeling applied to large-scale commercial processes. Most researchers focus only on polymerization mechanisms and reaction kinetics, and neglect physical properties and phase equilibrium. Both physical properties and phase equilib...

  19. Survey of electrochemical metal winning processes. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Vaaler, L.E.

    1979-03-01

    The subject program was undertaken to find electrometallurgical technology that could be developed into energy saving commercial metal winning processes. Metals whose current production processes consume significant energy (excepting copper and aluminum) are magnesium, zinc, lead, chromium, manganese, sodium, and titanium. The technology of these metals, with the exception of titanium, was reviewed. Growth of titanium demand has been too small to justify the installation of an electrolyte process that has been developed. This fact and the uncertainty of estimates of future demand dissuaded us from reviewing titanium technology. Opportunities for developing energy saving processes were found for magnesium, zinc, lead, and sodium. Costs for R and D and demonstration plants have been estimated. It appeared that electrolytic methods for chromium and manganese cannot compete energywise or economically with the pyrometallurgical methods of producing the ferroalloys, which are satisfactory for most uses of chromium and manganese.

  20. OPTIMISATION OF PROCESS PARAMETER CONDITIONS FOR BIODIESEL PRODUCTION BY REACTIVE EXTRACTION OF JATROPHA SEEDS

    Directory of Open Access Journals (Sweden)

    MUHAMMAD DANI SUPARDAN

    2017-03-01

    Full Text Available Biodiesel can be produced by reactive extraction of jatropha seeds to reduce the cost and processing time associated with conventional methods. In this study, the relationship between various parameters of reactive extraction of jatropha seeds is investigated. The effect of processing time, the moisture content of jatropha seeds and hexane to oil weight ratios are examined to determine the best performance for biodiesel yield. Response surface methodology was used to statistically evaluate and optimise the process parameter conditions. It was found that the biodiesel production achieved an optimum biodiesel yield of 73.7% under the following conditions: processing time of 160 min, moisture content of jatropha seeds of 1% and hexane to oil weight ratio of 7.2.

  1. A COMSOL-GEMS interface for modeling coupled reactive-transport geochemical processes

    Science.gov (United States)

    Azad, Vahid Jafari; Li, Chang; Verba, Circe; Ideker, Jason H.; Isgor, O. Burkan

    2016-07-01

    An interface was developed between COMSOL MultiphysicsTM finite element analysis software and (geo)chemical modeling platform, GEMS, for the reactive-transport modeling of (geo)chemical processes in variably saturated porous media. The two standalone software packages are managed from the interface that uses a non-iterative operator splitting technique to couple the transport (COMSOL) and reaction (GEMS) processes. The interface allows modeling media with complex chemistry (e.g. cement) using GEMS thermodynamic database formats. Benchmark comparisons show that the developed interface can be used to predict a variety of reactive-transport processes accurately. The full functionality of the interface was demonstrated to model transport processes, governed by extended Nernst-Plank equation, in Class H Portland cement samples in high pressure and temperature autoclaves simulating systems that are used to store captured carbon dioxide (CO2) in geological reservoirs.

  2. Process control for sheet-metal stamping process modeling, controller design and shop-floor implementation

    CERN Document Server

    Lim, Yongseob; Ulsoy, A Galip

    2014-01-01

    Process Control for Sheet-Metal Stamping presents a comprehensive and structured approach to the design and implementation of controllers for the sheet metal stamping process. The use of process control for sheet-metal stamping greatly reduces defects in deep-drawn parts and can also yield large material savings from reduced scrap. Sheet-metal forming is a complex process and most often characterized by partial differential equations that are numerically solved using finite-element techniques. In this book, twenty years of academic research are reviewed and the resulting technology transitioned to the industrial environment. The sheet-metal stamping process is modeled in a manner suitable for multiple-input multiple-output control system design, with commercially available sensors and actuators. These models are then used to design adaptive controllers and real-time controller implementation is discussed. Finally, experimental results from actual shopfloor deployment are presented along with ideas for further...

  3. Role of tip chemical reactivity on atom manipulation process in dynamic force microscopy.

    Science.gov (United States)

    Sugimoto, Yoshiaki; Yurtsever, Ayhan; Abe, Masayuki; Morita, Seizo; Ondráček, Martin; Pou, Pablo; Pérez, Ruben; Jelínek, Pavel

    2013-08-27

    The effect of tip chemical reactivity on the lateral manipulation of intrinsic Si adatoms toward a vacancy site on a Si(111)-(7 × 7) surface has been investigated by noncontact atomic force microscopy at room temperature. Here we measure the atom-hopping probabilities associated with different manipulation processes as a function of the tip-surface distance by means of constant height scans with chemically different types of tips. The interactions between different tips and Si atoms are evaluated by force spectroscopic measurements. Our results demonstrate that the ability to manipulate Si adatoms depends extremely on the chemical nature of the tip apex and is correlated with the maximal attractive force measured over Si adatoms. We rationalize the observed dependence of the atom manipulation process on tip-apex chemical reactivity by means of density functional theory calculations. The results of these calculations suggest that the ability to reduce the energy barrier associated with the Si adatom movement depends profoundly on tip chemical reactivity and that the level of energy barrier reduction is higher with tips that exhibit high chemical reactivity with Si adatoms. The results of this study provide a better way to control the efficiency of the atomic manipulation process for chemisorption systems.

  4. Principles for integrating reactive species into in vivo biological processes: Examples from exercise physiology.

    Science.gov (United States)

    Margaritelis, Nikos V; Cobley, James N; Paschalis, Vassilis; Veskoukis, Aristidis S; Theodorou, Anastasios A; Kyparos, Antonios; Nikolaidis, Michalis G

    2016-04-01

    The equivocal role of reactive species and redox signaling in exercise responses and adaptations is an example clearly showing the inadequacy of current redox biology research to shed light on fundamental biological processes in vivo. Part of the answer probably relies on the extreme complexity of the in vivo redox biology and the limitations of the currently applied methodological and experimental tools. We propose six fundamental principles that should be considered in future studies to mechanistically link reactive species production to exercise responses or adaptations: 1) identify and quantify the reactive species, 2) determine the potential signaling properties of the reactive species, 3) detect the sources of reactive species, 4) locate the domain modified and verify the (ir)reversibility of post-translational modifications, 5) establish causality between redox and physiological measurements, 6) use selective and targeted antioxidants. Fulfilling these principles requires an idealized human experimental setting, which is certainly a utopia. Thus, researchers should choose to satisfy those principles, which, based on scientific evidence, are most critical for their specific research question.

  5. Redox-inactive metal ions promoted the catalytic reactivity of non-heme manganese complexes towards oxygen atom transfer.

    Science.gov (United States)

    Choe, Cholho; Yang, Ling; Lv, Zhanao; Mo, Wanling; Chen, Zhuqi; Li, Guangxin; Yin, Guochuan

    2015-05-21

    Redox-inactive metal ions can modulate the reactivity of redox-active metal ions in a variety of biological and chemical oxidations. Many synthetic models have been developed to help address the elusive roles of these redox-inactive metal ions. Using a non-heme manganese(II) complex as the model, the influence of redox-inactive metal ions as a Lewis acid on its catalytic efficiency in oxygen atom transfer was investigated. In the absence of redox-inactive metal ions, the manganese(II) catalyst is very sluggish, for example, in cyclooctene epoxidation, providing only 9.9% conversion with 4.1% yield of epoxide. However, addition of 2 equiv. of Al(3+) to the manganese(II) catalyst sharply improves the epoxidation, providing up to 97.8% conversion with 91.4% yield of epoxide. EPR studies of the manganese(II) catalyst in the presence of an oxidant reveal a 16-line hyperfine structure centered at g = 2.0, clearly indicating the formation of a mixed valent di-μ-oxo-bridged diamond core, Mn(III)-(μ-O)2-Mn(IV). The presence of a Lewis acid like Al(3+) causes the dissociation of this diamond Mn(III)-(μ-O)2-Mn(IV) core to form monomeric manganese(iv) species which is responsible for improved epoxidation efficiency. This promotional effect has also been observed in other manganese complexes bearing various non-heme ligands. The findings presented here have provided a promising strategy to explore the catalytic reactivity of some di-μ-oxo-bridged complexes by adding non-redox metal ions to in situ dissociate those dimeric cores and may also provide clues to understand the mechanism of methane monooxygenase which has a similar diiron diamond core as the intermediate.

  6. Ca(II) Binding Regulates and Dominates the Reactivity of a Transition-Metal-Ion-Dependent Diesterase from Mycobacterium tuberculosis.

    Science.gov (United States)

    Pedroso, Marcelo M; Larrabee, James A; Ely, Fernanda; Gwee, Shuhui E; Mitić, Nataša; Ollis, David L; Gahan, Lawrence R; Schenk, Gerhard

    2016-01-18

    The diesterase Rv0805 from Mycobacterium tuberculosis is a dinuclear metallohydrolase that plays an important role in signal transduction by controlling the intracellular levels of cyclic nucleotides. As Rv0805 is essential for mycobacterial growth it is a promising new target for the development of chemotherapeutics to treat tuberculosis. The in vivo metal-ion composition of Rv0805 is subject to debate. Here, we demonstrate that the active site accommodates two divalent transition metal ions with binding affinities ranging from approximately 50 nm for Mn(II) to about 600 nm for Zn(II) . In contrast, the enzyme GpdQ from Enterobacter aerogenes, despite having a coordination sphere identical to that of Rv0805, binds only one metal ion in the absence of substrate, thus demonstrating the significance of the outer sphere to modulate metal-ion binding and enzymatic reactivity. Ca(II) also binds tightly to Rv0805 (Kd ≈40 nm), but kinetic, calorimetric, and spectroscopic data indicate that two Ca(II) ions bind at a site different from the dinuclear transition-metal-ion binding site. Ca(II) acts as an activator of the enzymatic activity but is able to promote the hydrolysis of substrates even in the absence of transition-metal ions, thus providing an effective strategy for the regulation of the enzymatic activity.

  7. SPARC fast reactor design : Design of two passively safe metal-fuelled sodium-cooled pool-type small modular fast reactors with Autonomous Reactivity Control

    OpenAIRE

    Lindström, Tobias

    2015-01-01

    In this master thesis a small modular sodium-cooled metal-fuelled pool-type fast reactor design, called SPARC - Safe and Passive with Autonomous Reactivity control, has been designed. The long term reactivity changes in the SPARC are managed by implementation of the the Autonomous Reactivity Control (ARC) system, which is the novelty of the design. The overall design is mainly based on the Integral Fast Reactor project (IFR), which experimentally demonstrated the passive safety characteristic...

  8. Process for recovering alkali metals and sulfur from alkali metal sulfides and polysulfides

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard; Alvare, Javier

    2016-10-25

    Alkali metals and sulfur may be recovered from alkali monosulfide and polysulfides in an electrolytic process that utilizes an electrolytic cell having an alkali ion conductive membrane. An anolyte solution includes an alkali monosulfide, an alkali polysulfide, or a mixture thereof and a solvent that dissolves elemental sulfur. A catholyte includes molten alkali metal. Applying an electric current oxidizes sulfide and polysulfide in the anolyte compartment, causes alkali metal ions to pass through the alkali ion conductive membrane to the catholyte compartment, and reduces the alkali metal ions in the catholyte compartment. Liquid sulfur separates from the anolyte solution and may be recovered. The electrolytic cell is operated at a temperature where the formed alkali metal and sulfur are molten.

  9. Interactions between ingredients in IMX-101: Reactive Chemical Processes Control Insensitive Munitions Properties

    Energy Technology Data Exchange (ETDEWEB)

    Maharrey, Sean P.; Wiese-Smith, Deneille; Highley, Aaron M.; Behrens, Richard,; Kay, Jeffrey J

    2014-03-01

    Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS) measurements have been conducted on a new Insensitive Munitions (IM) formulation. IMX-101 is the first explosive to be fully IM qualified under new NATO STANAG guidelines for fielded munitions. The formulation uses dinitroanisole (DNAN) as a new melt cast material to replace TNT, and shows excellent IM performance when formulated with other energetic ingredients. The scope of this work is to explain this superior IM performance by investigating the reactive processes occurring in the material when subjected to a well-controlled thermal environment. The dominant reactive processes observed were a series of complex chemical interactions between the three main ingredients (DNAN, NQ, and NTO) that occurs well below the onset of the normal decomposition process of any of the individual ingredients. This process shifts the thermal response of the formulations to a much lower temperature, where the kinetically controlled reaction processes are much slower. This low temperature shift has the effect of allowing the reactions to consume the reactive solids (NQ, NTO) well before the reaction rates increase and reach thermal runaway, resulting in a relatively benign response to the external stimuli. The main findings on the interaction processes are presented.

  10. SeSBench - An initiative to benchmark reactive transport models for environmental subsurface processes

    Science.gov (United States)

    Jacques, Diederik

    2017-04-01

    As soil functions are governed by a multitude of interacting hydrological, geochemical and biological processes, simulation tools coupling mathematical models for interacting processes are needed. Coupled reactive transport models are a typical example of such coupled tools mainly focusing on hydrological and geochemical coupling (see e.g. Steefel et al., 2015). Mathematical and numerical complexity for both the tool itself or of the specific conceptual model can increase rapidly. Therefore, numerical verification of such type of models is a prerequisite for guaranteeing reliability and confidence and qualifying simulation tools and approaches for any further model application. In 2011, a first SeSBench -Subsurface Environmental Simulation Benchmarking- workshop was held in Berkeley (USA) followed by four other ones. The objective is to benchmark subsurface environmental simulation models and methods with a current focus on reactive transport processes. The final outcome was a special issue in Computational Geosciences (2015, issue 3 - Reactive transport benchmarks for subsurface environmental simulation) with a collection of 11 benchmarks. Benchmarks, proposed by the participants of the workshops, should be relevant for environmental or geo-engineering applications; the latter were mostly related to radioactive waste disposal issues - excluding benchmarks defined for pure mathematical reasons. Another important feature is the tiered approach within a benchmark with the definition of a single principle problem and different sub problems. The latter typically benchmarked individual or simplified processes (e.g. inert solute transport, simplified geochemical conceptual model) or geometries (e.g. batch or one-dimensional, homogeneous). Finally, three codes should be involved into a benchmark. The SeSBench initiative contributes to confidence building for applying reactive transport codes. Furthermore, it illustrates the use of those type of models for different

  11. Ethylene irradiation: a new route to grow graphene on low reactivity metals.

    Science.gov (United States)

    Martínez-Galera, Antonio J; Brihuega, Iván; Gómez-Rodríguez, José M

    2011-09-14

    A novel technique for growing graphene on relatively inert metals, consisting in the thermal decomposition of low energy ethylene ions irradiated on hot metal surfaces in ultrahigh vacuum, is reported. By this route, we have grown graphene monolayers on Cu(111) and, for the first time, on Au(111) surfaces. For both noble metal substrates, but particularly for Au(111), our scanning tunneling microscopy and spectroscopy measurements provide sound evidence of a very weak graphene-metal interaction.

  12. Solution processed metal oxide thin film hole transport layers for high performance organic solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Steirer, K. Xerxes; Berry, Joseph J.; Chesin, Jordan P.; Lloyd, Matthew T.; Widjonarko, Nicodemus Edwin; Miedaner, Alexander; Curtis, Calvin J.; Ginley, David S.; Olson, Dana C.

    2017-01-10

    A method for the application of solution processed metal oxide hole transport layers in organic photovoltaic devices and related organic electronics devices is disclosed. The metal oxide may be derived from a metal-organic precursor enabling solution processing of an amorphous, p-type metal oxide. An organic photovoltaic device having solution processed, metal oxide, thin-film hole transport layer.

  13. Fatigability disrupts cognitive processes' regulation of inflammatory reactivity in old age.

    Science.gov (United States)

    Lin, Feng; Roiland, Rachel; Polesskaya, Oksana; Chapman, Benjamin; Johnson, Melissa; Brasch, Judith; Chen, Ding-Geng; Mapstone, Mark

    2014-12-01

    High fatigability, a dysfunctional adaption to fatigue, may lead to difficulties performing otherwise regularly encountered cognitive activities and may be related to pro-inflammatory reactivity. The purpose of the study was to investigate the effect of fatigability on cognitive processes and inflammatory response after an acute cognitive stress task in older adults. In an observational stress reactivity study conducted in a light- and temperature-controlled laboratory, we measured IL-6, self-reported acute fatigue, and frontally oriented cognitive processes in 55 community-dwelling individuals aged 75 years or older as part of a demanding set of cognitive tasks intended to induce stress. Subjects were classified into groups of low and high fatigability based on cluster analysis of their self-report acute fatigue before and after the cognitive tasks. The two clusters were comparable on levels of baseline IL-6 and cognitive processes; however, the high fatigability cluster had significantly higher levels of IL-6 response than the low fatigability cluster. After controlling for multiple covariates, fatigability moderated the relationship between speed of processing and IL-6 reactivity. Further exploratory analyses indicated significant adverse associations between speed of processing and attention and IL-6 reactivity in the group with low but not high fatigability. Although observational, these data are consistent with the notion that pro-inflammatory states in older adults might be reduced by improvements in cognitive processes. Because fatigability was associated with increased acute inflammatory response and disrupted the normal stress regulation provided by the cognitive processes, future randomized studies might examine whether fatigability alleviation reduces IL-6. Copyright © 2014 American Association for Geriatric Psychiatry. All rights reserved.

  14. Development of Metal Plate with Internal Structure Utilizing the Metal Injection Molding (MIM Process

    Directory of Open Access Journals (Sweden)

    Kwangho Shin

    2013-12-01

    Full Text Available In this study, we focus on making a double-sided metal plate with an internal structure, such as honeycomb. The stainless steel powder was used in the metal injection molding (MIM process. The preliminary studies were carried out for the measurement of the viscosity of the stainless steel feedstock and for the prediction of the filling behavior through Computer Aided Engineering (CAE simulation. PE (high density polyethylene (HDPE and low density polyethylene (LDPE and polypropylene (PP resins were used to make the sacrificed insert with a honeycomb structure using a plastic injection molding process. Additionally, these sacrificed insert parts were inserted in the metal injection mold, and the metal injection molding process was carried out to build a green part with rectangular shape. Subsequently, debinding and sintering processes were adopted to remove the sacrificed polymer insert. The insert had a suitable rigidity that was able to endure the filling pressure. The core shift analysis was conducted to predict the deformation of the insert part. The 17-4PH feedstock with a low melting temperature was applied. The glass transition temperature of the sacrificed polymer insert would be of a high grade, and this insert should be maintained during the MIM process. Through these processes, a square metal plate with a honeycomb structure was made.

  15. Reactive transport of metal contaminants in alluvium - Model comparison and column simulation

    Science.gov (United States)

    Brown, J.G.; Bassett, R.L.; Glynn, P.D.

    2000-01-01

    A comparative assessment of two reactive-transport models, PHREEQC and HYDROGEOCHEM (HGC), was done to determine the suitability of each for simulating the movement of acidic contamination in alluvium. For simulations that accounted for aqueous complexation, precipitation and dissolution, the breakthrough and rinseout curves generated by each model were similar. The differences in simulated equilibrium concentrations between models were minor and were related to (1) different units in model output, (2) different activity coefficients, and (3) ionic-strength calculations. When adsorption processes were added to the models, the rinseout pH simulated by PHREEQC using the diffuse double-layer adsorption model rose to a pH of 6 after pore volume 15, about 1 pore volume later than the pH simulated by HGC using the constant-capacitance model. In PHREEQC simulation of a laboratory column experiment, the inability of the model to match measured outflow concentrations of selected constituents was related to the evident lack of local geochemical equilibrium in the column. The difference in timing and size of measured and simulated breakthrough of selected constituents indicated that the redox and adsorption reactions in the column occurred slowly when compared with the modeled reactions. MINTEQA2 and PHREEQC simulations of the column experiment indicated that the number of surface sites that took part in adsorption reactions was less than that estimated from the measured concentration of Fe hydroxide in the alluvium.

  16. Challenges and Opportunities in Reactive Processing and Applications of Advanced Ceramic Materials

    Science.gov (United States)

    Singh, Mrityunjay

    2003-01-01

    Recently, there has been a great deal of interest in the research, development, and commercialization of innovative synthesis and processing technologies for advanced ceramics and composite materials. Reactive processing approaches have been actively considered due to their robustness, flexibility, and affordability. A wide variety of silicon carbide-based advanced ceramics and composites are currently being fabricated using the processing approaches involving reactive infiltration of liquid and gaseous species into engineered fibrous or microporous carbon performs. The microporous carbon performs have been fabricated using the temperature induced phase separation and pyrolysis of two phase organic (resin-pore former) mixtures and fiber reinforcement of carbon and ceramic particulate bodies. In addition, pyrolyzed native plant cellulose tissues also provide unique carbon templates for manufacturing of non-oxide and oxide ceramics. In spite of great interest in this technology due to their affordability and robustness, there is a lack of scientific basis for process understanding and many technical challenges still remain. The influence of perform properties and other parameters on the resulting microstructure and properties of final material is not well understood. In this presentation, mechanism of silicon-carbon reaction in various systems and the effect of perform microstructure on the mechanical properties of advanced silicon carbide based materials will be discussed. Various examples of applications of reactively processed advanced silicon carbide ceramics and composite materials will be presented.

  17. Xanthine oxidoreductase-catalyzed reactive species generation: A process in critical need of reevaluation.

    Science.gov (United States)

    Cantu-Medellin, Nadiezhda; Kelley, Eric E

    2013-06-10

    Nearly 30 years have passed since the discovery of xanthine oxidoreductase (XOR) as a critical source of reactive species in ischemia/reperfusion injury. Since then, numerous inflammatory disease processes have been associated with elevated XOR activity and allied reactive species formation solidifying the ideology that enhancement of XOR activity equates to negative clinical outcomes. However, recent evidence may shatter this paradigm by describing a nitrate/nitrite reductase capacity for XOR whereby XOR may be considered a crucial source of beneficial (•)NO under ischemic/hypoxic/acidic conditions; settings similar to those that limit the functional capacity of nitric oxide synthase. Herein, we review XOR-catalyzed reactive species generation and identify key microenvironmental factors whose interplay impacts the identity of the reactive species (oxidants vs. (•)NO) produced. In doing so, we redefine existing dogma and shed new light on an enzyme that has weathered the evolutionary process not as gadfly but a crucial component in the maintenance of homeostasis.

  18. Extreme metal music and anger processing

    Directory of Open Access Journals (Sweden)

    Leah eSharman

    2015-05-01

    Full Text Available The claim that listening to extreme music causes anger and expressions of anger such as aggression and delinquency has yet to be substantiated using controlled experimental methods. In this study, 39 extreme music listeners aged 18 to 34 years were subjected to an anger induction, followed by random assignment to 10 minutes of listening to extreme music from their own playlist, or 10 minutes of silence (control. Measures of emotion included heart rate and subjective ratings on the Positive and Negative Affect Scale (PANAS. Results showed that ratings of PANAS hostility, irritability, and stress increased during the anger induction, and decreased after the music or silence. Heart rate increased during the anger induction and was sustained (not increased in the music condition, and decreased in the silence condition. PANAS active and inspired ratings increased during music listening, an effect that was not seen in controls. The findings indicate that extreme music did not make angry participants angrier rather it appeared to match their physiological arousal and result in an increase in positive emotions. Listening to extreme music may represent a healthy way of processing anger for these listeners.

  19. Reactivity of pi-complexes of Ti, V, and Nb towards dithioacetic acid: Synthesis and structure of novel metal sulfur-containing complexes

    Science.gov (United States)

    Duraj, Stan A.; Andras, Maria T.; Hepp, Aloysius F.

    1990-01-01

    In order to use sulfur-containing resources economically and with minimal environmental damage, it is important to understand the desulfurization processes. Hydrodesulfurization, for example, is carried out on the surface of a heterogeneous metal sulfide catalyst. Studies of simple, soluble inorganic systems provide information regarding the structure and reactivity of sulfur-containing compounds with metal complexes. Further, consistent with recent trends in materials chemistry, many model compounds warrant further study as catalyst precursors. The reactivity of low-valent organometallic sandwich pi-complexes toward dithiocarboxylic acids is described. For example, treatment of bisbenzene vanadium with CH3CSSH affords a divanadium tetrakis(dithioacetate) complex. The crystallographically determined V-V bond distance, 2.800(2), is nearly the same as the V-V bond distance in a V(mu-nu squared-S2)2V' unit in the mineral patonite (VS4)n. The stability of the V2S4 core in the dimer is demonstrated by evidence of V2S4(+) in the mass spectrum (70 eV, solid probe) of the vanadium dimer. Several other systems relevant to HDS catalysis are also discussed.

  20. Novel forward osmosis process to effectively remove heavy metal ions

    KAUST Repository

    Cui, Yue

    2014-10-01

    In this study, a novel forward osmosis (FO) process for the removal of heavy metal ions from wastewater was demonstrated for the first time. The proposed FO process consists of a thin-film composite (TFC) FO membrane made from interfacial polymerization on a macrovoid-free polyimide support and a novel bulky hydroacid complex Na4[Co(C6H4O7)2]·r2H2O (Na-Co-CA) as the draw solute to minimize the reverse solute flux. The removal of six heavy metal solutions, i.e., Na2Cr2O7, Na2HAsO4, Pb(NO3)2, CdCl2, CuSO4, Hg(NO3)2, were successfully demonstrated. Water fluxes around 11L/m2/h (LMH) were harvested with heavy metals rejections of more than 99.5% when employing 1M Na-Co-CA as the draw solution to process 2000ppm(1 ppm=1 mg/L) heavy metal solutions at room temperature. This FO performance outperforms most nanofiltration (NF) processes. In addition, the high rejections were maintained at 99.5% when a more concentrated draw solution (1.5M) or feed solution (5000ppm) was utilized. Furthermore, rejections greater than 99.7% were still achieved with an enhanced water flux of 16.5LMH by operating the FO process at 60°C. The impressive heavy metal rejections and satisfactory water flux under various conditions suggest great potential of the newly developed FO system for the treatment of heavy metal wastewater. © 2014 Elsevier B.V.

  1. Separation of metals from incineration wastes using mineral industry processes

    Energy Technology Data Exchange (ETDEWEB)

    Scheizer, G. [Universite de Technologie, Aix-la-Chapelle (Germany)

    1996-12-01

    The incineration of municipal wastes in Federal Republic of Germany produced about 2.7 to 2.8 millions of tons of solid wastes in 1993 which still contain huge amounts of mineral and organic pollutants. Ashes represent the largest part of wastes with about 2.4 millions of tons. Vitrification is an innovative treatment technique which allows a 90% reduction of the waste volume, the complete removal of the organic matter content, and the storage of these waste in an environmentally neutral form. However, metals must be extracted from the ashes prior to the vitrification process. Most metals fall into the 2.4-2.7 g/cm{sup 3} and > 3 g/cm{sup 3} density ranges. The lighter fraction corresponds to aluminium particles and alloys, while the high density fraction is enriched in copper, copper alloys and more particularly in brass. The treatment process, after drying, consist in the use of high intensity magnetic separation devices (permanent neodymium-bore-iron magnets) for the removal of ferrous particles, and in the use of Foucault currents separation devices for non-magnetic metals. At the pilot-scale, the distribution of the processed wastes corresponds to: 62.6 % of non-metallized ashes, 35.5 % of magnetic products, and 1.9% of non-magnetic products. The possible recycling of the metal fraction must be demonstrated by further studies. (J.S.). Abstract only.

  2. Role of direct reactivity with metals in chemoprotection by N-acetylcysteine against chromium(VI), cadmium(II), and cobalt(II).

    Science.gov (United States)

    Luczak, Michal W; Zhitkovich, Anatoly

    2013-12-01

    The antioxidant N-acetylcysteine (NAC) is widely used for the assessment of the role of reactive oxygen species (ROS) in various biological processes and adverse drug reactions. NAC has been found to effectively inhibit the toxicity of carcinogenic metals, which was attributed to its potent ROS-suppressive properties. However, the absence of redox activity among some metals and findings from genetic models suggested a more diverse, smaller role of oxidative stress in metal toxicity. Here, we examined mechanisms of chemoprotection by NAC against Cd(II), Co(II), and Cr(VI) in human cells. We found that NAC displayed a broad-spectrum chemoprotective activity against all three metals, including suppression of cytotoxicity, apoptosis, p53 activation, and HSP72 and HIF-1α upregulation. Cytoprotection by NAC was independent of cellular glutathione. NAC strongly inhibited the uptake of all three metals in histologically different types of human cells, explaining its high chemoprotective potential. A loss of Cr(VI) accumulation by cells was caused by NAC-mediated extracellular reduction of chromate to membrane-impermeative Cr(III). Suppression of Co(II) uptake resulted from a rapid formation of Co(II)-NAC conjugates that were unable to enter cells. Our results demonstrate that NAC acts through more than one mechanism in preventing metal toxicity and its chemoprotective activity can be completely ROS-independent. Good clinical safety and effectiveness in Co(II) sequestration suggest that NAC could be useful in the prevention of tissue accumulation and toxic effects of Co ions released by cobalt-chromium hip prostheses.

  3. Composition and morphology of metal-containing diamond-like carbon films obtained by reactive magnetron sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Corbella, C. [FEMAN Group, Departament de Fisica Aplicada i Optica, Universitat de Barcelona, Av. Diagonal 647, E08028 Barcelona (Spain)]. E-mail: corbella@ub.edu; Pascual, E. [FEMAN Group, Departament de Fisica Aplicada i Optica, Universitat de Barcelona, Av. Diagonal 647, E08028 Barcelona (Spain); Oncins, G. [Serveis Cientificotecnics, Universitat de Barcelona, PCB, c/ Josep Samitier 1-5, E08028 Barcelona (Spain); Canal, C. [Departamento de Tecnologia de Tensioactivos IQAB-CSIC, c/ Jordi Girona 18-26, E08034 Barcelona (Spain); Andujar, J.L. [FEMAN Group, Departament de Fisica Aplicada i Optica, Universitat de Barcelona, Av. Diagonal 647, E08028 Barcelona (Spain); Bertran, E. [FEMAN Group, Departament de Fisica Aplicada i Optica, Universitat de Barcelona, Av. Diagonal 647, E08028 Barcelona (Spain)

    2005-06-22

    The addition of metal atoms within the matrix of diamond-like carbon films leads to the improvement of their mechanical properties. The present paper discusses the relationship between the composition and morphology of metal-containing (W, Nb, Mo, Ti) diamond-like carbon thin films deposited at room temperature by reactive magnetron sputtering from a metal target in an argon and methane atmosphere. Composition was measured either by electron microprobe technique or by X-ray photoelectron spectroscopy and shows a smooth variation with relative methane flow. High relative methane flows lead to a bulk saturation of carbon atoms, which leads to a lack of homogeneity in the films as confirmed by secondary ion mass spectrometry. Cross-section micrographs were observed by transmission electron microscopy and revealed a structure strongly influenced by the metal inserted and its abundance. The surface pattern obtained by scanning electrochemical potential microscopy provided the metallicity distribution. These measurements were completed with atomic force microscopy of the surface. Selected area electron diffraction and X-ray diffraction measurements provided data of the crystalline structure along with nano-crystallite size. High-resolution transmission electron microscopy provided images of these crystallites.

  4. Polyimide and Metals MEMS Multi-User Processes

    KAUST Repository

    Arevalo, Arpys

    2016-11-01

    The development of a polyimide and metals multi-user surface micro-machining process for Micro-electro-mechanical Systems (MEMS) is presented. The process was designed to be as general as possible, and designed to be capable to fabricate different designs on a single silicon wafer. The process was not optimized with the purpose of fabricating any one specific device but can be tweaked to satisfy individual needs depending on the application. The fabrication process uses Polyimide as the structural material and three separated metallization layers that can be interconnected depending on the desired application. The technology allows the development of out-of-plane compliant mechanisms, which can be combined with six variations of different physical principles for actuation and sensing on a single processed silicon wafer. These variations are: electrostatic motion, thermal bimorph actuation, capacitive sensing, magnetic sensing, thermocouple-based sensing and radio frequency transmission and reception.

  5. Effect of processing temperature on the bitumen/MDI-PEG reactivity

    Energy Technology Data Exchange (ETDEWEB)

    Martin-Alfonso, M.J.; Partal, P.; Navarro, F.J.; Garcia-Morales, M. [Departamento de Ingenieria Quimica, Facultad de Ciencias Experimentales, Campus de ' El Carmen' , Universidad de Huelva, 21071, Huelva (Spain); Bordado, J.C.M. [Chemical and Biological Engineering Department, IBB, Instituto Superior Tecnico, Av. Rovisco Pais 1049-001 Lisbon (Portugal); Diogo, A.C. [Materials Engineering Department, Instituto Superior Tecnico, Av. Rovisco Pais 1049-001 Lisbon (Portugal)

    2009-04-15

    Reactive polymers are lately gaining acceptance to give added value to a residue of the crude oil refining process such as bitumen. The resulting material should display enhanced mechanical properties to be considered for advanced applications in construction. In the present paper, we report the effect of processing temperature on the reaction between bitumen compounds and an isocyanate-based reactive polymer, synthesized by reaction of polymeric MDI (4,4'-diphenylmethane diisocyanate) with a low molecular weight polyethylene-glycol (PEG). Rheokinetics experiments, viscosity measurements at 60 C, atomic force microscopy (AFM) characterization, thin layer chromatography (TLC-FID) analysis and thermogravimetric studies (TGA) were performed on the reactive polymer and on samples of MDI-PEG modified bitumen containing 2 wt.% of the polymer. Results showed the existence of an optimum processing temperature arisen as a consequence of opposite effects: microstructural availability for the formation of a polymer-bitumen network, reaction ability and polymer thermal degradation. Consequently, this study aims to serve as a guideline for the refining and asphalt industries facing the stage of selecting the optimum processing parameters. (author)

  6. Assessing the reactivity of sodium alkyl-magnesiates towards quinoxaline: single electron transfer (SET) vs. nucleophilic alkylation processes.

    Science.gov (United States)

    Livingstone, Zoe; Hernán-Gómez, Alberto; Baillie, Sharon E; Armstrong, David R; Carrella, Luca M; Clegg, William; Harrington, Ross W; Kennedy, Alan R; Rentschler, Eva; Hevia, Eva

    2016-04-14

    By exploring the reactivity of sodium butyl-magnesiate (1) supported by the bulky chelating silyl(bisamido) ligand {Ph2Si(NAr*)2}(2-) (Ar* = 2,6-iPr2-C6H3) towards Quinoxaline (Qx), the ability of this bimetallic system to effectively promote SET processes has been disclosed. Thus 1 executes the single-electron reduction of Qx affording complex (2) whose structure in the solid state contains two quinaxolyl radical anions Qx˙ stabilised within a dimeric magnesiate framework. Combining multinuclear NMR and EPR measurements with DFT calculations, new insights into the constitution of 2 in solution and its magnetic behaviour have been gained. Further evidence on the SET reactivity of 1 was found when it was reacted with nitroxyl radical TEMPO which furnished contacted ion pair sodium magnesiate [(Ph2Si(NAr*)2)Mg(TEMPO(-))Na(THF)3] (4) where both metals are connected by an alkoxide bridge, resulting from reduction of TEMPO. The role that the different ligands present in 1 can play in these new SET reactions has also been assessed. Using an amination approach, the Bu group in 1 can be replaced by the more basic amide TMP allowing the isolation of (3) which was characterised by multinuclear NMR and X-ray crystallography. (1)H NMR monitoring of the reaction of 3 with Qx showed its conversion to 2, leaving the hydrogen atoms of the heterocycle untouched. Contrastingly, using sodium homoalkyl magnesiate [NaMg(CH2SiMe3)3] (5) led to the chemoselective C2 alkylation of this heterocycle, suggesting that the presence of the steric stabiliser {Ph2Si(NAr*)2}(2-) on the mixed-metal reagent is required in order to facilitate the Qx reduction.

  7. Metal-loaded polystyrene-based activated carbons as DBT removal media via reactive adsorption

    OpenAIRE

    2006-01-01

    [EN] To improve the desulfurization capability of activated carbons, new metal-loaded carbon-based sorbents containing sodium, cobalt, copper, and silver highly dispersed within the carbon matrix were prepared and tested at room temperature for dibenzothiophene (DBT) adsorption. The content of metals can be controlled by selective washing. The new adsorbents showed good adsorption capacities and selectivity towards DBT. The metals incorporated to the surface act not only as active sites for s...

  8. Soluble ions more than particulate cobalt-alloy implant debris induce monocyte costimulatory molecule expression and release of proinflammatory cytokines critical to metal-induced lymphocyte reactivity.

    Science.gov (United States)

    Caicedo, Marco S; Pennekamp, Peter H; McAllister, Kyron; Jacobs, Joshua J; Hallab, Nadim J

    2010-06-15

    Aseptic osteolysis has been associated with excessive immune reactivity to particulate implant debris; however, innate and adaptive immune mechanisms that underlie implant debris reactivity remain incompletely understood. Although particulate debris has been implicated as the major type of implant debris mediating macrophage-induced osteolysis, the degree to which metal ions affect a proinflammatory response (if at all) remains unknown. We hypothesized that both soluble and particulate metal implant debris will induce proinflammatory responses in human monocytes resulting in cytokine production and elevated expression of T cell costimulatory molecules, facilitating adaptive immune responses. We tested this hypothesis by characterizing the response of a human monocyte cell line (THP-1), isolated primary human monocytes and PBMCs challenged with Co-Cr-Mo alloy particles and soluble cobalt, chromium, molybdenum, and nickel ions. Our results indicate that soluble cobalt, nickel, and molybdenum can induce monocyte up-regulation of T cell costimulatory molecules (CD80, CD86, ICAM-1) in human monocytes/macrophages. Furthermore, cobalt, molybdenum ions, and Co-Cr-Mo alloy particles similarly induce elevated secretion of IL-1beta, TNFalpha, and IL-6. Antibody blockade of CD80 and CD86, crucial secondary molecules for adaptive responses, abrogated lymphocyte reactivity to metal challenge in metal reactive subjects. Also the addition of IL-1 receptor antagonist (IL-1ra), (which indirectly blocks pro-IL-1beta and thus IL-1beta release), significantly reduced lymphocyte reactivity in metal-reactive subjects. Thus, both soluble and particulate metal implant debris induce monocyte/macrophage proinflammatory responses that are metal and individual specific. This suggests metal-induced up-regulation of costimulatory molecules and proinflammatory cytokine production is necessary to induce lymphocyte activation/proliferation to metal implant debris.

  9. Abnormal proactive and reactive cognitive control during conflict processing in major depression.

    Science.gov (United States)

    Vanderhasselt, Marie-Anne; De Raedt, Rudi; De Paepe, Annick; Aarts, Kristien; Otte, Georges; Van Dorpe, Jan; Pourtois, Gilles

    2014-02-01

    According to the Dual Mechanisms of Control framework, cognitive control consists of two complementary components: proactive control refers to anticipatory maintenance of goal-relevant information, whereas reactive control acts as a correction mechanism that is activated when a conflict occurs. Possibly, the well-known diminished inhibitory control in response to negative stimuli in Major Depressive Disorder (MDD) patients stems from a breakdown in proactive control, and/or anomalies in reactive cognitive control. In our study, MDD patients specifically showed increased response latencies when actively inhibiting a dominant response to a sad compared with a happy face. This condition was associated with a longer duration of a dominant ERP topography (800-900 ms poststimulus onset) and a stronger activity in the bilateral dorsal anterior cingulate cortex, reflecting abnormal reactive control when inhibiting attention to a negative stimulus. Moreover, MDD patients showed abnormalities in proactive cognitive control when preparing for the upcoming imperative stimulus (abnormal modulation of the contingent negative variation component), accompanied by more activity in brain regions belonging to the default mode network. All together, deficits to inhibit attention to negative information in MDD might originate from an abnormal use of both proactive resources and reactive control processes.

  10. An evaluation of char reactivity and ash properties in biomass gasification. Fundamental processes in biomass gasification

    Energy Technology Data Exchange (ETDEWEB)

    Holst Soerensen, L.; Fjellerup, J.; Henriksen, U.; Moilanen, A.; Kurkela, E.; Winther, E.

    2000-09-01

    This work focus on the connection between char reactivity, ash agglomeration and sintering and the gas composition in the turbid environment in a circulating fluidized bed gasification process, where biomass is gasified, with focus on straw gasification. The model approach intends to combine equilibrium calculation programming of complex multicomponent-multiphase systems involving gas, solid and liquid solutions of salts and silicates with the concept of catalytic effects in fuel reactivity. Char gasification reactivity and ash characteristics have been tested experimentally in a bench scale fluidized bed, in different thermal balances and in high-temperature light-microscope equipment. Ten different Danish straw samples and some artificial samples and catalysts were tested. It was found that the most important difference between the straw behaviour, that seems to determine the reactivity and the sintering tendency, were the calculated solid bed mol-ratio, {gamma}{sub {kappa}}=SiO{sub 2}/K{sub 2}O. We suggest that a fuel has high agglomeration tendency if 2<{gamma}{kappa}<15 and very high agglomeration tendency if 3<{gamma}{kappa}<5. It has also been found that a number of additives if properly added are effective for the prevention of agglomeration and sintering of straw ash. A literature survey study on tar cracking from biomass gasification has been performed. (au)

  11. Ligand Symmetry Modulation for Designing a Mesoporous Metal-Organic Framework: Dual Reactivity to Transition and Lanthanide Metals for Enhanced Functionalization.

    Science.gov (United States)

    Du, Miao; Wang, Xi; Chen, Min; Li, Cheng-Peng; Tian, Jia-Yue; Wang, Zhuo-Wei; Liu, Chun-Sen

    2015-06-26

    A promising alternative strategy for designing mesoporous metal-organic frameworks (MOFs) has been proposed, by modifying the symmetry rather than expanding the length of organic linkers. By means of this approach, a unique MOF material based on the target [Zn8(ad)4] (ad = adeninate) clusters and C3-symmetric organic linkers can be obtained, with trigonal microporous (ca., 0.8 nm) and hexagonal mesoporous (ca., 3.0 nm) 1D channels. Moreover, the resulting 446-MOF shows distinct reactivity to transition and lanthanide metal ions. Significantly, the transmetalation of Co(II) or Ni(II) on the Zn(II) centers in 446-MOF can enhance the sorption capacities of CO2 and CH4 (16-21%), whereas the impregnation of Eu(III) and Tb(III) in the channels of 446-MOF will result in adjustable light-emitting behaviors.

  12. Application of laser assisted cold spraying process for metal deposition

    CSIR Research Space (South Africa)

    Tlotleng, Monnamme

    2014-02-01

    Full Text Available Laser assisted cold spraying (LACS) process is a hybrid technique that uses laser and cold spray to deposit solid powders on metal substrates. For bonding to occur, the particle velocities must be supersonic which are achieved by entraining...

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

    Science.gov (United States)

    Congdon, James W.

    2009-03-17

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

  14. Research on the processing experiments of laser metal deposition shaping

    Science.gov (United States)

    Zhang, Kai; Liu, Weijun; Shang, Xiaofeng

    2007-04-01

    Laser additive direct deposition of metals is a new rapid manufacturing technology, which combines with computer-aided design (CAD), laser cladding and rapid prototyping. The advanced technology can build fully dense metal components directly from CAD files with neither mould nor tool. Based on the theory of this technology, a promising rapid manufacturing system called "Laser Metal Deposition Shaping (LMDS)" has been constructed and developed successfully by Chinese Academy of Sciences, Shenyang Institute of Automation. Through the LMDS system, comprehensive experiments are carried out with nickel-based superalloy to systematically investigate the influences of the processing parameters on forming characteristics. By adjusting to the optimal processing parameters, fully dense and near-net-shaped metallic parts can be directly obtained through melting coaxially fed powder with a laser. Moreover, the microstructure and mechanical properties of as-formed samples are tested and analyzed synthetically. As a result, significant processing flexibility with the LMDS system over conventional processing capabilities is recognized, with potentially lower production cost, higher quality components, and shorter lead-time.

  15. METALS LEACHING FROM A MINERAL PROCESSING WASTE: A COLUMN STUDY

    Science.gov (United States)

    A mineral processing waste was used to study the effect of liquid to solid ratio (L/S) on the leaching behavior of metals. Leaching tests in the form of column and batch studies were carried out to investigate liquid to solid ratios ranging from 0.7 to 50. Although the waste pass...

  16. Impact of heavy metals on the oil products biodegradation process.

    Science.gov (United States)

    Zukauskaite, Audrone; Jakubauskaite, Viktorija; Belous, Olga; Ambrazaitiene, Dalia; Stasiskiene, Zaneta

    2008-12-01

    Oil products continue to be used as a principal source of energy. Wide-scale production, transport, global use and disposal of petroleum have made them major contaminants in prevalence and quantity in the environment. In accidental spills, actions are taken to remove or remediate or recover the contaminants immediately, especially if they occur in environmentally sensitive areas, for example, in coastal zones. Traditional methods to cope with oil spills are confined to physical containment. Biological methods can have an advantage over the physical-chemical treatment regimes in removing spills in situ as they offer biodegradation of oil fractions by the micro-organisms. Recently, biological methods have been known to play a significant role in bioremediation of oil-polluted coastal areas. Such systems are likely to be of significance in the effective management of sensitive coastal ecosystems chronically subjected to oil spillage. For this reason the aim of this paper is to present an impact of Mn, Cu, Co and Mo quantities on oil biodegradation effectiveness in coastal soil and to determine the relationship between metal concentrations and degradation of two oil products (black oil and diesel fuel). Soil was collected in the Baltic Sea coastal zone oil products degradation area (Klaipeda, Lithuania). The experiment consisted of two parts: study on the influence of micro-elements on the oil product biodegradation process; and analysis of the influence of metal concentration on the number of HDMs. The analysis performed and results obtained address the following areas: impact of metal on a population of hydrocarbon degrading micro-organisms, impact of metals on residual concentrations of oil products, influence of metals on the growth of micro-organisms, inter-relation of metal concentrations with degradation rates. Statistical analysis was made using ;Statgraphics plus' software. The influence of metals on the growth of micro-organisms, the biodegradation process

  17. Carbon Nanotube Bonding Strength Enhancement Using Metal "Wicking" Process

    Science.gov (United States)

    Lamb, James L.; Dickie, Matthew R.; Kowalczyk, Robert S.; Liao, Anna; Bronikowski, Michael J.

    2012-01-01

    Carbon nanotubes grown from a surface typically have poor bonding strength at the interface. A process has been developed for adding a metal coat to the surface of carbon nano tubes (CNTs) through a wicking process, which could lead to an enhanced bonding strength at the interface. This process involves merging CNTs with indium as a bump-bonding enhancement. Classical capillary theory would not normally allow materials that do not wet carbon or graphite to be drawn into the spacings by capillary action because the contact angle is greater than 90 degrees. However, capillary action can be induced through JPL's ability to fabricate oriented CNT bundles to desired spacings, and through the use of deposition techniques and temperature to control the size and mobility of the liquid metal streams and associated reservoirs. A reflow and plasma cleaning process has also been developed and demonstrated to remove indium oxide, and to obtain smooth coatings on the CNT bundles.

  18. A review of process advancement of novel metal spinning

    OpenAIRE

    Xia, Q.; Xiao, G; Van Long, H.; Cheng, X; X. Sheng

    2014-01-01

    Metal spinning technology has seen a rapid development in recent years. Novel spinning processes, such as non-axisymmetrical spinning, non-circular cross-section spinning and tooth-shaped spinning, are being developed. This has challenged the limitation of traditional spinning technology being used for manufacturing axisymmetrical, circular cross-section, and uniform wall-thickness parts. In this paper, the classification of the traditional spinning processes is proposed based on the material...

  19. Effects of Gravity on Processing Heavy Metal Fluoride Fibers

    Science.gov (United States)

    Tucker, Dennis S.; Workman, Gary L.; Smith, Guy A.

    1997-01-01

    The effects of gravity on the crystal nucleation of heavy metal fluoride fibers have been studied in preliminary experiments utilizing NASA's KC-135 reduced gravity aircraft and a microgravity sounding rocket flight. Commercially produced fibers were heated to the crystallization temperature in normal and reduced gravity. The fibers processed in normal gravity showed complete crystallization while the fibers processed in reduced gravity did not show signs of crystallization.

  20. Modelling and Validation of Synthesis of Poly Lactic Acid Using an Alternative Energy Source through a Continuous Reactive Extrusion Process

    Directory of Open Access Journals (Sweden)

    Satya P. Dubey

    2016-04-01

    Full Text Available PLA is one of the most promising bio-compostable and bio-degradable thermoplastic polymers made from renewable sources. PLA is generally produced by ring opening polymerization (ROP of lactide using the metallic/bimetallic catalyst (Sn, Zn, and Al or other organic catalysts in a suitable solvent. In this work, reactive extrusion experiments using stannous octoate Sn(Oct2 and tri-phenyl phosphine (PPh3 were considered to perform ROP of lactide. Ultrasound energy source was used for activating and/or boosting the polymerization as an alternative energy (AE source. Ludovic® software, designed for simulation of the extrusion process, had to be modified in order to simulate the reactive extrusion of lactide and for the application of an AE source in an extruder. A mathematical model for the ROP of lactide reaction was developed to estimate the kinetics of the polymerization process. The isothermal curves generated through this model were then used by Ludovic software to simulate the “reactive” extrusion process of ROP of lactide. Results from the experiments and simulations were compared to validate the simulation methodology. It was observed that the application of an AE source boosts the polymerization of lactide monomers. However, it was also observed that the predicted residence time was shorter than the experimental one. There is potentially a case for reducing the residence time distribution (RTD in Ludovic® due to the ‘liquid’ monomer flow in the extruder. Although this change in parameters resulted in validation of the simulation, it was concluded that further research is needed to validate this assumption.

  1. A Model-Based Methodology for Integrated Design and Operation of Reactive Distillation Processes

    DEFF Research Database (Denmark)

    Mansouri, Seyed Soheil; Sales-Cruz, Mauricio; Huusom, Jakob Kjøbsted

    2015-01-01

    and resolved. A new approach isto tackle process intensification and controllability issues in an integrated manner, in the early stages of process design. This integrated and simultaneous synthesis approach provides optimal operation and moreefficient control of complex intensified systems that suffice...... bubble point algorithm is used to compute the reactive vapor-liquid equilibrium data set.The operation of the RDC at the highest driving force and other candidate points is compared through openloop and closed-loop analysis. By application of this methodology it is shown that designing the process atthe......Process intensification is a new approach that has the potential to improve existing processes as well as new designs of processes to achieve more profitable and sustainable production. However, many issues with respect to their implementation and operation is not clear; for example, the question...

  2. Reactivity of Dinitrogen Bound to Mid- and Late-Transition-Metal Centers

    NARCIS (Netherlands)

    Khoenkhoen, N.; de Bruin, B.; Reek, J.N.H.; Dzik, W.I.

    2015-01-01

    This review presents a comprehensive overview of the reactions of N-2 within the coordination sphere of transition metals of groups 6 to 9. Many of these metals mediate the reaction of N-2 with protons under reductive conditions, which can lead to the (catalytic) formation of ammonia or hydrazine, a

  3. Innovative reactive distillation process for the production of the MTBE substitute isooctane from isobutene

    Energy Technology Data Exchange (ETDEWEB)

    Chalakova, M. [Magdeburg Univ. (Germany). Process Systems Engineering; Kaur, R.; Mahajani, S. [Indian Inst. of Technology, Mumbai (India); Freund, H. [Max-Planck-Institute for Dynamics of Complex Technical Systems, Magdeburg (Germany); Sundmacher, K. [Magdeburg Univ. (Germany). Process Systems Engineering]|[Max-Planck-Institute for Dynamics of Complex Technical Systems, Magdeburg (Germany)

    2007-07-01

    Isooctane is a promising candidate to replace MTBE as gasoline additive if it can be produced in economically and environmentally efficient processes. A promising reaction way at mild conditions is the so called indirect alkylation of isobutene (IB). In the present work two innovative reactive distillation (RD) concepts where the reactions are carried out either simultaneously (fully integrated) or sequentially (partially integrated) are designed. Suitable operation conditions are identified and a comparison with the conventional process scheme under performance and economic aspects is carried out. (orig.)

  4. Transformation of quiescent adult oligodendrocyte precursor cells into malignant glioma through a multistep reactivation process.

    Science.gov (United States)

    Galvao, Rui Pedro; Kasina, Anita; McNeill, Robert S; Harbin, Jordan E; Foreman, Oded; Verhaak, Roel G W; Nishiyama, Akiko; Miller, C Ryan; Zong, Hui

    2014-10-07

    How malignant gliomas arise in a mature brain remains a mystery, hindering the development of preventive and therapeutic interventions. We previously showed that oligodendrocyte precursor cells (OPCs) can be transformed into glioma when mutations are introduced perinatally. However, adult OPCs rarely proliferate compared with their perinatal counterparts. Whether these relatively quiescent cells have the potential to transform is unknown, which is a critical question considering the late onset of human glioma. Additionally, the premalignant events taking place between initial mutation and a fully developed tumor mass are particularly poorly understood in glioma. Here we used a temporally controllable Cre transgene to delete p53 and NF1 specifically in adult OPCs and demonstrated that these cells consistently give rise to malignant gliomas. To investigate the transforming process of quiescent adult OPCs, we then tracked these cells throughout the premalignant phase, which revealed a dynamic multistep transformation, starting with rapid but transient hyperproliferative reactivation, followed by a long period of dormancy, and then final malignant transformation. Using pharmacological approaches, we discovered that mammalian target of rapamycin signaling is critical for both the initial OPC reactivation step and late-stage tumor cell proliferation and thus might be a potential target for both glioma prevention and treatment. In summary, our results firmly establish the transforming potential of adult OPCs and reveal an actionable multiphasic reactivation process that turns slowly dividing OPCs into malignant gliomas.

  5. Reactivities of d~0 transition metal complexes toward oxygen:Synthetic and mechanistic studies

    Institute of Scientific and Technical Information of China (English)

    CHEN ShuJian; ZHANG XinHao; LIN ZhenYang; WU YunDong; XUE ZiLing

    2009-01-01

    Transition metals such as Fe in porphyrin complexes are known to bind or react with O_2,and such reactions are critical to many biological functions and catalytic oxidation using O_2.The transition metals in these reactions often contain valence d electrons,and oxidation of metals is an important step.In recent years,reactions of O_2 with d~0 transition metal complexes such as Hf(NR_2)_4 (R=alkyl) have been used to make metal oxide thin films as insulating gate materials in new microelectronic devices.This feature article discusses our recent studies of such reactions and the formation of TiO_2 thin films.In contrast to the reactions of many d~n complexes where metals are often oxidized,reactions of d~0 complexes such as Hf(Nme_2)_4 and Ta(Nme_2)_4(SiR_3) with O_2 usually lead to the oxidation of ligands,forming,e.g.,-ONMe_2 and-OSiR_3 from-Nme_2 and-SiR_3 ligands,respectively.Mechanistic and theoretical studies of these reactions have revealed pathways in the formation of the metal oxide thin films as microelectronic materials.

  6. Reactivities of d~0 transition metal complexes toward oxygen:Synthetic and mechanistic studies

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Transition metals such as Fe in porphyrin complexes are known to bind or react with O2,and such reactions are critical to many biological functions and catalytic oxidation using O2.The transition metals in these reactions often contain valence d electrons,and oxidation of metals is an important step.In recent years,reactions of O2 with d0 transition metal complexes such as Hf(NR2)4(R=alkyl) have been used to make metal oxide thin films as insulating gate materials in new microelectronic devices.This feature article discusses our recent studies of such reactions and the formation of TiO2 thin films.In contrast to the reactions of many dn complexes where metals are often oxidized,reactions of d0 complexes such as Hf(NMe2)4 and Ta(NMe2)4(SiR3) with O2 usually lead to the oxidation of ligands,forming,e.g.,-ONMe2 and -OSiR3 from-NMe2 and-SiR3 ligands,respectively.Mechanistic and theoretical studies of these reactions have revealed pathways in the formation of the metal oxide thin films as microelectronic materials.

  7. Advanced Wear Simulation for Bulk Metal Forming Processes

    Directory of Open Access Journals (Sweden)

    Behrens Bernd-Arno

    2016-01-01

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

  8. Controlled rejuvenation of amorphous metals with thermal processing.

    Science.gov (United States)

    Wakeda, Masato; Saida, Junji; Li, Ju; Ogata, Shigenobu

    2015-05-26

    Rejuvenation is the configurational excitation of amorphous materials and is one of the more promising approaches for improving the deformability of amorphous metals that usually exhibit macroscopic brittle fracture modes. Here, we propose a method to control the level of rejuvenation through systematic thermal processing and clarify the crucial feasibility conditions by means of molecular dynamics simulations of annealing and quenching. We also experimentally demonstrate rejuvenation level control in Zr(55)Al(10)Ni(5)Cu(30) bulk metallic glass. Our local heat-treatment recipe (rising temperature above 1.1T(g), followed by a temperature quench rate exceeding the previous) opens avenue to modifying the glass properties after it has been cast and processed into near component shape, where a higher local cooling rate may be afforded by for example transient laser heating, adding spatial control and great flexibility to the processing.

  9. Method for conducting electroless metal-plating processes

    Science.gov (United States)

    Petit, George S.; Wright, Ralph R.

    1978-01-01

    This invention is an improved method for conducting electroless metal-plating processes in a metal tank which is exposed to the plating bath. The invention solves a problem commonly encountered in such processes: how to determine when it is advisable to shutdown the process in order to clean and/or re-passivate the tank. The new method comprises contacting the bath with a current-conducting, non-catalytic probe and, during plating operations, monitoring the gradually changing difference in electropotential between the probe and tank. It has been found that the value of this voltage is indicative of the extent to which nickel-bearing decomposition products accumulate on the tank. By utilizing the voltage to determine when shutdown for cleaning is advisable, the operator can avoid premature shutdown and at the same time avoid prolonging operations to the point that spontaneous decomposition occurs.

  10. Mechanisms of acoustic processing of a metal melt containing nanoparticles

    Science.gov (United States)

    Kudryashova, O.; Vorozhtsov, S.; Dubkova, Ya.; Stepkina, M.

    2016-11-01

    Wave processing with the frequencies from subsound (vibration) to ultrasound is used to produce nanopowder-modified composite alloys. This work considers mechanisms of such processing of metal melts, which lead to deagglomeration and wettability of particles of a metal melt and to the destruction of growing crystals during solidification. The main dependences for the threshold of the turbulence and cavitation were obtained. Resonance phenomena that contribute to positive changes in the melt are discussed. Possible mechanisms of the destruction of growing crystals and agglomerates of particles at the high-frequency processing of the melt are considered, including the destruction of agglomerates in the front of an acoustic wave and the destruction of crystals by oscillating solid particles.

  11. Possible Processes For Acidity And Metal Contaminant Attenuation In A Polluted Estuarine Aquifer

    Science.gov (United States)

    Patrick, E.; Xiaomin, M.; Andrew, B.; Ling, L.; Andrew, B.

    2003-12-01

    Geochemical data obtained from an estuarine sandy aquifer situated below an old industrial landfill (Ayrshire, Scotland) indicated that acidic groundwater (pH acidic plume, elevated concentrations of dissolved heavy metals (Al, Zn, Cu, Cr, Cd) were observed. Water table monitoring and chemical data showed that the groundwater is intruded by estuarine water and is tidally influenced. While geochemical processes associated with acidic plumes and related metal contamination have been widely studied in inland aquifer systems, they have received much less attention in near shore aquifers. Rarely have processes taking place in tidally influenced acidic aquifers been investigated in detail in the field. The aim of the study was to identify the key processes controlling the migration of the acidic plume and reactive transport of contaminants on the path from the aquifer to the estuary. More specifically, the research work has focused on the role played by estuarine water intrusion on the geochemical processes occurring in the aquifer. Through integration of intense geophysical, hydrogeological and hydrogeochemical Investigations, a comprehensive field-monitoring program and laboratory experiments have been carried out. Data obtained were analysed using a geochemical modelling code, PHREEQC-2. In parallel, a model for multi-components reactive transport with density dependent flow was developed and applied to the site. Results from the field, laboratory, and modelling work indicated that oxidation of sulphurous waste located in the landfill at the pollution source is the origin of the groundwater acidity. The low pH plume and associated contaminants are slowly migrating towards the estuary. Retardation of the plume and pH buffering processes are clearly occurring in the aquifer. Ion exchange, precipitation, buffering mineral dissolution, and tidal forcing on the advective-dispersive transport were identified as the main factors influencing contaminant migration and

  12. Removal of heavy metal ions from oil shale beneficiation process water by ferrite process

    Energy Technology Data Exchange (ETDEWEB)

    Mehta, R.K.; Zhang, L.; Lamont, W.E.; Schultz, C.W. [Alabama Univ., University, AL (United States). Mineral Resources Inst.

    1991-12-31

    The ferrite process is an established technique for removing heavy metals from waste water. Because the process water resulting from oil shale beneficiation falls into the category of industrial waste water, it is anticipated that this process may turn out to be a potential viable treatment for oil shale beneficiation process water containing many heave metal ions. The process is chemoremedial because not only effluent water comply with quality standards, but harmful heavy metals are converted into a valuable, chemically stable by-product known as ferrite. These spinel ferrites have magnetic properties, and therefore can be use in applications such as magnetic marker, ferrofluid, microwave absorbing and scavenging material. Experimental results from this process are presented along with results of treatment technique such as sulfide precipitation.

  13. Removal of heavy metal ions from oil shale beneficiation process water by ferrite process

    Energy Technology Data Exchange (ETDEWEB)

    Mehta, R.K.; Zhang, L.; Lamont, W.E.; Schultz, C.W. (Alabama Univ., University, AL (United States). Mineral Resources Inst.)

    1991-01-01

    The ferrite process is an established technique for removing heavy metals from waste water. Because the process water resulting from oil shale beneficiation falls into the category of industrial waste water, it is anticipated that this process may turn out to be a potential viable treatment for oil shale beneficiation process water containing many heave metal ions. The process is chemoremedial because not only effluent water comply with quality standards, but harmful heavy metals are converted into a valuable, chemically stable by-product known as ferrite. These spinel ferrites have magnetic properties, and therefore can be use in applications such as magnetic marker, ferrofluid, microwave absorbing and scavenging material. Experimental results from this process are presented along with results of treatment technique such as sulfide precipitation.

  14. Development of chiral metal amides as highly reactive catalysts for asymmetric [3 + 2] cycloadditions

    Science.gov (United States)

    Yamashita, Yasuhiro; Yoshimoto, Susumu; Dutton, Mark J

    2016-01-01

    Summary Highly efficient catalytic asymmetric [3 + 2] cycloadditions using a chiral copper amide are reported. Compared with the chiral CuOTf/Et3N system, the CuHMDS system showed higher reactivity, and the desired reactions proceeded in high yields and high selectivities with catalyst loadings as low as 0.01 mol %. PMID:27559396

  15. Kinetic and mechanistic studies of reactive intermediates in photochemical and transition metal-assisted oxidation, decarboxylation and alkyl transfer reactions

    Science.gov (United States)

    Carraher, Jack McCaslin

    Reactive species like high-valent metal-oxo complexes and carbon and oxygen centered radicals are important intermediates in enzymatic systems, atmospheric chemistry, and industrial processes. Understanding the pathways by which these intermediates form, their relative reactivity, and their fate after reactions is of the utmost importance. Herein are described the mechanistic detail for the generation of several reactive intermediates, synthesis of precursors, characterization of precursors, and methods to direct the chemistry to more desirable outcomes yielding 'greener' sources of commodity chemicals and fuels. High-valent Chromium from Hydroperoxido-Chromium(III). The decomposition of pentaaquahydroperoxido chromium(III) ion (hereafter Cr aqOOH2+) in acidic aqueous solutions is kinetically complex and generates mixtures of products (Craq3+, HCrO 4-, H2O2, and O2). The yield of high-valent chromium products (known carcinogens) increased from a few percent at pH 1 to 70 % at pH 5.5 (near biological pH). Yields of H 2O2 increased with acid concentration. The reproducibility of the kinetic data was poor, but became simplified in the presence of H2O2 or 2,2‧-azinobis(3-ethylbenzothiazoline-6-sulfonate) dianion (ABTS2-). Both are capable of scavenging strongly oxidizing intermediates). The observed rate constants (pH 1, [O2] ≤ 0.03 mM) in the presence of these scavengers are independent of [scavenger] and within the error are the same (k,ABTS2- = (4.9 +/- 0.2) x 10-4 s-1 and kH2O2 = (5.3 +/- 0.7) x 10-4 s-1); indicating involvement of the scavengers in post-rate determining steps. In the presence of either scavenger, decomposition of CrOOH2+ obeyed a two-term rate law, k obs / s-1 = (6.7 +/- 0.7) x 10-4 + (7.6 +/- 1.1) x 10-4 [H+]. Effect of [H+] on the kinetics and the product distribution, cleaner kinetics in the presence of scavengers, and independence of kobs on [scavenger] suggest a dual-pathway mechanism for the decay of Craq OOH2+. The H+-catalyzed path

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

    Science.gov (United States)

    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.

  17. Sheets of branched poly(lactic acid obtained by one step reactive extrusion calendering process: Melt rheology analysis

    Directory of Open Access Journals (Sweden)

    J. Cailloux

    2013-03-01

    Full Text Available One-step reactive extrusion-calendering process (REX-Calendering was used in order to obtain sheets of 1mm from two PD,L-LA extrusion grades modified with a styrene-acrylic multifunctional oligomeric agent. In a preliminary internal mixer study, torque versus time was monitored in order to determine chain extender ratios and reaction time. Once all parameters were optimized, reactive extrusion experiments were performed. Independently of the processing method employed, under the same processing conditions, PD,L-LA with the lower D enantiomer molar content revealed a higher reactivity towards the reactive agent, induced by its higher thermal sensitivity. REXCalendering process seemed to minimize the degradations reactions during processing, although a competition between degradation and chain extension/branching reactions took place in both processes. Finally, the rheological characterization revealed a higher degree of modification in the melt rheological behaviour for REX-Calendered samples.

  18. Relationships among total recoverable and reactive metals and metalloid in St. Lawrence River sediment: bioaccumulation by chironomids and implications for ecological risk assessment.

    Science.gov (United States)

    Desrosiers, Mélanie; Gagnon, Christian; Masson, Stéphane; Martel, Louis; Babut, Marc P

    2008-01-15

    The availability and bioaccumulation of metals and metalloids, and the geochemical interactions among them, are essential to developing an ecological risk assessment (ERA) framework and determining threshold concentrations for these elements. The purpose of this study was to explore the relationships among total recoverable and reactive metals and metalloid in sediment and their bioaccumulation by chironomids. In the fall of 2004 and 2005, 58 stations located in the three fluvial lakes of the St. Lawrence River and its largest harbour area in Montreal, Canada, were sampled. Nine total recoverable and reactive metals (Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) and one metalloid (As) were measured in whole sediment using two extraction methods: HCl/HNO(3) and HCl 1N, respectively. The bioaccumulation of six metals (Cd, Cr, Cu, Ni, Pb and Zn) and As by chironomids was evaluated in a subset of 22 stations. Strong collinearities were observed between some total recoverable or reactive metal concentrations in sediment; two principal clusters, including collinear metals, were obtained. The first one included metals of mainly geological origin (Al, Cr, Fe, Mn, Ni), while the second one included As, Cd, Cu, Pb and Zn, which likely derive mainly from point sources of anthropogenic contamination. Each element also showed strong collinearity between their total recoverable and reactive forms (0.65Pb in sediment. Arsenic was an exception, with accumulation by chironomids being highly related to reactive sediment concentrations. Finally, we observed variable influences of explanatory factors (e.g. sediment grain size, Al, Fe, Mn, S, TOC), depending on which metal or metalloid was being predicted in chironomids. In this context, it is difficult to choose a universal predictive method to explain the bioaccumulation of specific metals, and more research is still needed into normalization procedures that consider a combination of explanatory factors.

  19. Characterising the reactivity of metallic iron in Fe0/As-rock/H O ...

    African Journals Online (AJOL)

    2011-06-03

    Jun 3, 2011 ... arsenic, azo dyes, bacteria, halogenated organic compounds, heavy metals, nitrates ..... ers during clean-up of copper containing solutions. Miner. Eng. 20 .... ment and interpretation of hydrogen evolution rates. Environ. Sci.

  20. The Chemophytostabilisation Process of Heavy Metal Polluted Soil.

    Science.gov (United States)

    Grobelak, Anna; Napora, Anna

    2015-01-01

    Industrial areas are characterised by soil degradation processes that are related primarily to the deposition of heavy metals. Areas contaminated with metals are a serious source of risk due to secondary pollutant emissions and metal leaching and migration in the soil profile and into the groundwater. Consequently, the optimal solution for these areas is to apply methods of remediation that create conditions for the restoration of plant cover and ensure the protection of groundwater against pollution. Remediation activities that are applied to large-scale areas contaminated with heavy metals should mainly focus on decreasing the degree of metal mobility in the soil profile and metal bioavailability to levels that are not phytotoxic. Chemophytostabilisation is a process in which soil amendments and plants are used to immobilise metals. The main objective of this research was to investigate the effects of different doses of organic amendments (after aerobic sewage sludge digestion in the food industry) and inorganic amendments (lime, superphosphate, and potassium phosphate) on changes in the metals fractions in soils contaminated with Cd, Pb and Zn during phytostabilisation. In this study, the contaminated soil was amended with sewage sludge and inorganic amendments and seeded with grass (tall fescue) to increase the degree of immobilisation of the studied metals. The contaminated soil was collected from the area surrounding a zinc smelter in the Silesia region of Poland (pH 5.5, Cd 12 mg kg-1, Pb 1100 mg kg-1, Zn 700 mg kg-1). A plant growth experiment was conducted in a growth chamber for 5 months. Before and after plant growth, soil subsamples were subjected to chemical and physical analyses. To determine the fractions of the elements, a sequential extraction method was used according to Zeien and Brümmer. Research confirmed that the most important impacts on the Zn, Cd and Pb fractions included the combined application of sewage sludge from the food industry and

  1. The Chemophytostabilisation Process of Heavy Metal Polluted Soil.

    Directory of Open Access Journals (Sweden)

    Anna Grobelak

    Full Text Available Industrial areas are characterised by soil degradation processes that are related primarily to the deposition of heavy metals. Areas contaminated with metals are a serious source of risk due to secondary pollutant emissions and metal leaching and migration in the soil profile and into the groundwater. Consequently, the optimal solution for these areas is to apply methods of remediation that create conditions for the restoration of plant cover and ensure the protection of groundwater against pollution. Remediation activities that are applied to large-scale areas contaminated with heavy metals should mainly focus on decreasing the degree of metal mobility in the soil profile and metal bioavailability to levels that are not phytotoxic. Chemophytostabilisation is a process in which soil amendments and plants are used to immobilise metals. The main objective of this research was to investigate the effects of different doses of organic amendments (after aerobic sewage sludge digestion in the food industry and inorganic amendments (lime, superphosphate, and potassium phosphate on changes in the metals fractions in soils contaminated with Cd, Pb and Zn during phytostabilisation. In this study, the contaminated soil was amended with sewage sludge and inorganic amendments and seeded with grass (tall fescue to increase the degree of immobilisation of the studied metals. The contaminated soil was collected from the area surrounding a zinc smelter in the Silesia region of Poland (pH 5.5, Cd 12 mg kg-1, Pb 1100 mg kg-1, Zn 700 mg kg-1. A plant growth experiment was conducted in a growth chamber for 5 months. Before and after plant growth, soil subsamples were subjected to chemical and physical analyses. To determine the fractions of the elements, a sequential extraction method was used according to Zeien and Brümmer. Research confirmed that the most important impacts on the Zn, Cd and Pb fractions included the combined application of sewage sludge from the

  2. Microstructure and strength of a deformation processed aluminum-20%tin metal-metal composite

    Science.gov (United States)

    Xu, Kai

    An Al-20vol.% Sn metal-metal composite was deformation processed by extrusion, swaging, and wire drawing to a total true strain of 7.4, resulting in a microstructure with Sn filaments in an Al matrix. Both the size and spacing of the Sn filaments decreased as deformation processing progressed. Immediately after deformation, the Sn second phase showed a convoluted, ribbon-shaped filamentary morphology, but the Sn filaments spheroidized during prolonged storage at room temperature. The driving force for spheroidization is chemical potential gradient due to curvature difference along Sn filaments. A critical wavelength of lambda crit = 2piR can be used to determine the spheroidization tendency of Sn cylinder. When lambda > 2piR, spheroidization is predicted to occur. The strength of these composites increased exponentially with the reduction in spacing of the Sn filaments. The relationship between UTS and deformation true strain is UTS = 72.6 exp(0.20eta). A Hall-Petch relationship between strength and filament spacing has been observed. Strengthening results from the filaments acting as barriers for dislocation motion. The primary shape instability modes are cylinderization of ribbons, boundary splitting, spheroidization of cylinders, and edge spheroidization of ribbons. The determining factors dictating which mechanism is active are grain boundary energy, interfacial energy, and ribbon cross section aspect ratio. The fiber texture was determined by orientation imaging microscopy to be for Al and for Sn. The 290 MPa ultimate tensile strength of the composite was greater than the rule-of-mixtures prediction. Comparisons are made with Al-Nb, Al-Ti and Al-Mg deformation processed metal metal composites and to various strengthening models for metal-metal composites.

  3. SOLVENT EXTRACTION PROCESS FOR SEPARATING ACTINIDE AND LANTHANIDE METAL VALUES

    Science.gov (United States)

    Hildebrandt, R.A.; Hyman, H.H.; Vogler, S.

    1962-08-14

    A process of countercurrently extracting an aqueous mineral acid feed solution for the separation of actinides from lanthanides dissolved therern is described. The feed solution is made acid-defrcient with alkali metal hydroxide prior to.contact with acid extractant; during extraction, however, acid is transferred from organic to aqueous solution and the aqueous solution gradually becomes acid. The acid-deficient phase ' of the process promotes the extraction of the actinides, while the latter acid phase'' of the process improves retention of the lanthanides in the aqueous solution. This provides for an improved separation. (AEC)

  4. Different strategies for recovering metals from CARON process residue

    Energy Technology Data Exchange (ETDEWEB)

    Cabrera, G., E-mail: gema.cabrera@uca.es [Biological and Enzymatic Reactors Group, Department of Chemical Engineering and Food Technology, Faculty of Sciences, University of Cadiz (Spain); Gomez, J.M., E-mail: josemanuel.montesdeoca@uca.es [Biological and Enzymatic Reactors Group, Department of Chemical Engineering and Food Technology, Faculty of Sciences, University of Cadiz (Spain); Hernandez, I., E-mail: ianeyahd@fbio.uh.cu [Laboratory of Metals, Department of Microbiology, Faculty of Biology, University of Havana (Cuba); Coto, O., E-mail: ocoto@fbio.uh.cu [Laboratory of Metals, Department of Microbiology, Faculty of Biology, University of Havana (Cuba); Cantero, D., E-mail: domingo.cantero@uca.es [Biological and Enzymatic Reactors Group, Department of Chemical Engineering and Food Technology, Faculty of Sciences, University of Cadiz (Spain)

    2011-05-30

    The capacity of Acidithiobacillus thiooxidans DMS 11478 to recover the heavy metals contained in the residue obtained from the CARON process has been evaluated. Different bioreactor configurations were studied: a two-stage batch system and two semi-continuous systems (stirred-tank reactor leaching and column leaching). In the two-stage system, 46.8% Co, 36.0% Mg, 26.3% Mn and 22.3% Ni were solubilised after 6 h of contact between the residue and the bacteria-free bioacid. The results obtained with the stirred-tank reactor and the column were similar: 50% of the Mg and Co and 40% of the Mn and Ni were solubilised after thirty one days. The operation in the column reactor allowed the solid-liquid ratio to be increased and the pH to be kept at low values (<1.0). Recirculation of the leachate in the column had a positive effect on metal removal; at sixty five days (optimum time) the solubilisation levels were as follows: 86% Co, 83% Mg, 72% Mn and Ni, 62% Fe and 23% Cr. The results corroborate the feasibility of the systems studied for the leaching of metals from CARON process residue and these methodologies can be considered viable for the recovery of valuable metals.

  5. Process, structure, property and applications of metallic glasses

    Directory of Open Access Journals (Sweden)

    B. Geetha Priyadarshini

    2016-07-01

    Full Text Available Metallic glasses (MGs are gaining immense technological significance due to their unique structure-property relationship with renewed interest in diverse field of applications including biomedical implants, commercial products, machinery parts, and micro-electro-mechanical systems (MEMS. Various processing routes have been adopted to fabricate MGs with short-range ordering which is believed to be the genesis of unique structure. Understanding the structure of these unique materials is a long-standing unsolved mystery. Unlike crystalline counterpart, the outstanding properties of metallic glasses owing to the absence of grain boundaries is reported to exhibit high hardness, excellent strength, high elastic strain, and anti-corrosion properties. The combination of these remarkable properties would significantly contribute to improvement of performance and reliability of these materials when incorporated as bio-implants. The nucleation and growth of metallic glasses is driven by thermodynamics and kinetics in non-equilibrium conditions. This comprehensive review article discusses the various attributes of metallic glasses with an aim to understand the fundamentals of relationship process-structure-property existing in such unique class of material.

  6. s-Process in Low Metallicity Stars. I. Theoretical Predictions

    CERN Document Server

    Bisterzo, S; Straniero, O; Cristallo, S; Kaeppeler, F

    2010-01-01

    A large sample of carbon enhanced metal-poor stars enriched in s-process elements (CEMP-s) have been observed in the Galactic halo. These stars of low mass (M ~ 0.9 Msun) are located on the main-sequence or the red giant phase, and do not undergo third dredge-up (TDU) episodes. The s-process enhancement is most plausibly due to accretion in a binary system from a more massive companion when on the asymptotic giant branch (AGB) phase (now a white dwarf). In order to interpret the spectroscopic observations, updated AGB models are needed to follow in detail the s-process nucleosynthesis. We present nucleosynthesis calculations based on AGB stellar models obtained with FRANEC (Frascati Raphson-Newton Evolutionary Code) for low initial stellar masses and low metallicities. For a given metallicity, a wide spread in the abundances of the s-process elements is obtained by varying the amount of 13C and its profile in the pocket, where the 13C(a, n)16O reaction is the major neutron source, releasing neutrons in radiat...

  7. A Study on Reactive Spray Deposition Technology Processing Parameters in the Context of Pt Nanoparticle Formation

    Science.gov (United States)

    Roller, Justin M.; Maric, Radenka

    2015-12-01

    Catalytic materials are complex systems in which achieving the desired properties (i.e., activity, selectivity and stability) depends on exploiting the many degrees of freedom in surface and bulk composition, geometry, and defects. Flame aerosol synthesis is a process for producing nanoparticles with ample processing parameter space to tune the desired properties. Flame dynamics inside the reactor are determined by the input process variables such as solubility of precursor in the fuel; solvent boiling point; reactant flow rate and concentration; flow rates of air, fuel and the carrier gas; and the burner geometry. In this study, the processing parameters for reactive spray deposition technology, a flame-based synthesis method, are systematically evaluated to understand the residence times, reactant mixing, and temperature profiles of flames used in the synthesis of Pt nanoparticles. This provides a framework for further study and modeling. The flame temperature and length are also studied as a function of O2 and fuel flow rates.

  8. Electronmicroscopic Study of Sand Erosion Processes in Metals.

    Science.gov (United States)

    1979-06-01

    AO—A073 k97 ISRAEL INST OF MEtALS HAIFA - ~ - - — Ffl 11/6 ELECTROI~~ICROSCOPIC STUDY OF SAND EROSION PROCESSES IN METALS, IU) UNCLASSIFIED 79...General Appearance 8 4.2.2 Local Erosion Processes and Hard Phase Par t icles 9 5. Further Discussion 10 S S-_ S _~S _~~SS ~~~ S ~~~~~~~~~~~~~~~~~~ __SS...research was to ga in addit iona l unders tan di ng of the mechanism of loca l mater ia l removal from eroded compos ite meta l l i c surface

  9. New synthesis ways of supported metallic catalysts and structure-reactivity relations in catalysis by metals; Nouvelles voies de syntheses de catalyseurs metalliques supportes et relations structure-reactivite en catalyse par les metaux

    Energy Technology Data Exchange (ETDEWEB)

    Uzio, D.

    2006-01-15

    This work deals with some research studies in the field of supported metallic catalysts. In all these works have been studied the characteristics bound to the active sites and the relations between these characteristics and the catalytic performances. The genesis of colloidal suspensions of transition metallic oxide has been used for the preparation of selective hydrogenation catalysts. At first studied in the case of palladium, this new synthesis way has been used for other metals such as Pt, Ni or Co. These studies have then been developed for preparing bimetallic catalysts (PdSn) with as supplementary aim the control of the homogeneity of the bimetallic character at the scale of nano-metric particles. These works have particularly allowed to specify the chemistry of the solutions of some metallic complexes and to rationalize the chemical processes carried out in the usual fabrication processes. Studies on size effects and the study of the reactivity of the nano and sub nano-metric particle have then been developed. Indeed, the clusters containing some atoms can see their intrinsic properties varied very strongly under the influence of several parameters as the number of atoms, the nature of the support, the reactional atmosphere. Using the knowledge acquired during the preceding works (chemistry of palladium aqueous solutions), the study of new methods of preparation of particles containing very few atoms has brought new data on the properties of hyper dispersed particles as well as on the principle of sensitivity to structure. The contribution of the support to the catalytic process for the hydrogenation of different substrates has been studied too. (O.M.)

  10. Flexible Reactive Berm (FRBerm) for Removal of Heavy Metals from Runoff Water

    Science.gov (United States)

    2016-03-01

    minerals, goethite and hematite , and remained immobilized (Ford et al. 1997, Martinez and McBride 1998). 2 Copper, Pb, Ni, and Zn have also been...width), m h = water depth immediately upstream of the filter, m The primary hydraulic features of sand filter socks are shown in Figure 6, where, v...untreated storm runoff water into the entire length of the trench. Therefore, each reactive barrier in the trench functioned more as a primary

  11. Chemical Cleaning of Metal Surfaces in Vacuum Systems by Exposure to Reactive Gases.

    Science.gov (United States)

    1987-11-10

    Phys. Letters 39 (1976) 113. 196. P.E. Luscher , Surface Sci. 66 (1977) 167. 197. M. Housley and C.A. King, Surface Sci. 62 (1977) 81, 93. 193. M.K. Debe... Physics and Astronomy Barrows Hall University of Maine Orono, ME 04469 ............... November 10, 1987 Reproduction in whole or in part is permitted...Exposure to Reactive Gases M. Grunze*, H. Ruppender and 0. Elshazly Laboratory for Surface Science and Technology and Department of Physics and

  12. Anti Zn antibodies: cross reactivity and competitive binding with heavy metals.

    Science.gov (United States)

    Sarada, N C; Thamaraiselvi, K; Vijayalakshmi, M A

    2008-01-15

    Monoclonal antibodies of IgM class, specific to IDA-Zn were used for evaluating their Zn(2+) binding efficiency in the presence of trace metal ions such as Cr(3+) Cr(6+), Cu(2+) and Cd(2+). In the present work, antibody raised against the hapten IDA-Zn(II) was pre-incubated with different metal ions and the binding capacity to the specific hapten was tested using ELISA and immobilized metal ion affinity chromatography (IMAC) techniques. IMAC was carried out with the free antibody and antibody pre-incubated with selected heavy metal ions using Sepharose IDA-Zn(2+) column and the same samples were tested using a hapten specific ELISA with non-protein hapten carrier. Different effects were observed after pre-incubation with metal ions. Cr(3+) exhibited synergistic binding where as antagonism was detected with Cd(2+). The synergistic effect observed with Cr(3+) suggests involvement of binding sites other than that of zinc and conformational changes that result from Cr(3+) binding. It is probable that, this binding event also increases the accessibility of the zinc binding sites on IgM. On the same lines, the antagonism observed with Cd(2+) could be attributed to structural changes resulting in reduced accessibility to zinc binding sites. In case of Cr(6+), no appreciable change in binding to IDA-Zn was observed while Cu(2+) showed competitive binding.

  13. Kinetic-Thermodynamic Analysis of the Reactive Distillation Process of the Cyclohexene Hydration Using the Zeolite Catalyst

    Institute of Scientific and Technical Information of China (English)

    叶建初; 黄佳丽; 林晗丹; 曹克腾; 沙勇

    2011-01-01

    Reactive distillation could be utilized to produce cyclohexanol through the cyclohexene hydration. By means of highly active zeolite catalyst HZSM-5, the kinetic-thermodynamic analysis of this reactive distillation has been carried out to get the characteristics of the reactive distillation. Results from kinetic and thermodynamic analysis indicate that the optimal pressure of this reactive distillation process should be set to higher pressure such as 0.3 or 0.4 MPa. To avoid the recovery of cyclohexanol at the top of the column, an unreactive section should be allocated at the upper column. In addition, the inert component benzene is more unfavorable to the reactive distillation process in comparison with the inert cyclohexane.

  14. Metal ion coordination in `R’ and `T’ state hybrid hemoglobins as revealed by optical, EPR and sulphhydryl reactivity studies

    Indian Academy of Sciences (India)

    S Ramasamy; Swarnalatha Venkateshrao; J M Rifkind; P T Manoharan

    2005-03-01

    The sulphhydryl environment in various mixed-metal hybrid hemoglobins, viz. 2(Cu)-2(FeCO), 2(FeCO)-2(Cu), 2(Cu)-2(Ni), 2(Ni)-2(Cu), was studied by reacting them with the sulphhydryl reagent, 4,4'-dithiodipyridine (4-PDS). The reactivity was compared with that of HbCO, NiHb and CuHb. It is found that there exists a correlation between conformational change and metal ion environment, not only at the extreme R and T states but also the intermediate conformations. EPR examinations of these hybrids show that both in 4R state-[Cu(II)-Fe(II)] and state-[Cu(II)-Ni(II)] hybrids at neutral pH and in the absence of IHP, CuPPIX, irrespective of the subunit in which it is present, has a mixed-metal ion environment: Species 1, a five-coordinated Cu2+ complex with strong proximal histidine bond and species 2, a four-coordinated complex without any covalent linkage with N F8-histidine.

  15. Microstructural behavior of nitriding compound layer for Nb-carbonitride coating grown by thermo-reactive diffusion process

    Science.gov (United States)

    Lee, Kyunghoon; Kang, Namhyun; Bae, Jong-Seong; Lee, Chang-Woo

    2016-09-01

    This study aims to understand the microstructural behavior of nitriding compound layer and its effect on Nb-carbonitride growth produced by the thermo-reactive diffusion (TRD) process. Gas nitriding was performed at 550 °C for 3 and 6 h, followed by TRD at 900 °C for 6 h. The nitriding compound layers had thicknesses of 10 and 16 μm for nitriding time of 3 and 6 h, respectively. The corresponding Nb-carbonitride layers produced by TRD were 7.2 and 11.2 μm thick, respectively. Reheating at 900 °C transformed the microstructure of the nitriding compounds to Fe3O4 and FeN0.0939. As reheating proceeded to 30 min, high concentration of nitrogen, initially existing in the nitride layer diffused to 80-90 μm into the substrate. Therefore, the TRD process produced NbN layer at the interfacial area due to intensively dissolved nitrogen from FeN0.0939. As the TRD proceeded, supply of C atoms from the base metal became competitive with the N diffusion. Thus, the TRD coating layer was grown to above the interface. Reheating at 900 °C for the 16-μm-thick nitride layer resulted in a nitrogen content ˜0.4 at% higher than that for the 10-μm-thick nitride layer, thereby producing a thicker Nb-carbonitride layer.

  16. Reactive transport modeling of coupled inorganic and organic processes in groundwater

    Energy Technology Data Exchange (ETDEWEB)

    Brun, Adam

    1997-12-31

    The main goals of this project are to develop and apply a reactive transport code for simulation of coupled organic and inorganic processes in the pollution plume in the ground water down-gradient from the Vejen landfill, Denmark. The detailed field investigations in this aquifer have previously revealed a complex pattern of strongly interdependent organic and inorganic processes. These processes occur simultaneously in a flow and transport system where the mixing of reactive species is influenced by the rather complex geology in the vicinity of the landfill. The removal of organic matter is influenced by the presence of various electron acceptors that also are involved in various inorganic geochemical reactions. It was concluded from the investigations that degradation of organic matter, complexation, mineral precipitation and dissolution, ion-exchange and inorganic redox reactions, as a minimum, should be included in the formulation of the model. The coupling of the organic and inorganic processes is developed based on a literature study. All inorganic processes are as an approximation described as equilibriumm processes. The organic processes are described by a maximum degradation rate that is decreased according to the availability of the participants in the processes, the actual pH, and the presence of inhibiting species. The reactive transport code consists of three separate codes, a flow and transport code, a geochemical code, and a biodegradation code. An iterative solution scheme couples the three codes. The coupled code was successfully verified for simple problems for which analytical solutions exist. For more complex problems the code was tested on synthetic cases and expected plume behavior was successfully simulated. Application of the code to the Vejen landfill aquifer was successful to the degree that the redox zonation down-gradient from the landfill was simulated correctly and that several of the simulated plumes showed a reasonable agreement with

  17. Early stage oxynitridation process of Si(001) surface by NO gas: Reactive molecular dynamics simulation study

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Haining; Kim, Seungchul; Lee, Kwang-Ryeol, E-mail: krlee@kist.re.kr [Computational Science Research Center, Korea Institute of Science and Technology, 5, Hwarangno 14-gil, Seongbuk-gu, Seoul 02792 (Korea, Republic of); Department of Nanomaterial Science and Technology, Korea University of Science and Technology, 217 Gajeong-ro, Yuseong-gu, Daejeon 34113 (Korea, Republic of); Srivastava, Pooja; Choi, Keunsu [Computational Science Research Center, Korea Institute of Science and Technology, 5, Hwarangno 14-gil, Seongbuk-gu, Seoul 02792 (Korea, Republic of)

    2016-03-28

    Initial stage of oxynitridation process of Si substrate is of crucial importance in fabricating the ultrathin gate dielectric layer of high quality in advanced MOSFET devices. The oxynitridation reaction on a relaxed Si(001) surface is investigated via reactive molecular dynamics (MD) simulation. A total of 1120 events of a single nitric oxide (NO) molecule reaction at temperatures ranging from 300 to 1000 K are statistically analyzed. The observed reaction kinetics are consistent with the previous experimental or calculation results, which show the viability of the reactive MD technique to study the NO dissociation reaction on Si. We suggest the reaction pathway for NO dissociation that is characterized by the inter-dimer bridge of a NO molecule as the intermediate state prior to NO dissociation. Although the energy of the inter-dimer bridge is higher than that of the intra-dimer one, our suggestion is supported by the ab initio nudged elastic band calculations showing that the energy barrier for the inter-dimer bridge formation is much lower. The growth mechanism of an ultrathin Si oxynitride layer is also investigated via consecutive NO reactions simulation. The simulation reveals the mechanism of self-limiting reaction at low temperature and the time evolution of the depth profile of N and O atoms depending on the process temperature, which would guide to optimize the oxynitridation process condition.

  18. Reactive transport modelling of biogeochemical processes and carbon isotope geochemistry inside a landfill leachate plume.

    Science.gov (United States)

    van Breukelen, Boris M; Griffioen, Jasper; Röling, Wilfred F M; van Verseveld, Henk W

    2004-06-01

    The biogeochemical processes governing leachate attenuation inside a landfill leachate plume (Banisveld, the Netherlands) were revealed and quantified using the 1D reactive transport model PHREEQC-2. Biodegradation of dissolved organic carbon (DOC) was simulated assuming first-order oxidation of two DOC fractions with different reactivity, and was coupled to reductive dissolution of iron oxide. The following secondary geochemical processes were required in the model to match observations: kinetic precipitation of calcite and siderite, cation exchange, proton buffering and degassing. Rate constants for DOC oxidation and carbonate mineral precipitation were determined, and other model parameters were optimized using the nonlinear optimization program PEST by means of matching hydrochemical observations closely (pH, DIC, DOC, Na, K, Ca, Mg, NH4, Fe(II), SO4, Cl, CH4, saturation index of calcite and siderite). The modelling demonstrated the relevance and impact of various secondary geochemical processes on leachate plume evolution. Concomitant precipitation of siderite masked the act of iron reduction. Cation exchange resulted in release of Fe(II) from the pristine anaerobic aquifer to the leachate. Degassing, triggered by elevated CO2 pressures caused by carbonate precipitation and proton buffering at the front of the plume, explained the observed downstream decrease in methane concentration. Simulation of the carbon isotope geochemistry independently supported the proposed reaction network.

  19. Process designing for laser forming of circular sheet metal

    Institute of Scientific and Technical Information of China (English)

    Q. Nadeem; W. J. Seong; S. J. Na

    2012-01-01

    Laser forming is a new type of flexible manufacturing process that has become viable for the shaping of metallic components.Process designing of laser forming involves finding a set of process parameters,including laser power,laser scanning paths,and scanning speed,given a prescribed shape.To date,research has focused on process designing for rectangular plates,and only a few studies are presented for axis-symmetric geometries like circular plates.In the present study,process designing for axis-symmetric geometries-with focus on class of shapes--is handled using a formerly proposed distance-based approach.A prescribed shape is achieved for geometries such as quarter-circular and half-circular ring plates.Experimental results verify the applicability of the proposed method for a class of shapes.%Laser forming is a new type of flexible manufacturing process that has become viable for the shaping of metallic components. Process designing of laser forming involves finding a set of process parameters, including laser power, laser scanning paths, and scanning speed, given a prescribed shape. To date, research has focused on process designing for rectangular plates, and only a few studies are presented for axis-symmetric geometries like circular plates. In the present study, process designing for axis-symmetric geometries-with focus on class of shapes-is handled using a formerly proposed distance-based approach. A prescribed shape is achieved for geometries such as quarter-circular and half-circular ring plates. Experimental results verify the applicability of the proposed method for a class of shapes.

  20. Direct selective laser sintering of high performance metals: Machine design, process development and process control

    Science.gov (United States)

    Das, Suman

    1998-11-01

    This dissertation describes the development of an advanced manufacturing technology known as Direct Selective Laser Sintering (Direct SLS). Direct SLS is a laser based rapid manufacturing technology that enables production of functional, fully dense, metal and cermet components via the direct, layerwise consolidation of constituent powders. Specifically, this dissertation focuses on a new, hybrid net shape manufacturing technique known as Selective Laser Sintering/Hot Isostatic Pressing (SLS/HIP). The objective of research presented in this dissertation was to establish the fundamental machine technology and processing science to enable direct SLS fabrication of metal components composed of high performance, high temperature metals and alloys. Several processing requirements differentiate direct SLS of metals from SLS of polymers or polymer coated powders. Perhaps the most important distinguishing characteristic is the regime of high temperatures involved in direct SLS of metals. Biasing the temperature of the feedstock powder via radiant preheat prior to and during SLS processing was shown to be beneficial. Preheating the powder significantly influenced the flow and wetting characteristics of the melt. During this work, it was conclusively established that powder cleanliness is of paramount importance for successful layerwise consolidation of metal powders by direct SLS. Sequential trials were conducted to establish optimal bake-out and degas cycles under high vacuum. These cycles agreed well with established practices in the powder metallurgy industry. A study of some of the important transport mechanisms in direct SLS of metals was undertaken to obtain a fundamental understanding of the underlying process physics. This study not only provides an explanation of phenomena observed during SLS processing of a variety of metallic materials but also helps in developing selection schemes for those materials that are most amenable to direct SLS processing. The

  1. Process of technology management in SMEs of the metal processing industry – the case study investigation

    Directory of Open Access Journals (Sweden)

    Krawczyk-Dembicka Elżbieta

    2017-03-01

    Full Text Available The main purpose of this work is to identify the factors that influence the process of technology management in the sector of small- and medium-sized enterprises of the metal processing industry, considering the shape and course required to achieve modern operation conditions by enterprises in the market.

  2. Synthesis and deposition of metal nanoparticles by gas condensation process

    Energy Technology Data Exchange (ETDEWEB)

    Maicu, Marina, E-mail: marina.maicu@fep.fraunhofer.de; Glöß, Daniel; Frach, Peter [Fraunhofer Institut für Elektronenstrahl und Plasmatechnik, FEP, Winterbergstraße 28, 01277 Dresden (Germany); Schmittgens, Ralph; Gerlach, Gerald [Institut für Festkörperelektronik, IFE, TU Dresden, Helmholtz Straße 18, 01069 Dresden (Germany); Hecker, Dominic [Fraunhofer Institut für Elektronenstrahl und Plasmatechnik, FEP, Winterbergstraße 28, 01277 Dresden, Germany and Institut für Festkörperelektronik, IFE, TU Dresden, Helmholtz Straße 18, 01069 Dresden (Germany)

    2014-03-15

    In this work, the synthesis of Pt and Ag nanoparticles by means of the inert gas phase condensation of sputtered atomic vapor is presented. The process parameters (power, sputtering time, and gas flow) were varied in order to study the relationship between deposition conditions and properties of the nanoparticles such as their quantity, size, and size distribution. Moreover, the gas phase condensation process can be combined with a plasma enhanced chemical vapor deposition procedure in order to deposit nanocomposite coatings consisting of metallic nanoparticles embedded in a thin film matrix material. Selected examples of application of the generated nanoparticles and nanocomposites are discussed.

  3. Architectural design of heterogeneous metallic nanocrystals--principles and processes.

    Science.gov (United States)

    Yu, Yue; Zhang, Qingbo; Yao, Qiaofeng; Xie, Jianping; Lee, Jim Yang

    2014-12-16

    CONSPECTUS: Heterogeneous metal nanocrystals (HMNCs) are a natural extension of simple metal nanocrystals (NCs), but as a research topic, they have been much less explored until recently. HMNCs are formed by integrating metal NCs of different compositions into a common entity, similar to the way atoms are bonded to form molecules. HMNCs can be built to exhibit an unprecedented architectural diversity and complexity by programming the arrangement of the NC building blocks ("unit NCs"). The architectural engineering of HMNCs involves the design and fabrication of the architecture-determining elements (ADEs), i.e., unit NCs with precise control of shape and size, and their relative positions in the design. Similar to molecular engineering, where structural diversity is used to create more property variations for application explorations, the architectural engineering of HMNCs can similarly increase the utility of metal NCs by offering a suite of properties to support multifunctionality in applications. The architectural engineering of HMNCs calls for processes and operations that can execute the design. Some enabling technologies already exist in the form of classical micro- and macroscale fabrication techniques, such as masking and etching. These processes, when used singly or in combination, are fully capable of fabricating nanoscopic objects. What is needed is a detailed understanding of the engineering control of ADEs and the translation of these principles into actual processes. For simplicity of execution, these processes should be integrated into a common reaction system and yet retain independence of control. The key to architectural diversity is therefore the independent controllability of each ADE in the design blueprint. The right chemical tools must be applied under the right circumstances in order to achieve the desired outcome. In this Account, after a short illustration of the infinite possibility of combining different ADEs to create HMNC design

  4. Carbon formation and metal dusting in advanced coal gasification processes

    Energy Technology Data Exchange (ETDEWEB)

    DeVan, J.H.; Tortorelli, P.F.; Judkins, R.R.; Wright, I.G.

    1997-02-01

    The product gases generated by coal gasification systems contain high concentrations of CO and, characteristically, have relatively high carbon activities. Accordingly, carbon deposition and metal dusting can potentially degrade the operation of such gasifier systems. Therefore, the product gas compositions of eight representative gasifier systems were examined with respect to the carbon activity of the gases at temperatures ranging from 480 to 1,090 C. Phase stability calculations indicated that Fe{sub 3}C is stable only under very limited thermodynamic conditions and with certain kinetic assumptions and that FeO and Fe{sub 0.877}S tend to form instead of the carbide. As formation of Fe{sub 3}C is a necessary step in the metal dusting of steels, there are numerous gasifier environments where this type of carbon-related degradation will not occur, particularly under conditions associated with higher oxygen and sulfur activities. These calculations also indicated that the removal of H{sub 2}S by a hot-gas cleanup system may have less effect on the formation of Fe{sub 3}C in air-blown gasifier environments, where the iron oxide phase can exist and is unaffected by the removal of sulfur, than in oxygen-blown systems, where iron sulfide provides the only potential barrier to Fe{sub 3}C formation. Use of carbon- and/or low-alloy steels dictates that the process gas composition be such that Fe{sub 3}C cannot form if the potential for metal dusting is to be eliminated. Alternatively, process modifications could include the reintroduction of hydrogen sulfide, cooling the gas to perhaps as low as 400 C and/or steam injection. If higher-alloy steels are used, a hydrogen sulfide-free gas may be processed without concern about carbon deposition and metal dusting.

  5. Sheets of branched poly(lactic acid) obtained by one step reactive extrusion calendering process: Melt rheology analysis

    OpenAIRE

    Cailloux, J.; Santana, O.O.; E. Franco-Urquiza; Bou, J. J.; F. Carrasco; J. Gamez-Perez; M. L. Maspoch

    2013-01-01

    One-step reactive extrusion-calendering process (REX-Calendering) was used in order to obtain sheets of 1mm from two PD,L-LA extrusion grades modified with a styrene-acrylic multifunctional oligomeric agent. In a preliminary internal mixer study, torque versus time was monitored in order to determine chain extender ratios and reaction time. Once all parameters were optimized, reactive extrusion experiments were performed. Independently of the processing method employed, under the same pro...

  6. Sterically demanding hetero-substituted [2]borametallocenophanes of group IV metals: synthesis, structure and reactivity.

    Science.gov (United States)

    Braunschweig, Holger; Dörfler, Rainer; Mies, Jan; Oechsner, Andreas

    2011-10-17

    We report the synthesis and characterisation of unprecedented unstrained [2]diborametallocenophanes of zirconium and hafnium that bear the bulky octamethylfluorenyl (η(5)-C(29)H(36)) system, the proligands of which were pre-constructed by a two-step synthesis. The compounds were fully characterised by NMR spectroscopy, MALDI-TOF mass spectrometry and X-ray diffraction analysis. Typical reactivities relevant to olefin polymerisation such as methylation and chloride abstraction were also investigated. Finally, a sterically demanding bis(octamethylfluorenyl) metallocene was prepared.

  7. Numerical Modeling of Inclusion Behavior in Liquid Metal Processing

    Science.gov (United States)

    Bellot, Jean-Pierre; Descotes, Vincent; Jardy, Alain

    2013-09-01

    Thermomechanical performance of metallic alloys is directly related to the metal cleanliness that has always been a challenge for metallurgists. During liquid metal processing, particles can grow or decrease in size either by mass transfer with the liquid phase or by agglomeration/fragmentation mechanisms. As a function of numerical density of inclusions and of the hydrodynamics of the reactor, different numerical modeling approaches are proposed; in the case of an isolated particle, the Lagrangian technique coupled with a dissolution model is applied, whereas in the opposite case of large inclusion phase concentration, the population balance equation must be solved. Three examples of numerical modeling studies achieved at Institut Jean Lamour are discussed. They illustrate the application of the Lagrangian technique (for isolated exogenous inclusion in titanium bath) and the Eulerian technique without or with the aggregation process: for precipitation and growing of inclusions at the solidification front of a Maraging steel, and for endogenous inclusions in the molten steel bath of a gas-stirred ladle, respectively.

  8. Reactivity of first-row transition metal monocations (Sc+, Ti+, V+, Zn+) with methyl fluoride: a computational study.

    Science.gov (United States)

    Redondo, Pilar; Varela-Álvarez, Adrián; Rayón, Víctor Manuel; Largo, Antonio; Sordo, José Ángel; Barrientos, Carmen

    2013-04-11

    The gas-phase reactivity of methyl fluoride with selected first-row transition metal monocations (Sc(+), Ti(+), V(+), and Zn(+)) has been theoretically investigated. Our thermochemical and kinetics study shows that early transition-metal cations exhibit a much more active chemistry than the latest transition metal monocation Zn(+). The strong C-F bond in methyl fluorine can be activated by scandium, titanium, and vanadium monocations yielding the metal fluorine cation, MF(+). However, the rate efficiencies vary dramatically along the period 0.73 (Sc), 0.91 (Ti), and 0.028 (V) in agreement with the experimental observation. The kinetics results show the relative importance of the entrance and exit channels, apart from the "inner" bottleneck, to control the global rate constant of these reactions. At the mPW1K/QZVPP level our computed kglobal (at 295 K), 1.99 × 10(-9) cm(3) molecule(-1) s(-1) (Sc(+)), 1.29 × 10(-9) cm(3) molecule(-1) s(-1) (Ti(+)), and 3.46 × 10(-10) cm(3) molecule(-1) s(-1) (V(+)) are in good agreement with the experimental data at the same temperature. For the reaction of Zn(+) and CH3F our predicted value for kouter, at 295 K, 3.79 × 10(-9) cm(3) molecule(-1) s(-1), is in accordance with the capture rate constant. Our study suggests that consideration of the lowest excited states for Ti(+) and V(+) is mandatory to reach agreement between calculations and experimental measurements.

  9. Reactive adsorption of NO2 on copper-based metal-organic framework and graphite oxide/metal-organic framework composites.

    Science.gov (United States)

    Levasseur, Benoit; Petit, Camille; Bandosz, Teresa J

    2010-12-01

    Composites of a copper-based metal-organic framework (MOF) and graphite oxide (GO) were tested for NO2 adsorption and retention of NO in dry and moist conditions. The samples were analyzed before and after exposure to NO2 by thermal analysis, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, and adsorption of nitrogen at -196 °C. In dry conditions, the composites exhibit an enhanced NO2 breakthrough capacity compared to MOF and GO separately. This improvement is linked to the increased porosity and the reactive adsorption of NO2 on copper, which leads to the formation of bidentate and monodentate nitrate. Even though less NO2 is adsorbed in moist conditions than in dry ones, the materials are more stable than in dry conditions and the NO retention is enhanced. Water in the challenge gas competes with NO2 to bind to copper, and thus, the number of reactive adsorption sites on which NO2 can be adsorbed/reacted decreases.

  10. NGNP Process Heat Utilization: Liquid Metal Phase Change Heat Exchanger

    Energy Technology Data Exchange (ETDEWEB)

    Piyush Sabharwall; Mike Patterson; Vivek Utgikar; Fred Gunnerson

    2008-09-01

    One key long-standing issue that must be overcome to fully realize the successful growth of nuclear power is to determine other benefits of nuclear energy apart from meeting the electricity demands. The Next Generation Nuclear Plant (NGNP) will most likely be producing electricity and heat for the production of hydrogen and/or oil retrieval from oil sands and oil shale to help in our national pursuit of energy independence. For nuclear process heat to be utilized, intermediate heat exchange is required to transfer heat from the NGNP to the hydrogen plant or oil recovery field in the most efficient way possible. Development of nuclear reactor - process heat technology has intensified the interest in liquid metals as heat transfer media because of their ideal transport properties. Liquid metal heat exchangers are not new in practical applications. An important rational for considering liquid metals is the potential convective heat transfer is among the highest known. Thus explains the interest in liquid metals as coolant for intermediate heat exchange from NGNP. For process heat it is desired that, intermediate heat exchangers (IHX) transfer heat from the NGNP in the most efficient way possible. The production of electric power at higher efficiency via the Brayton Cycle, and hydrogen production, requires both heat at higher temperatures and high effectiveness compact heat exchangers to transfer heat to either the power or process cycle. Compact heat exchangers maximize the heat transfer surface area per volume of heat exchanger; this has the benefit of reducing heat exchanger size and heat losses. High temperature IHX design requirements are governed in part by the allowable temperature drop between the outlet and inlet of the NGNP. In order to improve the characteristics of heat transfer, liquid metal phase change heat exchangers may be more effective and efficient. This paper explores the overall heat transfer characteristics and pressure drop of the phase change

  11. Cationic methyl complexes of the rare-earth metals: an experimental and computational study on synthesis, structure, and reactivity.

    Science.gov (United States)

    Kramer, Mathias U; Robert, Dominique; Arndt, Stefan; Zeimentz, Peter M; Spaniol, Thomas P; Yahia, Ahmed; Maron, Laurent; Eisenstein, Odile; Okuda, Jun

    2008-10-20

    Synthesis, structure, and reactivity of two families of rare-earth metal complexes containing discrete methyl cations [LnMe(2-x)(thf)n]((1+x)+) (x = 0, 1; thf = tetrahydrofuran) have been studied. As a synthetic equivalent for the elusive trimethyl complex [LnMe3], lithium methylates of the approximate composition [Li3LnMe6(thf)n] were prepared by treating rare-earth metal trichlorides [LnCl3(thf)n] with 6 equiv of methyllithium in diethyl ether. Heteronuclear complexes of the formula [Li3Ln2Me9L(n)] (Ln = Sc, Y, Tb; L = Et2O, thf) were isolated by crystallization from diethyl ether. Single crystal X-ray diffraction studies revealed a heterometallic aggregate of composition [Li3Ln2Me9(thf)n(Et2O)m] with a [LiLn2Me9](2-) core (Ln = Sc, Y, Tb). When tris(tetramethylaluminate) [Ln(AlMe4)3] (Ln = Y, Lu) was reacted with less than 1 equiv of [NR3H][BPh4], the dimethyl cations [LnMe2(thf)n][BPh4] were obtained. The coordination number as well as cis/trans isomer preference was studied by crystallographic and computational methods. Dicationic methyl complexes of the rare-earth metals of the formula [LnMe(thf)n][BAr4]2 (Ln = Sc, Y, La-Nd, Sm, Gd-Lu; Ar = Ph, C6H4F-4) were synthesized, by protonolysis of either the ate complex [Li3LnMe6(thf)n] (Ln = Sc, Y, Gd-Lu) or the tris(tetramethylaluminate) [Ln(AlMe4)3] (Ln = La-Nd, Sm, Dy, Gd) with ammonium borates [NR3H][BAr4] in thf. The number of coordinated thf ligands varied from n = 5 (Ln = Sc, Tm) to n = 6 (Ln = La, Y, Sm, Dy, Ho). The configuration of representative examples was determined by X-ray diffraction studies and confirmed by density-functional theory calculations. The highly polarized bonding between the methyl group and the rare-earth metal center results in the reactivity pattern dominated by the carbanionic character and the pronounced Lewis acidity: The dicationic methyl complex [YMe(thf)6](2+) inserted benzophenone as an electrophile to give the alkoxy complex [Y(OCMePh2)(thf)5](2+). Nucleophilic addition of

  12. Evidence of the self-heating effect on surface reactivity and gas sensing of metal oxide nanowire chemiresistors.

    Science.gov (United States)

    Strelcov, Evgheni; Dmitriev, Serghei; Button, Bradley; Cothren, Joshua; Sysoev, Victor; Kolmakov, Andrei

    2008-09-03

    The effect of Joule self-heating of the semiconducting metal oxide nanowire (here (and below unless specified), due to the generality of the effect, we use the term 'nanowire' without specification as to whether the nanobelt or other class of quasi-1D nanostructure is considered) conductometric gas sensor on its surface reactivity and kinetics is demonstrated. Due to small thermal capacitance and hampered thermal losses from the nanowire to its surroundings, the sensor was able to operate without a heater, consuming only a few microwatts of power. These results demonstrate the importance of the self-heating effect in nanowire electronics and its potential use in chemical and bio-sensing, where the ultra-small size of the active element and minimal power consumption are crucial.

  13. Metal Alloy Compositions And Process Background Of The Invention

    Science.gov (United States)

    Flemings, Merton C.; Martinez-Ayers, Raul A.; de Figueredo, Anacleto M.; Yurko, James A.

    2003-11-11

    A skinless metal alloy composition free of entrapped gas and comprising primary solid discrete degenerate dendrites homogeneously dispersed within a secondary phase is formed by a process wherein the metal alloy is heated in a vessel to render it a liquid. The liquid is then rapidly cooled while vigorously agitating it under conditions to avoid entrapment of gas while forming solid nuclei homogeneously distributed in the liquid. Agitation then is ceased when the liquid contains a small fraction solid or the liquid-solid alloy is removed from the source of agitation while cooling is continued to form the primary solid discrete degenerate dendrites in liquid secondary phase. The solid-liquid mixture then can be formed such as by casting.

  14. Process for electroless deposition of metals on zirconium materials

    Science.gov (United States)

    Donaghy, Robert E.

    1978-01-01

    A process for the electroless deposition of a metal layer on an article comprised of zirconium or a zirconium alloy is disclosed. The article is activated in an aged aqueous solution comprising from about 10 to about 20 grams per liter ammonium bifluoride and from about 0.75 to about 2 grams per liter of sulfuric acid. The solution is aged by immersion of pickled zirconium in the solution for at least about 10 minutes. The loosely adhering film formed on the article in the activating step is removed and the article is contacted with an electroless plating solution containing the metal to be deposited on the article upon sufficient contact with the article.

  15. Process for electrolytic deposition of metals on zirconium materials

    Science.gov (United States)

    Donaghy, Robert E.

    1979-01-30

    A process for the electrolytic deposition of a metal layer on an article comprised of zirconium or a zirconium alloy is disclosed. The article is activated in an aged aqueous solution comprising from about 10 to about 20 grams per liter ammonium bifluoride and from about 0.75 to about 2 grams per liter of sulfuric acid. The solution is aged by immersion of pickled zirconium in the solution for at least about 10 minutes. The loosely adhering film formed on the article in the activating step is removed and the article is contacted with an electrolytic plating solution containing the metal to be deposited on the article in the presence of an electrode receiving current.

  16. Metal chelate process to remove pollutants from fluids

    Science.gov (United States)

    Chang, Shih-Ger T.

    1994-01-01

    The present invention relates to improved methods using an organic iron chelate to remove pollutants from fluids, such as flue gas. Specifically, the present invention relates to a process to remove NO.sub.x and optionally SO.sub.2 from a fluid using a metal ion (Fe.sup.2+) chelate wherein the ligand is a dimercapto compound wherein the --SH groups are attached to adjacent carbon atoms (HS--C--C--SH) or (SH--C--CCSH) and contain a polar functional group so that the ligand of DMC chelate is water soluble. Alternatively, the DMC' is covalently attached to a water insoluble substrate such as a polymer or resin, e.g., polystyrene. The chelate is regenerated using electroreduction or a chemical additive. The dimercapto compound bonded to a water insoluble substrate is also useful to lower the concentration or remove hazardous metal ions from an aqueous solution.

  17. Metal chelate process to remove pollutants from fluids

    Science.gov (United States)

    Chang, S.G.T.

    1994-12-06

    The present invention relates to improved methods using an organic iron chelate to remove pollutants from fluids, such as flue gas. Specifically, the present invention relates to a process to remove NO[sub x] and optionally SO[sub 2] from a fluid using a metal ion (Fe[sup 2+]) chelate wherein the ligand is a dimercapto compound wherein the --SH groups are attached to adjacent carbon atoms (HS--C--C--SH) or (SH--C--CCSH) and contain a polar functional group so that the ligand of DMC chelate is water soluble. Alternatively, the DMC is covalently attached to a water insoluble substrate such as a polymer or resin, e.g., polystyrene. The chelate is regenerated using electroreduction or a chemical additive. The dimercapto compound bonded to a water insoluble substrate is also useful to lower the concentration or remove hazardous metal ions from an aqueous solution. 26 figures.

  18. Elimination of the reactivation process in the adhesion of chlorinated SBS rubber with polychloroprene adhesives

    Directory of Open Access Journals (Sweden)

    2007-04-01

    Full Text Available Chlorination treatment of a thermoplastic styrene-butadiene-styrene rubber (SBS with a 3 wt% solution of trichloroisocyanuric acid (TCI in methyl ethyl ketone (MEK introduces chlorinated and oxidized moieties on the rubber surface which increase its surface energy and produces surface microroughness. Consequently adhesion properties, evaluated by T-peel strength measurements in chlorinated SBS/solvent based-polyurethane adhesive/leather joints, are enhanced. In this study, two solvent-based polychloroprene adhesives (PCP0 and PCP30R have been considered as an alternative to the commonly used solvent-based polyurethane adhesive (PU. A thermoreactive phenolic resin was added to one of the polychloroprene adhesive formulations (PCP30R. This tackifier resin favors chlorination of the adhesive and reinforces the interface between the chlorinated adhesive and the chlorinated rubber surface. Besides, PCP30R adhesive does not need adhesive reactivation and considerable high T-peel strength value (5.7±0.3 kN/m was obtained. Elimination of the reactivation process implies a considerable improvement of the manufacturing process in the footwear industry.

  19. Preparation of macroporous methacrylate-based monoliths for chromatographic applications by the Reactive Gelation Process.

    Science.gov (United States)

    Bechtle, M; Butté, A; Storti, G; Morbidelli, M

    2010-07-09

    Polymeric monoliths are a relatively new separation medium for chromatographic applications. The innovative approach to produce such monoliths, the Reactive Gelation Process, presented by Marti et al. [1] for polystyrene macroporous materials is applied to a methacrylate-based material. It is shown that it is possible to create a macroporous structure by Reactive Gelation also with this polymer even if the properties of the material are different. Besides the analysis of the material by SEM and BET, several chromatographic methods are used to analyze the material properties. The ISEC experiments showed a much smaller size exclusion effect than in conventional packed beds. The permeability of the material is comparable to a packed bed with 4.13 μm particles. The column efficiency is not changing for increasing flow rates. Because of the high efficiency of the material, shorter columns are needed and therefore the comparatively low permeability is compensated. The monolith also exhibits a significant adsorption capacity for hydrophobic interaction, which makes it suitable for chromatographic purification processes.

  20. The trade-offs of emotional reactivity for youths' social information processing in the context of maternal depression.

    Science.gov (United States)

    Flynn, Megan; Rudolph, Karen D

    2012-01-01

    Although research demonstrates that emotional experiences can influence cognitive processing, little is known about individual differences in this association, particularly in youth. The present study examined how the emotional backdrop of the caregiving environment, as reflected in exposure to maternal depression and anxiety, was linked to biases in youths' cognitive processing of mother-referent information. Further, we investigated whether this association differed according to variation in youths' emotional reactivity to stress. Youth (50 boys, 46 girls; M age = 12.36, SD = 1.05) completed a behavioral task assessing cognitive bias. Semi-structured interviews were administered to assess (a) youths' emotional reactivity to naturally occurring stressors, and (b) maternal depression and anxiety. Hierarchical multiple regression analyses revealed that emotional reactivity to interpersonal stressors moderated the linkage between maternal depression and cognitive bias such that maternal depression predicted a greater negative bias in youth exhibiting high and average, but not low, levels of emotional reactivity. At low levels of maternal depression, youth with heightened interpersonal emotional reactivity showed a greater positive cognitive bias. This pattern of effects was specific to interpersonal (but not non-interpersonal) emotional reactivity and to maternal depression (but not anxiety). These findings illuminate one personal characteristic of youth that moderates emotion-cognition linkages, and reveal that emotional reactivity both enhances and impairs youths' cognitive processing as a function of socialization context.

  1. The trade-offs of emotional reactivity for youths’ social information processing in the context of maternal depression

    Directory of Open Access Journals (Sweden)

    Megan eFlynn

    2012-07-01

    Full Text Available Although research demonstrates that emotional experiences can influence cognitive processing, little is known about individual differences in this association, particularly in youth. The present study examined how the emotional backdrop of the caregiving environment, as reflected in exposure to maternal depression and anxiety, was linked to biases in youths’ cognitive processing of mother-referent information. Further, we investigated whether this association differed according to variation in youths’ emotional reactivity to stress. Youth (50 boys, 46 girls; M age = 12.36, SD = 1.05 completed a behavioral task assessing cognitive bias. Semi-structured interviews were administered to assess (a youths’ emotional reactivity to naturally occurring stressors, and (b maternal depression and anxiety. Hierarchical multiple regression analyses revealed that emotional reactivity to interpersonal stressors moderated the linkage between maternal depression and cognitive bias such that maternal depression predicted a greater negative bias in youth exhibiting high and average, but not low, levels of emotional reactivity. At low levels of maternal depression, youth with heightened interpersonal emotional reactivity showed a greater positive cognitive bias. This pattern of effects was specific to interpersonal (but not noninterpersonal emotional reactivity and to maternal depression (but not anxiety. These findings illuminate one personal characteristic of youth that moderates emotion-cognition linkages, and reveal that emotional reactivity both enhances and impairs youths’ cognitive processing as a function of socialization context.

  2. Metal-Free sp(2)-C-H Borylation as a Common Reactivity Pattern of Frustrated 2-Aminophenylboranes.

    Science.gov (United States)

    Chernichenko, Konstantin; Lindqvist, Markus; Kótai, Bianka; Nieger, Martin; Sorochkina, Kristina; Pápai, Imre; Repo, Timo

    2016-04-13

    C-H borylation is a powerful and atom-efficient method for converting affordable and abundant chemicals into versatile organic reagents used in the production of fine chemicals and functional materials. Herein we report a facile C-H borylation of aromatic and olefinic C-H bonds with 2-aminophenylboranes. Computational and experimental studies reveal that the metal-free C-H insertion proceeds via a frustrated Lewis pair mechanism involving heterolytic splitting of the C-H bond by cooperative action of the amine and boryl groups. The adapted geometry of the reactive B and N centers results in an unprecedentently low kinetic barrier for both insertion into the sp(2)-C-H bond and intramolecular protonation of the sp(2)-C-B bond in 2-ammoniophenyl(aryl)- or -(alkenyl)borates. This common reactivity pattern serves as a platform for various catalytic reactions such as C-H borylation and hydrogenation of alkynes. In particular, we demonstrate that simple 2-aminopyridinium salts efficiently catalyze the C-H borylation of hetarenes with catecholborane. This reaction is presumably mediated by a borenium species isoelectronic to 2-aminophenylboranes.

  3. CO2 gasification reactivity of biomass char: catalytic influence of alkali, alkaline earth and transition metal salts.

    Science.gov (United States)

    Lahijani, Pooya; Zainal, Zainal Alimuddin; Mohamed, Abdul Rahman; Mohammadi, Maedeh

    2013-09-01

    This study investigates the influence of alkali (Na, K), alkaline earth (Ca, Mg) and transition (Fe) metal nitrates on CO2 gasification reactivity of pistachio nut shell (PNS) char. The preliminary gasification experiments were performed in thermogravimetric analyzer (TGA) and the results showed considerable improvement in carbon conversion; Na-char>Ca-char>Fe-char>K-char>Mg-char>raw char. Based on TGA studies, NaNO3 (with loadings of 3-7 wt%) was selected as the superior catalyst for further gasification studies in bench-scale reactor; the highest reactivity was devoted to 5 wt% Na loaded char. The data acquired for gasification rate of catalyzed char were fitted with several kinetic models, among which, random pore model was adopted as the best model. Based on obtained gasification rate constant and using the Arrhenius plot, activation energy of 5 wt% Na loaded char was calculated as 151.46 kJ/mol which was 53 kJ/mol lower than that of un-catalyzed char. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. Large-Scale Reactive Atomistic Simulation of Shock-induced Initiation Processes in Energetic Materials

    Science.gov (United States)

    Thompson, Aidan

    2013-06-01

    Initiation in energetic materials is fundamentally dependent on the interaction between a host of complex chemical and mechanical processes, occurring on scales ranging from intramolecular vibrations through molecular crystal plasticity up to hydrodynamic phenomena at the mesoscale. A variety of methods (e.g. quantum electronic structure methods (QM), non-reactive classical molecular dynamics (MD), mesoscopic continuum mechanics) exist to study processes occurring on each of these scales in isolation, but cannot describe how these processes interact with each other. In contrast, the ReaxFF reactive force field, implemented in the LAMMPS parallel MD code, allows us to routinely perform multimillion-atom reactive MD simulations of shock-induced initiation in a variety of energetic materials. This is done either by explicitly driving a shock-wave through the structure (NEMD) or by imposing thermodynamic constraints on the collective dynamics of the simulation cell e.g. using the Multiscale Shock Technique (MSST). These MD simulations allow us to directly observe how energy is transferred from the shockwave into other processes, including intramolecular vibrational modes, plastic deformation of the crystal, and hydrodynamic jetting at interfaces. These processes in turn cause thermal excitation of chemical bonds leading to initial chemical reactions, and ultimately to exothermic formation of product species. Results will be presented on the application of this approach to several important energetic materials, including pentaerythritol tetranitrate (PETN) and ammonium nitrate/fuel oil (ANFO). In both cases, we validate the ReaxFF parameterizations against QM and experimental data. For PETN, we observe initiation occurring via different chemical pathways, depending on the shock direction. For PETN containing spherical voids, we observe enhanced sensitivity due to jetting, void collapse, and hotspot formation, with sensitivity increasing with void size. For ANFO, we

  5. Antibody reactivity to the major fish allergen parvalbumin is determined by isoforms and impact of thermal processing.

    Science.gov (United States)

    Saptarshi, Shruti R; Sharp, Michael F; Kamath, Sandip D; Lopata, Andreas L

    2014-04-01

    The EF-hand calcium binding protein, parvalbumin, is a major fish allergen. Detection of this allergen is often difficult due to its structural diversity among various fish species. The aim of this study was to evaluate the cross-reactivity of parvalbumin in a comprehensive range of bony and cartilaginous fish, from the Asia-Pacific region, and conduct a molecular analysis of this highly allergenic protein. Using the monoclonal anti-parvalbumin antibody PARV-19, we demonstrated the presence of monomeric and oligomeric parvalbumin in all fish analysed, except for gummy shark a cartilaginous fish. Heat processing of this allergen greatly affected its antibody reactivity. While heating caused a reduction in antibody reactivity to multimeric forms of parvalbumins for most bony fish, a complete loss of reactivity was observed for cartilaginous fish. Molecular analysis demonstrated that parvalbumin cross-reactivity, among fish species, is due to the molecular phylogenetic association of this major fish allergen.

  6. Development and characterization of polymers-metallic hot embossing process for manufacturing metallic micro-parts

    Science.gov (United States)

    Sahli, M.; Millot, C.; Gelin, J.-C.; Barrière, T.

    2011-01-01

    In the recent years, hot embossing process becomes a promising process for the replication of polymer micro-structures associated to its manufacturing capability related to a relatively low component cost. This rising demand has prompted the development of various micro-manufacturing techniques in an attempt to get micro-parts in large batch. The paper investigates the way to get metallic micro-parts through the hot embossing process. The micro-manufacturing process consists in three stages. In the first one, the different metallic feedstocks with 50 to 60% powder loading in volume have been prepared with adapted polymers/powders formulations. In a second stage, an elastomeric master has been used to obtain micro-parts on a plastic loaded substrate with developed mixture based on polypropylene, paraffin wax and stearic acid. Finally, a thermal debinding stage in nitrogen atmosphere followed by a solid state pre-sintering stage has been applied, in order to eliminate the pores between powder particles in the debinded components. Then the porous components are agglomerated by solid state diffusion after heating to a temperature slightly lower than the melting temperature related to the material used in the process, to form an homogenous structure when full densification is achieved. The advantages of this approach include: rapid manufacturing of injection tools with high-quality, easy demoulding of metallic parts from the elastomeric moulds and great flexibility related to the choices of material. The paper describes all the processing stages and the way to characterize the geometrical, physical and mechanical properties of the resulting micro-parts.

  7. Flexible Reactive Berm (FRBerm) for Removal of Heavy Metals from Runoff Water

    Science.gov (United States)

    2016-10-01

    Support of Remediation by Natural Attenuation at Site 9431-F at Fort Jackson South Carolina, June 1999. Shacklette, H.T. and J.G. Boerngen. 1984...15 Figure 13. Occurrence and Concentration of Munition-Associated Heavy Metals by Soil Particle Size in Sediment from the Center Kinder... Pollutant Discharge Elimination System NTU Nephelometric Turbidity Unit SAFR Small Arms Firing Range SDWA Safe Drinking Water Act SEL Severe Effect

  8. Resonance raman spectra and photochemical reactivity of transition metal α-diimine complexes

    Science.gov (United States)

    Stufkens, D. J.

    In this article the application of resonance Raman spectroscopy to the study of metal to ligand charge transfer (MLCT) transitions of α-diimine complexes is described. From these spectra information is obtained about the character of the MLCT transitions and about the properties of the excited states. It is shown how these resonance Raman spectra can be used to interpret and predict the MLCT photo-chemistry of α-diimine and imine complexes.

  9. Preparative soft and reactive landing of gas-phase ions on plasma-treated metal surfaces.

    Science.gov (United States)

    Volný, Michael; Elam, W Timothy; Ratner, Buddy D; Turecek, Frantisek

    2005-08-01

    Soft landing of singly charged gas-phase ions on dry metal surfaces that were pretreated in situ by oxygen plasma results in 0.1-2% total yields of recovered intact compounds. Lysine, peptides, crystal violet dye, and a biotin conjugate are found to survive soft landing of hyperthermal ions of up to 50-eV kinetic energy. Soft landing at 40-50-eV ion kinetic energies of a fluorescence-labeled biotin conjugate results in an immobilized fraction that cannot be washed from the surface and is found to contain an intact biotin moiety. The present results represent an approximately 10(4) fold improvement in soft-landing efficiency and indicate that plasma-treated metal surfaces can be useful for preparative separation of organic and biological molecules by mass spectrometry. The substantial improvement in soft-landing yields results from a high transmission of electrosprayed ions into the vacuum system, efficient and nondestructive discharge of ions on the metal oxide surface, and facile analyte recovery in the absence of a matrix.

  10. Polypropylene/natural rubber thermoplastic vulcanizates by eco-friendly and sustainable electron induced reactive processing

    Science.gov (United States)

    Mondal, Manas; Gohs, Uwe; Wagenknecht, Udo; Heinrich, Gert

    2013-07-01

    TPVs are a special class of thermoplastic and elastomer blend where cross-linking of elastomeric phase takes place during melt mixing process known as dynamic vulcanization (DV). A 50/50 blend of natural rubber (NR) and polypropylene (PP) were dynamically vulcanized using Electron Induced Reactive Processing (EIReP) as a function of absorbed dose (150, 250, and 350 kGy) at fixed electron energy (1.5 MeV) and dose per rotation. Different methods like tensile test, DSC, melt rheology, and SEM have been employed to understand the structure-property relationship of the prepared samples. The results suggest that EIReP is a novel technique to offer handful of additional features without compromising the end user property.

  11. Method for atmospheric pressure reactive atom plasma processing for surface modification

    Science.gov (United States)

    Carr, Jeffrey W.

    2009-09-22

    Reactive atom plasma processing can be used to shape, polish, planarize and clean the surfaces of difficult materials with minimal subsurface damage. The apparatus and methods use a plasma torch, such as a conventional ICP torch. The workpiece and plasma torch are moved with respect to each other, whether by translating and/or rotating the workpiece, the plasma, or both. The plasma discharge from the torch can be used to shape, planarize, polish, and/or clean the surface of the workpiece, as well as to thin the workpiece. The processing may cause minimal or no damage to the workpiece underneath the surface, and may involve removing material from the surface of the workpiece.

  12. Cognitive Impairments in Occupational Burnout - Error Processing and Its Indices of Reactive and Proactive Control.

    Science.gov (United States)

    Golonka, Krystyna; Mojsa-Kaja, Justyna; Gawlowska, Magda; Popiel, Katarzyna

    2017-01-01

    The presented study refers to cognitive aspects of burnout as the effects of long-term work-related stress. The purpose of the study was to investigate electrophysiological correlates of burnout to explain the mechanisms of the core burnout symptoms: exhaustion and depersonalization/cynicism. The analyzed error-related electrophysiological markers shed light on impaired cognitive mechanisms and the specific changes in information-processing in burnout. In the EEG study design (N = 80), two components of error-related potential (ERP), error-related negativity (ERN), and error positivity (Pe), were analyzed. In the non-clinical burnout group (N = 40), a significant increase in ERN amplitude and a decrease in Pe amplitude were observed compared to controls (N = 40). Enhanced error detection, indexed by increased ERN amplitude, and diminished response monitoring, indexed by decreased Pe amplitude, reveal emerging cognitive problems in the non-clinical burnout group. Cognitive impairments in burnout subjects relate to both reactive and unconscious (ERN) and proactive and conscious (Pe) aspects of error processing. The results indicate a stronger 'reactive control mode' that can deplete resources for proactive control and the ability to actively maintain goals. The analysis refers to error processing and specific task demands, thus should not be extended to cognitive processes in general. The characteristics of ERP patterns in burnout resemble psychophysiological indexes of anxiety (increased ERN) and depressive symptoms (decreased Pe), showing to some extent an overlapping effect of burnout and related symptoms and disorders. The results support the scarce existing data on the psychobiological nature of burnout, while extending and specifying its cognitive characteristics.

  13. Cognitive Impairments in Occupational Burnout – Error Processing and Its Indices of Reactive and Proactive Control

    Science.gov (United States)

    Golonka, Krystyna; Mojsa-Kaja, Justyna; Gawlowska, Magda; Popiel, Katarzyna

    2017-01-01

    The presented study refers to cognitive aspects of burnout as the effects of long-term work-related stress. The purpose of the study was to investigate electrophysiological correlates of burnout to explain the mechanisms of the core burnout symptoms: exhaustion and depersonalization/cynicism. The analyzed error-related electrophysiological markers shed light on impaired cognitive mechanisms and the specific changes in information-processing in burnout. In the EEG study design (N = 80), two components of error-related potential (ERP), error-related negativity (ERN), and error positivity (Pe), were analyzed. In the non-clinical burnout group (N = 40), a significant increase in ERN amplitude and a decrease in Pe amplitude were observed compared to controls (N = 40). Enhanced error detection, indexed by increased ERN amplitude, and diminished response monitoring, indexed by decreased Pe amplitude, reveal emerging cognitive problems in the non-clinical burnout group. Cognitive impairments in burnout subjects relate to both reactive and unconscious (ERN) and proactive and conscious (Pe) aspects of error processing. The results indicate a stronger ‘reactive control mode’ that can deplete resources for proactive control and the ability to actively maintain goals. The analysis refers to error processing and specific task demands, thus should not be extended to cognitive processes in general. The characteristics of ERP patterns in burnout resemble psychophysiological indexes of anxiety (increased ERN) and depressive symptoms (decreased Pe), showing to some extent an overlapping effect of burnout and related symptoms and disorders. The results support the scarce existing data on the psychobiological nature of burnout, while extending and specifying its cognitive characteristics. PMID:28507528

  14. Reactive processing of textile-natural fiber reinforced anionic polyamide-6 composites

    Energy Technology Data Exchange (ETDEWEB)

    Kan, Ze; Chen, Peng; Liu, Zhengying; Feng, Jianmin; Yang, Mingbo [College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610065, Sichuan (China)

    2015-05-22

    Nowadays natural fiber, used in reinforced composites, is widely concerned. However, no natural fiber reinforced reactive thermoplastic polymer grades had been prepared so far. Through our studies, it was demonstrated that there was a severe retardation and discoloration occurred in the reactive processing between anionic polyamide-6 (APA-6) and natural fiber, which result in incomplete polymerization when put together. In order to solve the problem, two methods were adopted in this paper, which are fiber pretreatment and usage of a new-style initiator called caprolactam magnesium bromide. The former is to remove sizing agent and impurities on the surface of fiber, and the latter is to weaken the side reactions between APA-6 and natural fiber by the nature of its lower reactivity and weaker alkaline. In cooperation with both methods, the severe retardation and discoloration had been improved significantly, so that the polymerization of APA-6 in natural fiber was occurred smoothly. Following textile-natural fiber reinforced APA-6 composites with an average thickness of 2.5 mm and a fiber volume content of 50% was prepared by vacuum assisted resin transfer molding (VARTM). The soxhlet extraction, dilute solution viscometry and differential scanning calorimeter (DSC) measurements respectively suggested the degree of conversion, viscosity-average molar mass and crystallization of composites was up to 94%, 11.3×104 and 50%. Remarkable improvement of mechanical properties were achieved through dynamic mechanical analysis (DMA), tensile and three-point bending test. Favorable interfacial adhesion and wettability were revealed by scanning electron microscopy (SEM) observation. Therefore, all of the above good performance make this new-style and environmentally friendly composites have broad application prospects.

  15. Estimation of reactive surface area using a combined method of laboratory analyses and digital image processing

    Science.gov (United States)

    Ma, Jin; Kong, Xiang-Zhao; Saar, Martin O.

    2017-04-01

    Fluid-rock interactions play an important role in the engineering processes such as chemical stimulation of enhanced geothermal systems and carbon capture, utilization, and storage. However, these interactions highly depend on the accessible reactive surface area of the minerals that are generally poorly constrained for natural geologic samples. In particular, quantifying surface area of each reacting mineral within whole rock samples is challenging due to the heterogeneous distribution of minerals and pore space. In this study, detailed laboratory analyses were performed on sandstone samples from deep geothermal sites in Lithuania. We measure specific surface area of whole rock samples using a gas adsorption method (so-called B.E.T.) with N2 at a temperature of 77.3K. We also quantify their porosity and pore size distribution by a Helium gas pycnometer and a Hg porosimetry, respectively. Rock compositions are determined by a combination of X-ray fluorescence (XRF) and quantitative scanning electron microscopy (SEM) - Energy-dispersive X-ray spectroscopy (EDS), which are later geometrically mapped on images of two-dimensional SEM- Backscattered electrons (BSE) with a resolution of 1.2 μm and three-dimensional micro-CT with a resolution of 10.3 μm to produce a digital mineral map for further constraining the accessibility of reactive minerals. Moreover, we attempt to link the whole rock porosity, pore size distribution, and B.E.T. specific surface area with the digital mineral maps. We anticipate these necessary analyses to provide in-depth understanding of fluid sample chemistry from later hydrothermal reactive flow-through experiments on whole rock samples at elevated pressure and temperature.

  16. Molecular Mechanism of Heavy Metal Toxicity and Tolerance in Plants: Central Role of Glutathione in Detoxification of Reactive Oxygen Species and Methylglyoxal and in Heavy Metal Chelation

    Directory of Open Access Journals (Sweden)

    Mohammad Anwar Hossain

    2012-01-01

    Full Text Available Heavy metal (HM toxicity is one of the major abiotic stresses leading to hazardous effects in plants. A common consequence of HM toxicity is the excessive accumulation of reactive oxygen species (ROS and methylglyoxal (MG, both of which can cause peroxidation of lipids, oxidation of protein, inactivation of enzymes, DNA damage and/or interact with other vital constituents of plant cells. Higher plants have evolved a sophisticated antioxidant defense system and a glyoxalase system to scavenge ROS and MG. In addition, HMs that enter the cell may be sequestered by amino acids, organic acids, glutathione (GSH, or by specific metal-binding ligands. Being a central molecule of both the antioxidant defense system and the glyoxalase system, GSH is involved in both direct and indirect control of ROS and MG and their reaction products in plant cells, thus protecting the plant from HM-induced oxidative damage. Recent plant molecular studies have shown that GSH by itself and its metabolizing enzymes—notably glutathione S-transferase, glutathione peroxidase, dehydroascorbate reductase, glutathione reductase, glyoxalase I and glyoxalase II—act additively and coordinately for efficient protection against ROS- and MG-induced damage in addition to detoxification, complexation, chelation and compartmentation of HMs. The aim of this review is to integrate a recent understanding of physiological and biochemical mechanisms of HM-induced plant stress response and tolerance based on the findings of current plant molecular biology research.

  17. Process Optimization for Valuable Metal Recovery from Dental Amalgam Residues

    Directory of Open Access Journals (Sweden)

    C.M. Parra–Mesa

    2009-07-01

    Full Text Available In this paper, the methodology used for optimizing leaching in a semi pilot plant is presented. This leaching process was applied to recover value metals from dental amalgam residues. 23 factorial design was used to characterize the process during the first stage and in the second one, a central compound rotational design was used for modeling copper percentage dissolved, a function of the nitric acid concentration, leaching time and temperature. This model explained the 81% of the response variability, which is considered satisfactory given the complexity of the process kinetics and, furthermore, it allowed the definition of the operation conditions for better copper recovery, which this was of 99.15%, at a temperature of 55°C, a concentration of 30% by weight and a time of 26 hours.

  18. Processing of Refractory Metal Alloys for JOYO Irradiations

    Energy Technology Data Exchange (ETDEWEB)

    RF Luther; ME Petrichek

    2006-02-21

    This is a summary of the refractory metal processing experienced by candidate Prometheus materiats as they were fabricated into specimens destined for testing within the JOYO test reactor, ex-reactor testing at Oak Ridge National Laboratory (ORNL), or testing within the NRPCT. The processing is described for each alloy from the point of inception to the point where processing was terminated due to the cancellation of Naval Reactor's involvement in the Prometheus Project. The alloys included three tantalum-base alloys (T-111, Ta-10W, and ASTAR-811C), a niobium-base alloy, (FS-85), and two molybdenum-rhenium alloys, one containing 44.5 w/o rhenium, and the other 47.5 w/o rhenium. Each of these alloys was either a primary candidate or back-up candidate for cladding and structural applications within the space reactor. Their production was intended to serve as a forerunner for large scale production ingots that were to be procured from commercial refractory metal vendors such as Wah Chang.

  19. Superior metallic alloys through rapid solidification processing (RSP) by design

    Energy Technology Data Exchange (ETDEWEB)

    Flinn, J.E. [Idaho National Engineering Laboratory, Idaho Falls, ID (United States)

    1995-05-01

    Rapid solidification processing using powder atomization methods and the control of minor elements such as oxygen, nitrogen, and carbon can provide metallic alloys with superior properties and performance compared to conventionally processing alloys. Previous studies on nickel- and iron-base superalloys have provided the baseline information to properly couple RSP with alloy composition, and, therefore, enable alloys to be designed for performance improvements. The RSP approach produces powders, which need to be consolidated into suitable monolithic forms. This normally involves canning, consolidation, and decanning of the powders. Canning/decanning is expensive and raises the fabrication cost significantly above that of conventional, ingot metallurgy production methods. The cost differential can be offset by the superior performance of the RSP metallic alloys. However, without the performance database, it is difficult to convince potential users to adopt the RSP approach. Spray casting of the atomized molten droplets into suitable preforms for subsequent fabrication can be cost competitive with conventional processing. If the fine and stable microstructural features observed for the RSP approach are preserved during spray casing, a cost competitive product can be obtained that has superior properties and performance that cannot be obtained by conventional methods.

  20. Different reactive oxygen species lead to distinct changes of cellular metal ions in the eukaryotic model organism Saccharomyces cerevisiae.

    Science.gov (United States)

    Wu, Ming J; O'Doherty, Patrick J; Murphy, Patricia A; Lyons, Victoria; Christophersen, Melinda; Rogers, Peter J; Bailey, Trevor D; Higgins, Vincent J

    2011-01-01

    Elemental uptake and export of the cell are tightly regulated thereby maintaining the ionomic homeostasis. This equilibrium can be disrupted upon exposure to exogenous reactive oxygen species (ROS), leading to reduction or elevation of the intracellular metal ions. In this study, the ionomic composition in the eukaryotic model organism Saccharomyces cerevisiae was profiled using the inductively-coupled plasma optical emission spectrometer (ICP-OES) following the treatment with individual ROS, including hydrogen peroxide, cumen hydroperoxide, linoleic acid hydroperoxide (LAH), the superoxide-generating agent menadione, the thiol-oxidising agent diamide [diazine-dicarboxylic acid-bis(dimethylamide)], dimedone and peroxynitrite. The findings demonstrated that different ROS resulted in distinct changes in cellular metal ions. Aluminium (Al(3+)) level rose up to 50-fold after the diamide treatment. Cellular potassium (K(+)) in LAH-treated cells was 26-fold less compared to the non-treated controls. The diamide-induced Al(3+) accumulation was further validated by the enhanced Al(3+) uptake along the time course and diamide doses. Pre-incubation of yeast with individual elements including iron, copper, manganese and magnesium failed to block diamide-induced Al(3+) uptake, suggesting Al(3+)-specific transporters could be involved in Al(3+) uptake. Furthermore, LAH-induced potassium depletion was validated by a rescue experiment in which addition of potassium increased yeast growth in LAH-containing media by 26% compared to LAH alone. Taken together, the data, for the first time, demonstrated the linkage between ionomic profiles and individual oxidative conditions.

  1. INVESTIGATION OF METAL CHIP HEATING PROCESS (Part 2

    Directory of Open Access Journals (Sweden)

    O. M. Dyakonov

    2008-01-01

    Full Text Available A physical and mathematical model of metal chip heating process in a continuous muffle furnace has been worked out. The model describes a conjugated heat- and mass transfer in the given  furnace (conductive, convective, radiant, heating of chips and furnace parts, lubricant-coolant evaporation, oil vapour combustion, flue gas movement. The received set of equations is a completed one that allows to solve a specified problem that is to find an optimum height for a furnace with the given productivity  and minimum natural gas consumption. 

  2. Numerical Simulation of Chip Formation in Metal Cutting Process

    Directory of Open Access Journals (Sweden)

    HUANG Meixia

    2012-07-01

    Full Text Available In order to study the chip formation mechanism in metal cutting process, based on finite element software ABAQUS, establish finite element model, and carry out numerical simulation on serrated chip formation of Ni-base superalloy GH4169 and ribbon chip formation of 45# steel respectively.In addition, analyze the influence law of three factors (cutting speed, feed rate, back cutting depth on cutting force and the distribution rule of cutting heat in serrated chip formation of GH4169.  

  3. Comparative Study of the Effects of Long and Short Term Biological Processes on the Cycling of Colloidal Trace Metals

    Science.gov (United States)

    Pinedo, P.; Sanudo-Wilhelmy, S. A.; West, A.

    2013-05-01

    colloidal and truly dissolved fractions was strongly influenced by the distribution of DOC and chlorophyll-a concentration. On the other hand, ~93% of Cu was found in the truly dissolved pool, suggesting little correlation between Cu speciation and chlorophyll-a concentration. Together, the findings from our study of both long and short term biological processes show differential fractionation of Cu, which has a low nutrient value and a high affinity for dissolved constituents compared to Fe, which has a much higher cellular requirements and high particle reactivity. Overall, this study points out that both long and short term biological processes have an important bearing on understanding the mobility of trace metals in the ocean, with implications for how we should collect and interpret water-quality data, and for how cyclical variation in metal concentrations may affect aquatic ecology.

  4. Kinetic theory of transport processes in partially ionized reactive plasma, II: Electron transport properties

    Science.gov (United States)

    Zhdanov, V. M.; Stepanenko, A. A.

    2016-11-01

    The previously obtained in (Zhdanov and Stepanenko, 2016) general transport equations for partially ionized reactive plasma are employed for analysis of electron transport properties in molecular and atomic plasmas. We account for both elastic and inelastic interaction channels of electrons with atoms and molecules of plasma and also the processes of electron impact ionization of neutral particles and three-body ion-electron recombination. The system of scalar transport equations for electrons is discussed and the expressions for non-equilibrium corrections to electron ionization and recombination rates and the diagonal part of the electron pressure tensor are derived. Special attention is paid to analysis of electron energy relaxation during collisions with plasma particles having internal degrees of freedom and the expression for the electron coefficient of inelastic energy losses is deduced. We also derive the expressions for electron vector and tensorial transport fluxes and the corresponding transport coefficients for partially ionized reactive plasma, which represent a generalization of the well-known results obtained by Devoto (1967). The results of numerical evaluation of contribution from electron inelastic collisions with neutral particles to electron transport properties are presented for a series of molecular and atomic gases.

  5. Modeling and analysis of time-dependent processes in a chemically reactive mixture

    Science.gov (United States)

    Ramos, M. P.; Ribeiro, C.; Soares, A. J.

    2017-08-01

    In this paper, we study the propagation of sound waves and the dynamics of local wave disturbances induced by spontaneous internal fluctuations in a reactive mixture. We consider a non-diffusive, non-heat conducting and non-viscous mixture described by an Eulerian set of evolution equations. The model is derived from the kinetic theory in a hydrodynamic regime of a fast chemical reaction. The reactive source terms are explicitly computed from the kinetic theory and are built in the model in a proper way. For both time-dependent problems, we first derive the appropriate dispersion relation, which retains the main effects of the chemical process, and then investigate the influence of the chemical reaction on the properties of interest in the problems studied here. We complete our study by developing a rather detailed analysis using the Hydrogen-Chlorine system as reference. Several numerical computations are included illustrating the behavior of the phase velocity and attenuation coefficient in a low-frequency regime and describing the spectrum of the eigenmodes in the small wavenumber limit.

  6. Sheets of branched poly(lactic acid) obtained by one step reactive extrusion calendering process: Physical Aging and Fracture Behaviour

    OpenAIRE

    Cailloux, Jonathan; Santana Pérez, Orlando Onofre; FRANCO URQUIZA, EDGAR ADRIAN; Bou Serra, Jordi; Carrasco Alonso, Félix Ángel; Maspoch Rulduà, Mª Lluïsa

    2014-01-01

    The architectural modifications of a linear poly(D,L-Lactide) acid (PD,L-LA) commercial grade were induced by a one-step reactive extrusion-calendering process using a styrene-glycidyl acrylate copolymer as reactive agent. The melt degradation was counteracted by chain extension and branching reactions, leading to a stabilization of the melt properties and an increase in the molecular weight. For such modified samples [poly(lactic acid) (PLA)-reactive extrusion (REX)], the rate of physical ag...

  7. Cross-Reactive Sensor Array for Metal Ion Sensing Based on Fluorescent SAMs

    Directory of Open Access Journals (Sweden)

    Mercedes Crego-Calama

    2007-09-01

    Full Text Available Fluorescent self assembled monolayers (SAMs on glass were previouslydeveloped in our group as new sensing materials for metal ions. These fluorescent SAMs arecomprised by fluorophores and small molecules sequentially deposited on a monolayer onglass. The preorganization provided by the surface avoids the need for complex receptordesign, allowing for a combinatorial approach to sensing systems based on small molecules.Now we show the fabrication of an effective microarray for the screening of metal ions andthe properties of the sensing SAMs. A collection of fluorescent sensing SAMs wasgenerated by combinatorial methods and immobilized on the glass surfaces of a custom-made 140 well microtiter-plate. The resulting libraries are easily measured and show variedresponses to a series cations such as Cu2+ , Co2+ , Pb2+ , Ca2+ and Zn2+ . These surfaces are notdesigned to complex selectively a unique analyte but rather they are intended to producefingerprint type responses to a range of analytes by less specific interactions. The unselectiveresponses of the library to the presence of different cations generate a characteristic patternfor each analyte, a “finger print” response.

  8. Cross-Reactive Sensor Array for Metal Ion Sensing Based on Fluorescent SAMs

    Science.gov (United States)

    Basabe-Desmonts, Lourdes; van der Baan, Frederieke; Zimmerman, Rebecca S.; Reinhoudt, David N.; Crego-Calama, Mercedes

    2007-01-01

    Fluorescent self assembled monolayers (SAMs) on glass were previously developed in our group as new sensing materials for metal ions. These fluorescent SAMs are comprised by fluorophores and small molecules sequentially deposited on a monolayer on glass. The preorganization provided by the surface avoids the need for complex receptor design, allowing for a combinatorial approach to sensing systems based on small molecules. Now we show the fabrication of an effective microarray for the screening of metal ions and the properties of the sensing SAMs. A collection of fluorescent sensing SAMs was generated by combinatorial methods and immobilized on the glass surfaces of a custom-made 140 well microtiter-plate. The resulting libraries are easily measured and show varied responses to a series cations such as Cu2+, Co2+, Pb2+, Ca2+ and Zn2+. These surfaces are not designed to complex selectively a unique analyte but rather they are intended to produce fingerprint type responses to a range of analytes by less specific interactions. The unselective responses of the library to the presence of different cations generate a characteristic pattern for each analyte, a “finger print” response.

  9. Electronic Structure of Transition Metal Clusters, Actinide Complexes and Their Reactivities

    Energy Technology Data Exchange (ETDEWEB)

    Krishnan Balasubramanian

    2009-07-18

    This is a continuing DOE-BES funded project on transition metal and actinide containing species, aimed at the electronic structure and spectroscopy of transition metal and actinide containing species. While a long term connection of these species is to catalysis and environmental management of high-level nuclear wastes, the immediate relevance is directly to other DOE-BES funded experimental projects at DOE-National labs and universities. There are a number of ongoing gas-phase spectroscopic studies of these species at various places, and our computational work has been inspired by these experimental studies and we have also inspired other experimental and theoretical studies. Thus our studies have varied from spectroscopy of diatomic transition metal carbides to large complexes containing transition metals, and actinide complexes that are critical to the environment. In addition, we are continuing to make code enhancements and modernization of ALCHEMY II set of codes and its interface with relativistic configuration interaction (RCI). At present these codes can carry out multi-reference computations that included up to 60 million configurations and multiple states from each such CI expansion. ALCHEMY II codes have been modernized and converted to a variety of platforms such as Windows XP, and Linux. We have revamped the symbolic CI code to automate the MRSDCI technique so that the references are automatically chosen with a given cutoff from the CASSCF and thus we are doing accurate MRSDCI computations with 10,000 or larger reference space of configurations. The RCI code can also handle a large number of reference configurations, which include up to 10,000 reference configurations. Another major progress is in routinely including larger basis sets up to 5g functions in thee computations. Of course higher angular momenta functions can also be handled using Gaussian and other codes with other methods such as DFT, MP2, CCSD(T), etc. We have also calibrated our RECP

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

    Energy Technology Data Exchange (ETDEWEB)

    Simunovic, Srdjan [ORNL; Nycz, Andrzej [ORNL; Noakes, Mark W [ORNL; Chin, Charlie [Dassault Systemes; Oancea, Victor [Dassault Systemes

    2017-01-01

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

  11. Homoleptic rare-earth metal(III) tetramethylaluminates: structural chemistry, reactivity, and performance in isoprene polymerization.

    Science.gov (United States)

    Zimmermann, Melanie; Frøystein, Nils Age; Fischbach, Andreas; Sirsch, Peter; Dietrich, H Martin; Törnroos, Karl W; Herdtweck, Eberhardt; Anwander, Reiner

    2007-01-01

    The complexes [Ln(AlMe4)3] (Ln=Y, La, Ce, Pr, Nd, Sm, Ho, Lu) have been synthesized by an amide elimination route and the structures of [Lu{(micro-Me)2AlMe2}3], [Sm{(micro-Me)2AlMe2}3], [Pr{(micro-Me)2AlMe2}3], and [La{(micro-Me)2AlMe2}2{(micro-Me)3AlMe}] determined by X-ray crystallography. These structures reveal a distinct Ln3+ cation size-dependency. A comprehensive insight into the intrinsic properties and solution coordination phenomena of [Ln(AlMe4)3] complexes has been gained from extended dynamic 1H and 13C NMR spectroscopic studies, as well as 1D 89Y, 2D 1H/89Y, and 27Al NMR spectroscopic investigations. [Ce(AlMe4)3] and [Pr(AlMe4)3] have been used as alkyl precursors for the synthesis of heterobimetallic alkylated rare-earth metal complexes. Both carboxylate and siloxide ligands can be introduced by methane elimination reactions that give the heterobimetallic complexes [Ln{(O2CAriPr)2(micro-AlMe2)}2(AlMe4)(C6H14)n] and [Ln{OSi(OtBu)3}(AlMe3)(AlMe4)2], respectively. [Pr{OSi(OtBu)3}(AlMe3)(AlMe4)2] has been characterized by X-ray structure analysis. All of the cerium and praseodymium complexes are used as precatalysts in the stereospecific polymerization of isoprene (1-3 equivalents of Et2AlCl as co-catalyst) and compared to the corresponding neodymium-based initiators reported previously. The superior catalytic performance of the homoleptic complexes leads to quantitative yields of high-cis-1,4-polyisoprene (>98%) in almost all of the polymerization experiments. In the case of the binary catalyst mixtures derived from carboxylate or siloxide precatalysts quantitative formation of polyisoprene is only observed for nLn:nCl=1:2. The influence of the metal size is illustrated for the heterobimetallic lanthanum, cerium, praseodymium, neodymium, and gadolinium carboxylate complexes, and the highest activities are observed for praseodymium as a metal center in the presence of one equivalent of Et2AlCl.

  12. Reactive Transport and Coupled THM Processes in Engineering Barrier Systems (EBS)

    Energy Technology Data Exchange (ETDEWEB)

    Steefel, Carl; Rutqvist, Jonny; Tsang, Chin-Fu; Liu, Hui-Hai; Sonnenthal, Eric; Houseworth, Jim; Birkholzer, Jens

    2010-08-31

    Geological repositories for disposal of high-level nuclear wastes generally rely on a multi-barrier system to isolate radioactive wastes from the biosphere. The multi-barrier system typically consists of a natural barrier system, including repository host rock and its surrounding subsurface environment, and an engineering barrier system (EBS). EBS represents the man-made, engineered materials placed within a repository, including the waste form, waste canisters, buffer materials, backfill and seals (OECD, 2003). EBS plays a significant role in the containment and long-term retardation of radionuclide release. EBS is involved in complex thermal, hydrogeological, mechanical, chemical and biological processes, such as heat release due to radionuclide decay, multiphase flow (including gas release due to canister corrosion), swelling of buffer materials, radionuclide diffusive transport, waste dissolution and chemical reactions. All these processes are related to each other. An in-depth understanding of these coupled processes is critical for the performance assessment (PA) for EBS and the entire repository. Within the EBS group of Used Fuel Disposition (UFD) Campaign, LBNL is currently focused on (1) thermal-hydraulic-mechanical-chemical (THMC) processes in buffer materials (bentonite) and (2) diffusive transport in EBS associated with clay host rock, with a long-term goal to develop a full understanding of (and needed modeling capabilities to simulate) impacts of coupled processes on radionuclide transport in different components of EBS, as well as the interaction between near-field host rock (e.g., clay) and EBS and how they effect radionuclide release. This final report documents the progress that LBNL has made in its focus areas. Specifically, Section 2 summarizes progress on literature review for THMC processes and reactive-diffusive radionuclide transport in bentonite. The literature review provides a picture of the state-of-the-art of the relevant research areas

  13. Process model for carbothermic production of silicon metal

    Energy Technology Data Exchange (ETDEWEB)

    Andresen, B.

    1995-09-12

    This thesis discusses an advanced dynamical two-dimensional cylinder symmetric model for the high temperature part of the carbothermic silicon metal process, and its computer encoding. The situation close to that which is believed to exist around one of three electrodes in full-scale industrial furnaces is modelled. This area comprises a gas filled cavity surrounding the lower tip of the electrode, the metal pool underneath and the lower parts of the materials above. The most important phenomena included are: Heterogeneous chemical reactions taking place in the high-temperature zone (above 1860 {sup o}C), Evaporation and condensation of silicon, Transport of materials by dripping, Turbulent or laminar fluid flow, DC electric arcs, Heat transport by convection, conduction and radiation. The results from the calculations, such as production rates, gas- and temperature distributions, furnace- and particle geometries, fluid flow fields etc, are presented graphically. In its present state the model is a prototype. The process is very complex, and the calculations are time consuming. The governing equations are coded into a Fortran 77 computer code applying the commercial 3D code FLUENT as a basis. 64 refs., 110 figs., 11 tabs.

  14. Study of Reactive Melt Processing Behavior of Externally Plasticized Cellulose Acetate in Presence of Isocyanate

    Directory of Open Access Journals (Sweden)

    Rafael Erdmann

    2014-12-01

    Full Text Available Two types of externally plasticized cellulose acetate (CA were chemically modified using 4,4'-methylene diphenyl diisocyanate (MDI as crosslinking agent. Crosslinking was performed in the molten state by means of melt mixing in an internal mixer. The viscoelastic properties of the non-crosslinked, externally plasticized CA show typical temperature dependence, similar to conventional thermoplastics. A strong increase in storage modulus is observed with increasing crosslink density indicating that the crosslinked compounds exhibit predominately elastic response. The complex viscosity also increases considerably with increasing crosslink density and does not reach the typical Newtonian plateau at low radial frequencies any more. The viscoelastic properties correlate well with the data recorded online during reactive melt processing in the internal mixer. In comparison to the non-crosslinked CA, the crosslinked compounds show higher glass transition temperature, higher VICAT softening temperatures, improved thermal stability and lower plasticizer evaporation at evaluated temperatures.

  15. Selective organic synthesis through generation and reactivity control of hyper-coordinate metal species.

    Science.gov (United States)

    Hiyama, Tamejiro

    2008-01-01

    This paper is a review of my 40 years of research at Kyoto, Sagamihara, and Yokohama, all based on the generation of hyper-coordinate metal species such as ate complexes and pentacoordinate silicates. The topics are: (i) carbenoid reagents for carbon-carbon bond-forming reactions, (ii) nucleophilic substitution at acetal carbons using aluminate reagents, (iii) preparation of magnesium enolates and its reaction with nitriles, (iv) Cr(II) reagents for reduction of organic halides and highly selective carbon-carbon bond formation, (v) organic synthesis with organosilion reagents/fluoride ions, (vi) cross-coupling reaction of organosilicon compounds, and (vii) silicon-based conjugate addition to alpha,beta-unsaturated carbonyl acceptors.

  16. Isolation of Metals from Liquid Wastes: Reactive Scavenging in Turbulent Thermal Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Jost O.L. Wendt; Alan R. Kerstein; Alexander Scheeline; Arne Pearlstein; William Linak

    2003-08-06

    The Overall project demonstrated that toxic metals (cesium Cs and strontium Sr) in aqueous and organic wastes can be isolated from the environment through reaction with kaolinite based sorbent substrates in high temperature reactor environments. In addition, a state-of-the art laser diagnostic tool to measure droplet characteristic in practical 'dirty' laboratory environments was developed, and was featured on the cover of a recent edition of the scientific journal ''applied Spectroscopy''. Furthermore, great strides have been made in developing a theoretical model that has the potential to allow prediction of the position and life history of every particle of waste in a high temperature, turbulent flow field, a very challenging problem involving as it does, the fundamentals of two phase turbulence and of particle drag physics.

  17. Numerical Tool Path Optimization for Conventional Sheet Metal Spinning Processes

    Science.gov (United States)

    Rentsch, Benedikt; Manopulo, Niko; Hora, Pavel

    2016-08-01

    To this day, conventional sheet metal spinning processes are designed with a very low degree of automation. They are usually executed by experienced personnel, who actively adjust the tool paths during production. The practically unlimited freedom in designing the tool paths enables the efficient manufacturing of complex geometries on one hand, but is challenging to translate into a standardized procedure on the other. The present study aims to propose a systematic methodology, based on a 3D FEM model combined with a numerical optimization strategy, in order to design tool paths. The accurate numerical modelling of the spinning process is firstly discussed, followed by an analysis of appropriate objective functions and constraints required to obtain a failure free tool path design.

  18. Impact of melt treatment on semi-solid metal processing

    Energy Technology Data Exchange (ETDEWEB)

    Nafisi, Sahrooz [Center for University Research on Aluminum, CURAL, University of Quebec at Chicoutimi, Chicoutimi, Quebec, Canada G7H 2B1 (Canada)]. E-mail: snafisi@ampr-institute.com; Ghomashchi, Reza [Center for University Research on Aluminum, CURAL, University of Quebec at Chicoutimi, Chicoutimi, Quebec, Canada G7H 2B1 (Canada)]. E-mail: reza.ghomashchi@ampr-institute.com

    2007-06-14

    The concurrent presence of liquid and primary solid particles is the principal requirement for semisolid metal (SSM) processing. It is proposed that in addition to the temperature sensitivity of the solid fraction and the SSM temperature process window, partitioning of the solidification range is also essential. The solidification range of hypoeutectic Al-Si alloys is divided into two distinct temperature intervals of {alpha}-Al primary particles formation and eutectic and post-eutectic reactions zone. The primary particles are formed in three steps of {alpha}-Al nucleation, dendrite to rosette/globular transformation and coarsening of the primary {alpha}-Al particles over the entire solidification range. Furthermore the effects of inoculation and modification on these temperature intervals are discussed and elaborated for hypoeutectic Al-Si alloys.

  19. The reactivity study of peptide A3-capped gold and silver nanoparticles with heavy metal ions

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Hongyu [New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006 (China); Tang, Zhenghua, E-mail: zhht@scut.edu.cn [New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006 (China); Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006 (China); Wang, Likai; Zhou, Weijia; Li, Ligui [New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006 (China); Zhang, Yongqing [Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006 (China); Chen, Shaowei, E-mail: shaowei@ucsc.edu [New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006 (China); Department of Chemistry and Biochemistry, University of California, 1156 High Street, Santa Cruz, CA 95064 (United States)

    2016-08-15

    Highlights: • Apparent color change upon the addition of Hg{sup 2+} or As{sup 3+} ions into A3-AuNPs solution. • Distinct color change of A3-AgNPs solution only in the presence of Hg{sup 2+} ions. • The Hg{sup 2+} concentration limit of A3-AgNPs about 40 times lower than A3-AuNPs. • Based on the DLS, TEM and XPS results, two reaction mechanisms have been proposed. - Abstract: Peptide A3-capped gold and silver nanoparticles were prepared by chemical reduction of metal salt precursors. The nanoparticles exhibited apparent but distinctly different color changes upon the addition of selected heavy metal ions. For gold nanoparticles, the solution color was found to change from red to blue in the presence of Hg{sup 2+} or As{sup 3+} ions, accompanied with broadening and a red-shift of the surface plasmon resonance peak. In contrast, silver nanoparticles showed an apparent color change from yellow to colorless only in the presence of Hg{sup 2+}, along with a blue-shift and diminishment of the surface plasmon resonance peak. The Hg{sup 2+} reaction concentration limit of silver nanoparticle was about 40 times lower than that of gold nanoparticle. Based on the dynamic light scattering, transmission electron microscopy and X-ray photoelectron spectroscopic results, the reaction mechanism has been proposed. Such a sensitive variation of the nanoparticle optical properties to selective ions might be exploited for ion detection for potential applications.

  20. Influence of the ageing process on the resistive and reactive properties of the respiratory system

    Directory of Open Access Journals (Sweden)

    Caio Vinicius Villalón e Tramont

    2009-11-01

    Full Text Available INTRODUCTION: In an increasingly old society, the study of the respiratory system changes and new techniques dedicated to older patients are of interest in physiologic studies as well as in the diagnosis of respiratory diseases. OBJECTIVES: (1 To investigate the impact of ageing on the resistive and reactive properties of the respiratory system, and (2 to compare the easiness of accomplishment of spirometry and forced oscillation for assessing lung function. METHODS: We conducted a cross-sectional study in which forced oscillation was used to investigate respiratory system resistive and reactive properties, while spirometry was used as a reference test to evaluate 80 normal subjects aged between 20 and 86 years. A questionnaire was used to evaluate the easiness of accomplishment of spirometry and forced oscillation. RESULTS: There was a significant increase in the respiratory system resonance frequency (p<0.003 and a reduction in the mean reactance (p<0.004 with increasing age. Respiratory system resistance and dynamic compliance were not related to the ageing process. The easiness of accomplishment of forced oscillation measurements was greater than that of spirometry. This result was particularly relevant in subjects over 70 years old (p<0.05. CONCLUSIONS: Respiratory system resistance and dynamic compliance are not modified with ageing. On the other hand, respiratory system homogeneity decreases during the ageing process. Forced oscillation is easy to perform and provides information complementary to spirometry. This technique may be a promising alternative and/or complement to other conventional exams used to evaluate older people who are unable to adequately perform spirometric tests.

  1. Treatment of Synthetic Wastewater Containing Reactive Red 198 by Electrocoagulation Process

    Directory of Open Access Journals (Sweden)

    N.M Mahmoodi

    2011-04-01

    Full Text Available "nBackground and Objectives: Discharge of textile colored wastewater industries without providing enough treatment in water bodies, is harmful for human and aquatic organisms and poses serious damages to the environment. Most of conventional wastewater treatment methods don't have enough efficiency to remove textile dyes from colored wastewater; thus in this research the efficiency of electrocoagulation treatment process with aluminum electrodes for treatment of a synthetic wastewater containing C.I. Reactive Red 198 in batch reactor was studied."nMaterial and Methods: The experiment conducted in a Plexiglas reactor with a working volume of 2L that equipped with 4 aluminum electrodes. The effects of operating parameters such as voltage, time of reaction, initial dye concentration and interelectrode distance on the color removal efficiency, electrical energy consumption and electrode consumption were investigated."nResults: in the optimum operational condition electrocoagulation, is able to remove color and COD as high as 99.1 and 84.3% in aluminum electrode in 75 minutes at 20 volt and 2 cm interelectrode distance, respectively. Under this condition, operating cost was 2986 rails per cubic meter of treated wastewater. Increase in the interelectrode distance and initial dye concentration,lead to the decrease in efficiency of dye and COD removal.While as the voltage and time of reaction increased, energy consumption, electrode consumption, final pH and color removal, increased too."nConclusion: electrocoagulation process by aluminum electrode is an efficient and suitable method for reactive dye removal from colored wastewater.

  2. Synthesis, structure, and reactivity of tris(amidate) mono(amido) and tetrakis(amidate) complexes of group 4 transition metals.

    Science.gov (United States)

    Payne, Philippa R; Thomson, Robert K; Medeiros, Diane M; Wan, Geoff; Schafer, Laurel L

    2013-11-28

    The syntheses of a series of tris(amidate) mono(amido) titanium and zirconium complexes are reported. The binding motif of the amidate ligand has been determined to depend on the size of the metal centre for these sterically demanding N,O-chelating ligands; the larger zirconium metal centre supports three κ(2)-(N,O) bound amidate ligands while the titanium analogue has one ligand bound in a κ(1)-(O) fashion to alleviate steric strain. Reactivity studies indicate that, despite high steric crowding about the tris(amidate) mono(amido) zirconium metal centre, transamination of the reactive dimethylamido ligand can be achieved using aniline. This complex is also an active precatalyst for intramolecular alkene hydroamination, in which protonolysis of one amidate ligand in the presence of excess amine is observed as an initiation step prior to catalytic turnover. Eight-coordinate homoleptic κ(2)-amidate complexes of zirconium and hafnium have also been prepared.

  3. Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O2 dissociation on Ag(111).

    Science.gov (United States)

    Xin, Hongliang; Linic, Suljo

    2016-06-21

    Many commercial heterogeneous catalysts are complex structures that contain metal active sites promoted by multiple additives. Developing fundamental understanding about the impact of these perturbations on the local surface reactivity is crucial for catalyst development and optimization. In this contribution, we develop a general framework for identifying underlying mechanisms that control the changes in the surface reactivity of a metal site (more specifically the adsorbate-surface interactions) upon a perturbation in the local environment. This framework allows us to interpret fairly complex interactions on metal surfaces in terms of specific, physically transparent contributions that can be evaluated independently of each other. We use Cs-promoted dissociation of O2 as an example to illustrate our approach. We concluded that the Cs adsorbate affects the outcome of the chemical reaction through a strong alkali-induced electric field interacting with the static dipole moment of the O2/Ag(111) system.

  4. Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O2 dissociation on Ag(111)

    Science.gov (United States)

    Xin, Hongliang; Linic, Suljo

    2016-06-01

    Many commercial heterogeneous catalysts are complex structures that contain metal active sites promoted by multiple additives. Developing fundamental understanding about the impact of these perturbations on the local surface reactivity is crucial for catalyst development and optimization. In this contribution, we develop a general framework for identifying underlying mechanisms that control the changes in the surface reactivity of a metal site (more specifically the adsorbate-surface interactions) upon a perturbation in the local environment. This framework allows us to interpret fairly complex interactions on metal surfaces in terms of specific, physically transparent contributions that can be evaluated independently of each other. We use Cs-promoted dissociation of O2 as an example to illustrate our approach. We concluded that the Cs adsorbate affects the outcome of the chemical reaction through a strong alkali-induced electric field interacting with the static dipole moment of the O2/Ag(111) system.

  5. Expanding the role of reactive transport models in critical zone processes

    Science.gov (United States)

    Li, Li; Maher, Kate; Navarre-Sitchler, Alexis; Druhan, Jennifer; Meile, Christof; Lawrence, Corey; Moore, Joel; Perdrial, Julia; Sullivan, Pamela; Thompson, Aaron; Jin, Lixin; Bolton, Edward W.; Brantley, Susan L.; Dietrich, William E.; Mayer, K. Ulrich; Steefel, Carl; Valocchi, Albert J.; Zachara, John M.; Kocar, Benjamin D.; McIntosh, Jennifer; Tutolo, Benjamin M.; Kumar, Mukesh; Sonnenthal, Eric; Bao, Chen; Beisman, Joe

    2017-01-01

    Models test our understanding of processes and can reach beyond the spatial and temporal scales of measurements. Multi-component Reactive Transport Models (RTMs), initially developed more than three decades ago, have been used extensively to explore the interactions of geothermal, hydrologic, geochemical, and geobiological processes in subsurface systems. Driven by extensive data sets now available from intensive measurement efforts, there is a pressing need to couple RTMs with other community models to explore non-linear interactions among the atmosphere, hydrosphere, biosphere, and geosphere. Here we briefly review the history of RTM development, summarize the current state of RTM approaches, and identify new research directions, opportunities, and infrastructure needs to broaden the use of RTMs. In particular, we envision the expanded use of RTMs in advancing process understanding in the Critical Zone, the veneer of the Earth that extends from the top of vegetation to the bottom of groundwater. We argue that, although parsimonious models are essential at larger scales, process-based models offer tools to explore the highly nonlinear coupling that characterizes natural systems. We present seven testable hypotheses that emphasize the unique capabilities of process-based RTMs for (1) elucidating chemical weathering and its physical and biogeochemical drivers; (2) understanding the interactions among roots, micro-organisms, carbon, water, and minerals in the rhizosphere; (3) assessing the effects of heterogeneity across spatial and temporal scales; and (4) integrating the vast quantity of novel data, including “omics” data (genomics, transcriptomics, proteomics, metabolomics), elemental concentration and speciation data, and isotope data into our understanding of complex earth surface systems. With strong support from data-driven sciences, we are now in an exciting era where integration of RTM framework into other community models will facilitate process

  6. Reactive cognitive-control processes in free-report consonant-vowel dichotic listening.

    Science.gov (United States)

    Westerhausen, René; Passow, Susanne; Kompus, Kristiina

    2013-12-01

    The relevance of cognitive-control processes has been frequently discussed and studied in the context of dichotic listening. Experimental and clinical studies indicate that directing attention to either of the two simultaneously presented phonological stimuli, but especially to the left-ear stimulus increases the requirements for cognitive-control processes. Here, we extend this view by reporting the results of a behavioural and a functional magnetic-resonance imaging (fMRI) experiment designed to analyse the involvement of cognitive-control processes also in a free-report dichotic-listening paradigm. It was hypothesised that dichotically presented pairs of stop-consonant-vowel syllables would provide different demands for cognitive-control processes as a function of the spectro-temporal overlap of the two stimuli. Accordingly, in Experiment 1 it was shown that dichotic syllables of high (e.g., /ba/ and /ga/) as opposed to low spectro-temporal overlap (e.g., /ba/ and /ka/) produce significantly faster and more correct answers, and are more often perceived as one syllable. In Experiment 2 it was further shown that pairs of low as compared to high spectro-temporal overlap trigger a more pronounced activation predominately in left-hemispheric, speech-associated brain regions, namely left posterior inferior sulcus/gyrus, bilaterally in pre-supplementary motor and mid-cingulate cortex as well as in the inferior parietal lobe. Taken together, behavioural and functional data indicate a stronger involvement of reactive cognitive control in the processing of low-overlap as opposed to high-overlap stimulus pairs. This supports the notion that higher-order, speech-related cognitive-control processes also are involved in a free-report dichotic-listening paradigm. Copyright © 2013 Elsevier Inc. All rights reserved.

  7. Reactivity of CO2 Activated on Transition Metals and Sulfur Ligands.

    Science.gov (United States)

    Kobayashi, Katsuaki; Tanaka, Koji

    2015-06-01

    Dicationic dicarbonyl [Ru(bpy)2(CO)2](2+) (bpy = 2,2'- bipyridyl) exists as equilibrium mixtures with [Ru(bpy)2(CO)(COOH)](+) and [Ru(bpy)2(CO)(CO2)](0) depending on the pH in H2O. Those three complexes work as the precursors to CO, HCOOH production, and CO2 carrier, respectively, in electro- and photochemical CO2 reduction in aqueous solutions. However, [Ru(bpy)2(CO)2](2+) loses the catalytic activity toward CO2 reduction under aprotic conditions because [Ru(bpy)2(CO)2](2+) is not regenerated from [Ru(bpy)2(CO)(CO2)](0) in the absence of proton sources. Analogous monocarbonylruthenium complexes such as [Ru(tpy)(bpy)(CO)](2+) and [Ru(bpy)2(qu)(CO)](2+) catalyze CO2 reduction in the absence and presence of proton sources. Both complexes are reproduced through oxide transfer from the corresponding Ru-CO2 to CO2 in CO2 reduction and produce the same amount of CO and CO3(2-) in the absence of proton donors. The reduction of CO2 catalyzed by polypyridylrhenium complexes in the presence of proton sources takes place via essentially the similar mechanism as that in the case of ruthenium complexes. On the other hand, CO evolution in CO2 reduction under aprotic conditions is ascribed to the dissociation of CO from a dimeric Re-C(O)OC(O)O-Re scaffold. Visible-light irradiation to a catalytic system composed of [Ru(bpy)2(CO)2](2+)/[Ru(bpy)3](2+)/Me2NH2(+)/Me2NH as the catalyst, photosensitizer, proton donor, and nucleophile in addition to the electron donor, respectively, in CO2-saturated CH3CN selectively produces N,N-dimethylformamide without concomitant CO and HCOOH formation. Structurally robust μ3-S of reduced metal-sulfur clusters provides a suitable site for reductive activation of CO2 with retention of the framework. Indeed, CO2 activated on μ3-S of [Fe6Mo2S8(SEt)3](5-) is fixed at the carbonyl carbon of thioesters trapped on a neighboring iron of the cluster, and α-keto acids are produced catalytically. Furthermore, two-electron reduction of [(CpMen)3M3S3](2+) (n

  8. The Conjugation Stress of Ligand via Metal Core as the Cause of Changes in the Reactivity of Coordinated 1-Hetero-1,3-Dienes

    Directory of Open Access Journals (Sweden)

    A.I. Kuramshin

    2016-06-01

    Full Text Available Using quantum-chemical calculations carried out for interpretation of the experimentally discovered reactivity of 1-hetero-1,3-dienes that are mono- and bidentally coordinated with the transition metal core, we have revealed that the difference in hydrophosphorylation directions of the free organic molecule and the same molecule involved in the coordination sphere of the transition metal can be explained by either weakening or complete loss of conjugation between the C=C and C=X fragments as a result of coordination. In the case of monodentate coordination of heterodiene with the transition metal according to the eta(2(C,C-type, the conjugation weakening is suggested to be maximum for the transition metal characterized by the minimum electronegativity, which predetermines the increased contribution of the metalcyclopropane resonance structure into the general bonding mode. Organometallic compounds having the heterodiene ligand bidentally coordinated demonstrate the conjugation weakening parallel to the metal radius.

  9. Block Copolymer Modified Epoxy Amine System for Reactive Rotational Molding: Structures, Properties and Processability

    Science.gov (United States)

    Lecocq, Eva; Nony, Fabien; Tcharkhtchi, Abbas; Gérard, Jean-François

    2011-05-01

    Poly(styrene-butadiene-methylmethacrylate) (SBM) and poly(methylmethacrylate-butyle-acrylate-methylmethacrylate) (MAM) triblock copolymers have been dissolved in liquid DGEBA epoxy resin which is subsequently polymerized by meta-xylene diamine (MXDA) or Jeffamine EDR-148. A chemorheology study of these formulations by plate-plate rheology and by thermal analysis has allowed to conclude that the addition of these copolymer blocks improve the reactive rotational moulding processability without affecting the processing time. Indeed, it prevents the pooling of the formulation at the bottom of the mould and a too rapid build up of resin viscosity of these thermosetting systems. The morphology of the cured blends examined by scanning electron microscopy (SEM) shows an increase of fracture surface area and thereby a potential increase of the toughness with the modification of epoxy system. Dynamic mechanical spectroscopy (DMA) and opalescence of final material show that the block PMMA, initially miscible, is likely to induce phase separation from the epoxy-amine matrix. Thereby, the poor compatibilisation between the toughener and the matrix has a detrimental effect on the tensile mechanical properties. The compatibilisation has to be increased to improve in synergy the processability and the final properties of these block copolymer modified formulations. First attempts could be by adapting the length and ratio of each block.

  10. Decolorization and degradation of reactive yellow HF aqueous solutions by electrochemical advanced oxidation processes.

    Science.gov (United States)

    Bedolla-Guzman, A; Feria-Reyes, R; Gutierrez-Granados, S; Peralta-Hernández, Juan M

    2017-05-01

    Textile manufacturing is the one responsible for water bodies' contamination through the discharge of colored wastes. This work presents the study of reactive yellow HF (RYHF) dye degradation under two different electrochemical advanced oxidation processes (EAOP), namely anodic oxidation (AO) and electro-Fenton (EF)/boron-doped diamond (BDD) process. For the AO, 100 and 300 mg/L solutions using Pt and BDD as anodes in a 100 mL stirred tank cell were used, with a supporting electrolyte of 0.05 mol/L of Na2SO4 at pH 3 under 30 and 50 mA/cm(2) current density. The EF/BDD process was carried out in a flow reactor at 4 and 7 L/min to degrade 100, 200, and 300 mg/L RYHF solutions under 50 and 80 mA/cm(2). UV-Vis determinations were used for decolorization evaluation, while high-performance liquid chromatography (HPLC) method provided information on dye degradation rate.

  11. Information processing schemes based on monolayer protected metallic nanoclusters.

    Science.gov (United States)

    Cervera, Javier; Mafé, Salvador

    2011-09-01

    Nanostructures are potentially useful as building blocks to complement future electronics because of their high versatility and packing densities. The fabrication and characterization of particular nanostructures and the use of new theoretical tools to describe their properties are receiving much attention. However, the integration of these individual systems into general schemes that could perform simple tasks is also necessary because modern electronics operation relies on the concerted action of many basic units. We review here new conceptual schemes that can allow information processing with ligand or monolayer protected metallic nanoclusters (MPCs) on the basis of the experimentally demonstrated and theoretically described electrical characteristics of these nanostructures. In particular, we make use of the tunnelling current through a metallic nanocluster attached to the electrodes by ligands. The nanostructure is described as a single electron transistor (SET) that can be gated by an external potential. This fact permits exploiting information processing schemes in approximately defined arrays of MPCs. These schemes include: (i) binary, multivalued, and reversible logic gates; (ii) an associative memory and a synchronization circuit; and (iii) two signal processing nanodevices based on parallel arrays of MPCs and nanoswitches. In each case, the practical operation of the nanodevice is based on the SET properties of MPCs reported experimentally. We examine also some of the practical problems that should be addressed in future experimental realizations: the stochastic nature of the electron tunnelling, the relatively low operation temperatures, and the limited reliability caused by the weak signals involved and the nanostructure variability. The perspectives to solve these problems are based on the potentially high degree of scalability of the nanostructures.

  12. Rare-earth metal hydrides supported by silicon-bridged boratabenzene fluorenyl ligands: synthesis, structure and reactivity.

    Science.gov (United States)

    Wang, Chunhong; Xiang, Li; Leng, Xuebing; Chen, Yaofeng

    2017-01-24

    The reactions of rare-earth metal benzyl complexes supported by silicon-bridged boratabenzene fluorenyl ligands with PhSiH3 in toluene gave the corresponding dinuclear hydrides [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}Ln(μ-H)(THF)]2 (3-Ln; Ln = La, Nd, Gd), wherein the rare-earth metal ions are linked by both silicon-bridged boratabenzene fluorenyl ligands and hydrido ligands. The reactivity of these hydrides toward unsaturated substrates was studied. Among these, alkynides [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}Ln(μ-CCPh)]2 (4-Ln; Ln = La, Nd) were obtained via the σ-bond metathesis reaction, when 3-Ln (Ln = La, Nd) was treated with phenylacetylene. While reacting with 3-hexyne, the mono-addition product [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}Ln]2(μ-H)[μ-C(Et)[double bond, length as m-dash]C(H)Et] (5-Ln; Ln = La, Nd) was formed. Further investigations on the reactivity of 3-La displayed that benzonitrile and tert-butyl isonitrile readily inserted into the La-H bonds, affording an azomethine complex [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}La{μ-N[double bond, length as m-dash]C(H)Ph}]2 (6-La) and an N-tert-butylformimidoyl complex [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}La{μ,η(2)-C(H)[double bond, length as m-dash]N(t)Bu}]2 (7-La), respectively. The reaction with N,N'-diisopropylcarbodiimide at room temperature or at 75 °C gave a dimeric complex [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}La]2(μ-H)[μ-N((i)Pr)CHN((i)Pr)] (8-La) or a monomeric complex [Me2Si(C13H8)(C5H4BNEt2)]La[N((i)Pr)CHN((i)Pr)] (9-La), respectively.

  13. Optimization of Gas Metal Arc Welding Process Parameters

    Science.gov (United States)

    Kumar, Amit; Khurana, M. K.; Yadav, Pradeep K.

    2016-09-01

    This study presents the application of Taguchi method combined with grey relational analysis to optimize the process parameters of gas metal arc welding (GMAW) of AISI 1020 carbon steels for multiple quality characteristics (bead width, bead height, weld penetration and heat affected zone). An orthogonal array of L9 has been implemented to fabrication of joints. The experiments have been conducted according to the combination of voltage (V), current (A) and welding speed (Ws). The results revealed that the welding speed is most significant process parameter. By analyzing the grey relational grades, optimal parameters are obtained and significant factors are known using ANOVA analysis. The welding parameters such as speed, welding current and voltage have been optimized for material AISI 1020 using GMAW process. To fortify the robustness of experimental design, a confirmation test was performed at selected optimal process parameter setting. Observations from this method may be useful for automotive sub-assemblies, shipbuilding and vessel fabricators and operators to obtain optimal welding conditions.

  14. Part height control of laser metal additive manufacturing process

    Science.gov (United States)

    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.

  15. Studies on Dyeing Process Variables for Salt Free Reactive Dyeing of Glycine Modified Cationized Cotton Muslin Fabric

    Science.gov (United States)

    Samanta, Ashis Kumar; Kar, Tapas Ranjan; Mukhopadhyay, Asis; Shome, Debashis; Konar, Adwaita

    2015-04-01

    Bleached cotton muslin fabric with or without pre-oxidized with NaIO4 (oxy-cotton) was chemically modified with glycine (amino acid) by pad dry calendar process to investigate the changes in textile properties and its dyeability with reactive dye. This glycine modified cotton incorporates new functional groups producing -NH3 + or -C=NH+ -ion (cationic groups) in acid bath to obtain cationized cotton making it amenable to a newer route of salt free reactive dyeing in acid bath. In the present work the process variables of reactive dyeing in the salt free acid bath for dyeing of amine (glycine) modified cationized cotton were studied and optimized. The present study also includes thorough investigation of changes in important textile related properties and dyeability with reactive dye after such chemical modifications. Between oxidized and unoxidized cotton muslin fabric, unoxidized cotton fabric shows better reactive dye uptake in both conventional alkaline bath dyeing and nonconventional salt free acid bath dyeing particularly for high exhaustion class of reactive dye with acceptable level of colour fastness and overall balance of other textile related properties. Moreover, application of dye fixing agent further improves surface colour depth (K/S) of the glycine treated cotton fabric for HE brand of reactive dyes. Corresponding reaction mechanisms for such modifications were supported by FTIR spectroscopy. Finally unoxidized cotton and pre-oxidized cotton further treated with glycine (amino acid) provide a new route of acid bath salt free reactive dyeing showing much higher dye uptake and higher degree of surface cover with amino acid residue anchored to modified cotton.

  16. Removal of Reactive Red 141 Dye from Synthetic Wastewater by Electrocoagulation Process: Investigation of Operational Parameters

    Directory of Open Access Journals (Sweden)

    Elham Rahmanpour Salmani

    2016-01-01

    Full Text Available Release of textile industries waste especially their dying effluent impose a serious pollution on the environment. Reactive dyes are one of the most used dyes which are recalcitrant to conventional treatment processes. In the performed project, the effectiveness of electrocoagulation process was studied on decolorization. RR141 was selected as model dye and treatment process was performed in a simple batch of electrocoagulation (EC cell using iron electrodes. Central Composite Design (CCD was used to plan study runs. Experiments were done under 5 levels of various operational parameters at bench scale. Initial concentration of dye was varied among 50 and 500ppm, pH ranging from 4-12; retention time was ranged between 3-30 minutes, 1-3cm was selected as the distance between electrodes, and current intensity studied under the range of 5-30 mA/cm2. EC treatment process of dyestuff wastewater was satisfactory at high levels of current density, pH, and retention time. While increasing the initial dye concentration and electrodes gap had a negative effect on decolorization performance. Determined optimal conditions to treat 200ml of sample were including pH: 9.68, electrode gap: 1.58cm, dye concentration: 180ppm, retention time: 10.82 minutes, and current intensity: 22.76mA/cm2. Successful removal of the model dye about 99.88% was recorded in the mentioned values of variables. Simple design and operation of the experiments can be an interesting option for implementation and applying of inexpensive electrocoagulation treatment process which was successful to reach nearly a complete decolorization.

  17. Different Reactive Oxygen Species Lead to Distinct Changes of Cellular Metal Ions in the Eukaryotic Model Organism Saccharomyces cerevisiae

    Directory of Open Access Journals (Sweden)

    Peter J. Rogers

    2011-11-01

    Full Text Available Elemental uptake and export of the cell are tightly regulated thereby maintaining the ionomic homeostasis. This equilibrium can be disrupted upon exposure to exogenous reactive oxygen species (ROS, leading to reduction or elevation of the intracellular metal ions. In this study, the ionomic composition in the eukaryotic model organism Saccharomyces cerevisiae was profiled using the inductively-coupled plasma optical emission spectrometer (ICP-OES following the treatment with individual ROS, including hydrogen peroxide, cumen hydroperoxide, linoleic acid hydroperoxide (LAH, the superoxide-generating agent menadione, the thiol-oxidising agent diamide [diazine-dicarboxylic acid-bis(dimethylamide], dimedone and peroxynitrite. The findings demonstrated that different ROS resulted in distinct changes in cellular metal ions. Aluminium (Al3+ level rose up to 50-fold after the diamide treatment. Cellular potassium (K+ in LAH-treated cells was 26-fold less compared to the non-treated controls. The diamide-induced Al3+ accumulation was further validated by the enhanced Al3+ uptake along the time course and diamide doses. Pre-incubation of yeast with individual elements including iron, copper, manganese and magnesium failed to block diamide-induced Al3+ uptake, suggesting Al3+-specific transporters could be involved in Al3+ uptake. Furthermore, LAH-induced potassium depletion was validated by a rescue experiment in which addition of potassium increased yeast growth in LAH-containing media by 26% compared to LAH alone. Taken together, the data, for the first time, demonstrated the linkage between ionomic profiles and individual oxidative conditions.

  18. Development of analytical code for core disruptive accident of metallic fuel core and evaluation of upper limitation of coolant void reactivity

    Energy Technology Data Exchange (ETDEWEB)

    Ueda, Nobuyuki [Central Research Inst. of Electric Power Industry, Komae, Tokyo (Japan). Komae Research Lab

    2001-06-01

    In the event of HCDA (Hypothetical Core Damage Accident) the safety of the metallic core must be ensured. Coolant void reactivity, which produces a positive reactivity effect, must be restrained to exclude 'energetic sequence' (uncontrollable power generation). As this reactivity and the core performance are in a state of confrontation, an upper limit must be determined through safety analyses. The larger the coolant void reactivity becomes, the more the core performance improves. A core dynamics analysis code named CANIS has been developed to analysis metallic fuel properties, irradiation behavior, and transient behavior in the initiating phase of HCDA. ULOF (Unprotected Loss Of Flow) events, which are considered major HCDA initiators, are analyzed with various parameters of cladding failure conditions and molten fuel dispersion velocities. The results indicate, the cladding failure condition is the most sensitive safety parameter. The coolant void reactivity of 12$ is acceptable in the condition that cladding fails at 1,000 degC. And the upper value is limited to 8$ for the conservative condition of a 1,200 degC failure criteria. (author)

  19. Optimized process parameters for fabricating metal particles reinforced 5083 Al composite by friction stir processing.

    Science.gov (United States)

    Bauri, Ranjit; Yadav, Devinder; Shyam Kumar, C N; Janaki Ram, G D

    2015-12-01

    Metal matrix composites (MMCs) exhibit improved strength but suffer from low ductility. Metal particles reinforcement can be an alternative to retain the ductility in MMCs (Bauri and Yadav, 2010; Thakur and Gupta, 2007) [1,2]. However, processing such composites by conventional routes is difficult. The data presented here relates to friction stir processing (FSP) that was used to process metal particles reinforced aluminum matrix composites. The data is the processing parameters, rotation and traverse speeds, which were optimized to incorporate Ni particles. A wide range of parameters covering tool rotation speeds from 1000 rpm to 1800 rpm and a range of traverse speeds from 6 mm/min to 24 mm/min were explored in order to get a defect free stir zone and uniform distribution of particles. The right combination of rotation and traverse speed was found from these experiments. Both as-received coarse particles (70 μm) and ball-milled finer particles (10 μm) were incorporated in the Al matrix using the optimized parameters.

  20. Optimized process parameters for fabricating metal particles reinforced 5083 Al composite by friction stir processing

    Directory of Open Access Journals (Sweden)

    Ranjit Bauri

    2015-12-01

    Full Text Available Metal matrix composites (MMCs exhibit improved strength but suffer from low ductility. Metal particles reinforcement can be an alternative to retain the ductility in MMCs (Bauri and Yadav, 2010; Thakur and Gupta, 2007 [1,2]. However, processing such composites by conventional routes is difficult. The data presented here relates to friction stir processing (FSP that was used to process metal particles reinforced aluminum matrix composites. The data is the processing parameters, rotation and traverse speeds, which were optimized to incorporate Ni particles. A wide range of parameters covering tool rotation speeds from 1000 rpm to 1800 rpm and a range of traverse speeds from 6 mm/min to 24 mm/min were explored in order to get a defect free stir zone and uniform distribution of particles. The right combination of rotation and traverse speed was found from these experiments. Both as-received coarse particles (70 μm and ball-milled finer particles (10 μm were incorporated in the Al matrix using the optimized parameters.

  1. Ultrafast photoinduced processes in fullerene-metal nanostructures

    Science.gov (United States)

    Chekalin, Sergey; Kompanets, Victor; Starodubtsev, Nickolai

    2006-01-01

    Investigation of photo-induced processes in Sn nanocrystals covered by a submonolayer of C 60 anions was performed with femtosecond pump-probe method. Samples in thin films were excited by 150 fs laser pulse at 400 nm (10 9 W/cm2). Dynamics of difference transmission and reflection has been measured in the spectral range of 1 100-1700 nm. The dynamics of relaxation are quite different for various nanostructures depending on the deposition mode and the ratio of tin and fullerene content. Relaxation, observed in the samples, is explained by electron transfer from excited anions to metal followed by energy transfer from excited C 60 molecules to anions in the ground state.

  2. Modeling of Fume Formation from Shielded Metal Arc Welding Process

    Science.gov (United States)

    Sivapirakasam, S. P.; Mohan, Sreejith; Santhosh Kumar, M. C.; Surianarayanan, M.

    2017-04-01

    In this study, a semi-empirical model of fume formation rate (FFR) from a shielded metal arc welding (SMAW) process has been developed. The model was developed for a DC electrode positive (DCEP) operation and involves the calculations of droplet temperature, surface area of the droplet, and partial vapor pressures of the constituents of the droplet to predict the FFR. The model was further extended for predicting FFR from nano-coated electrodes. The model estimates the FFR for Fe and Mn assuming constant proportion of other elements in the electrode. Fe FFR was overestimated, while Mn FFR was underestimated. The contribution of spatters and other mechanism in the arc responsible for fume formation were neglected. A good positive correlation was obtained between the predicted and experimental FFR values which highlighted the usefulness of the model.

  3. Modeling of Fume Formation from Shielded Metal Arc Welding Process

    Science.gov (United States)

    Sivapirakasam, S. P.; Mohan, Sreejith; Santhosh Kumar, M. C.; Surianarayanan, M.

    2017-01-01

    In this study, a semi-empirical model of fume formation rate (FFR) from a shielded metal arc welding (SMAW) process has been developed. The model was developed for a DC electrode positive (DCEP) operation and involves the calculations of droplet temperature, surface area of the droplet, and partial vapor pressures of the constituents of the droplet to predict the FFR. The model was further extended for predicting FFR from nano-coated electrodes. The model estimates the FFR for Fe and Mn assuming constant proportion of other elements in the electrode. Fe FFR was overestimated, while Mn FFR was underestimated. The contribution of spatters and other mechanism in the arc responsible for fume formation were neglected. A good positive correlation was obtained between the predicted and experimental FFR values which highlighted the usefulness of the model.

  4. Enhancement of surface integrity of titanium alloy with copper by means of laser metal deposition process

    CSIR Research Space (South Africa)

    Erinosho, MF

    2016-04-01

    Full Text Available The laser metal deposition process possesses the combination of metallic powder and laser beam respectively. However, these combinations create an adhesive bonding that permanently solidifies the laser-enhanced-deposited powders. Titanium alloys (Ti...

  5. Impact of Lewis base on chemical reactivity and separation efficiency for hydrated fourth-row transition metal (II) complexes: an ONIOM DFT/MM study.

    Science.gov (United States)

    He, Dingsheng; Ma, Ming

    2014-04-24

    In this paper, two-layer ONIOM combinations of high-level quantum mechanics (QM) and inexpensive molecular mechanics (MM) are successfully used to investigate the structural characters of metal (M, all the transition metals in the fourth period)-H2O-Lewis base (A(-)) complexes. Global and local descriptors of chemical reactivity and selectivity from conceptual density functional theory are employed to show the properties of the active complexes of M(H2O)2A2 and to study the effect of the Lewis base for the separation of transition metal ions. It is shown that chemical potential, hardness, electrophilicity, as well as the dual and multiphilic descriptors are adequate for characterizing the global and local reactivity trends of the M(H2O)2A2 complex. It is found that the reactivity is well localized at the metallic center in M(H2O)2A2 and the dual descriptor (ΔfM(r)) can also be used to characterize the directional attack of the electrophile and nucleophile except for the selectivity of the reaction. On the basis of the values of ωM and Δsk, and the sign of ΔfM(r), the selectivity of the nucleophilic reagent (R(-)) for M(II) in M(H2O)2A2 (from high to low) follows this order: Cu(II) > Ni(II) > Co(II) > Fe(II) ≫ Mn(II) > Zn(II) > Cr(II). The Lewis base (A(-)) improves chemical reactivity and selectivity because of changing the reaction path and forming an intermediate, which possesses the higher antibonding character and the larger HOMO/LUMO gap. NBO or AIMALL analysis and Frontier orbital theory results presented here provided more theoretical support for the above reactivity and selectivity studies.

  6. Modelling of the reactive sputtering process with non-uniform discharge current density and different temperature conditions

    Science.gov (United States)

    Vašina, P; Hytková, T; Eliáš, M

    2009-05-01

    The majority of current models of the reactive magnetron sputtering assume a uniform shape of the discharge current density and the same temperature near the target and the substrate. However, in the real experimental set-up, the presence of the magnetic field causes high density plasma to form in front of the cathode in the shape of a toroid. Consequently, the discharge current density is laterally non-uniform. In addition to this, the heating of the background gas by sputtered particles, which is usually referred to as the gas rarefaction, plays an important role. This paper presents an extended model of the reactive magnetron sputtering that assumes the non-uniform discharge current density and which accommodates the gas rarefaction effect. It is devoted mainly to the study of the behaviour of the reactive sputtering rather that to the prediction of the coating properties. Outputs of this model are compared with those that assume uniform discharge current density and uniform temperature profile in the deposition chamber. Particular attention is paid to the modelling of the radial variation of the target composition near transitions from the metallic to the compound mode and vice versa. A study of the target utilization in the metallic and compound mode is performed for two different discharge current density profiles corresponding to typical two pole and multipole magnetics available on the market now. Different shapes of the discharge current density were tested. Finally, hysteresis curves are plotted for various temperature conditions in the reactor.

  7. Impaired neural reward processing in children and adolescents with reactive attachment disorder: A pilot study.

    Science.gov (United States)

    Mizuno, Kei; Takiguchi, Shinichiro; Yamazaki, Mika; Asano, Mizuki; Kato, Shiho; Kuriyama, Kikuko; Watanabe, Yasuyoshi; Sadato, Norihiro; Tomoda, Akemi

    2015-10-01

    Reactive attachment disorder (RAD) is characterized by markedly disturbed and developmentally inappropriate social relatedness due to parental maltreatment. RAD patients often display a high number of comorbid attention deficit/hyperactivity disorder (ADHD) symptoms, and certain RAD symptoms are difficult to discriminate from ADHD. One of the core characteristics of ADHD is a decrease in neural reward processing due to dopamine dysfunction. The aim of the present study was to determine whether the brain activity involved in reward processing in RAD patients is impaired in comparison with ADHD patients and typically developed controls. Five RAD patients, 17 typically developed (TD) controls and 17 ADHD patients aged 10-16 years performed tasks with high and low monetary reward while undergoing functional magnetic resonance imaging. ADHD patients were tested before and after 3 months treatment with osmotic release oral system-methylphenidate. Before treatment, ADHD patients showed that striatal and thalamus activities only in the tasks with low monetary reward were lower than TD controls. RAD patients showed decrease in activity of the caudate, putamen and thalamus during both the high and low monetary reward conditions in comparison with all the other groups. In RAD patients, the activity of the putamen was associated with the severity of posttraumatic stress and overt dissociation. Reward sensitivity was markedly decreased in children and adolescents with RAD, as evidenced by a diminished neural response during reward perception. This suggests that dopaminergic dysfunction exists in these patients, and may inform future dopaminergic treatment strategies for RAD.

  8. Calculation of reactivity by digital processing; Calcul de la reactivite par traitement numerique

    Energy Technology Data Exchange (ETDEWEB)

    Hedde, J. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1968-12-01

    With a view to exploring the new possibilities offered by digital techniques, a description is given of the optimum theoretical conditions of a computation of the realtime reactivity using counting samples (obtained from a nuclear reactor). The degree to which these optimum conditions can be attained depends on the complexity of the processing which can be accepted. A compromise thus has to be made between the accuracy required and the simplicity of the equipment carrying out the processing. An example is given, using a relatively simple structure, which gives an idea of the accuracy of the results obtained over a wide range of reactor power. (author) [French] Dans le but d'explorer les possibilites nouvelles des techniques numeriques, on decrit les conditions theoriques optimales d'un calcul de la reactivite en temps reel a partir d'echantillons de comptage (en provenance d'un reacteur nucleaire). Ces conditions optimales peuvent etre approchees d'autant mieux que l'on accepte un traitement plus complexe. Un compromis est donc a faire entre la precision desiree et la simplicite du materiel assurant le traitement. Un exemple adoptant une structure de complexite reduite permet de juger de la precision des resultats obtenus sur une importante plage d'evolution de la puissance. (auteur)

  9. Silicon solar cells textured by reactive ion etching and processed with screen printing

    Energy Technology Data Exchange (ETDEWEB)

    Burgers, A.R.; Tool, C.J.J.; Hylton, J.D.; Weeber, A.W. [ECN Solar and Wind, Netherlands Energy Research Foundation ECN, Petten (Netherlands); Verholen, A.G.B.J.; Gardeniers, J.G.E.; De Boer, M.J.; Elwenspoek, M.C. [MESA Research Institute for Micro Electronics, Materials- and Molecular Engineering, and Sensors and Actuators, University of Twente, Enschede (Netherlands)

    1998-07-01

    Reactive Ion Etching (RIE) can texture multicrystalline silicon wafers very well. RIE has the advantage over alkaline etches that it is not sensitive to the crystallographic orientation. RIE has the advantage over acid etches that it can be controlled much better. This work describes multicrystalline silicon solar cells textured by RIE and processed with an industrial process sequence consisting of mainly screen-printing steps. We also made mini-modules of the RIE textured cells. The RIE texturing parameters can be varied to give different textures. Care must be taken that the texture is sufficiently rough to give a low encapsulated reflectance but not so rough that carriers generated by light absorbed in the texture recombine at the surface and cannot be collected at the p-n junction. The screen printing on RIE textured cells was successful. We were able to make cells with both low reflectance and good quantum efficiency. Due to encapsulation problems we were not able to demonstrate an efficiency gain yet. 10 refs.

  10. Reactive control processes contributing to residual switch cost and mixing cost across the adult lifespan.

    Science.gov (United States)

    Whitson, Lisa R; Karayanidis, Frini; Fulham, Ross; Provost, Alexander; Michie, Patricia T; Heathcote, Andrew; Hsieh, Shulan

    2014-01-01

    In task-switching paradigms, performance is better when repeating the same task than when alternating between tasks (switch cost) and when repeating a task alone rather than intermixed with another task (mixing cost). These costs remain even after extensive practice and when task cues enable advanced preparation (residual costs). Moreover, residual reaction time mixing cost has been consistently shown to increase with age. Residual switch and mixing costs modulate the amplitude of the stimulus-locked P3b. This mixing effect is disproportionately larger in older adults who also prepare more for and respond more cautiously on these "mixed" repeat trials (Karayanidis et al., 2011). In this paper, we analyze stimulus-locked and response-locked P3 and lateralized readiness potentials to identify whether residual switch and mixing cost arise from the need to control interference at the level of stimulus processing or response processing. Residual mixing cost was associated with control of stimulus-level interference, whereas residual switch cost was also associated with a delay in response selection. In older adults, the disproportionate increase in mixing cost was associated with greater interference at the level of decision-response mapping and response programming for repeat trials in mixed-task blocks. These findings suggest that older adults strategically recruit greater proactive and reactive control to overcome increased susceptibility to post-stimulus interference. This interpretation is consistent with recruitment of compensatory strategies to compensate for reduced repetition benefit rather than an overall decline on cognitive flexibility.

  11. Pore Formation Process of Porous Ti3SiC2 Fabricated by Reactive Sintering

    Directory of Open Access Journals (Sweden)

    Huibin Zhang

    2017-02-01

    Full Text Available Porous Ti3SiC2 was fabricated with high purity, 99.4 vol %, through reactive sintering of titanium hydride (TiH2, silicon (Si and graphite (C elemental powders. The reaction procedures and the pore structure evolution during the sintering process were systematically studied by X-ray diffraction (XRD and scanning electron microscope (SEM. Our results show that the formation of Ti3SiC2 from TiH2/Si/C powders experienced the following steps: firstly, TiH2 decomposed into Ti; secondly, TiC and Ti5Si3 intermediate phases were generated; finally, Ti3SiC2 was produced through the reaction of TiC, Ti5Si3 and Si. The pores formed in the synthesis procedure of porous Ti3SiC2 ceramics are derived from the following aspects: interstitial pores left during the pressing procedure; pores formed because of the TiH2 decomposition; pores formed through the reactions between Ti and Si and Ti and C powders; and the pores produced accompanying the final phase synthesized during the high temperature sintering process.

  12. 279 Watt Metal-Wrap-Through module using industrial processes

    Energy Technology Data Exchange (ETDEWEB)

    Guillevin, N.; Heurtault, B.; Geerligs, L.J.; Anker, J.; Van Aken, B.B.; Bennett, I.J.; Jansen, M.J.; Berkeveld, L.D.; Weeber, A.W.; Bultman, J.H. [ECN Solar Energy, PO Box 1, 1755 ZG Petten (Netherlands); Wenchao, Zhao; Jianming, Wang; Ziqian, Wang; Yingle, Chen; Yanlong, Shen; Zhiyan, Hu; Gaofei, Li; Jianhui, Chen; Bo, Yu; Shuquan, Tian; Jingfeng, Xiong [Yingli Solar, 3399 Chaoyang North Street, Baoding (China)

    2012-09-15

    This paper describes results of metal wrap through (MWT) cells produced from n-type Czochralski silicon wafers, and modules produced from those cells. The use of n-type silicon as base material allows for high efficiencies: for front emitter contacted industrial cells, efficiencies up to 20% have been reported. MWT cells allow even higher cell efficiency due to reduced front metal coverage, and additionally full back-contacting of the MWT cells in a module results in reduced cell to module (CTM) fill factor losses. MWT cells were produced by industrial process technologies. The efficiency of the MWT cells reproducibly exceeds the efficiency of front contact cells based on the same technology by about 0.2-0.3%, and routes for further improvement are analyzed. 60-cell modules were produced from both types of cells (MWT and H-pattern front emitter). In a direct module performance comparison, the MWT module, based on integrated backfoil, produced 3% higher power output than the comparable tabbed front emitter contact module. CTM current differences arise from the higher packing density, and in this experiment from a lower reflectance of the backfoil, in MWT modules. CTM FF differences are related to resistive losses in copper circuitry on the backfoil versus tabs. The CTM FF loss of the MWT module was reduced by 2.2%abs compared to the tabbed front emitter contact module. Finally, simple process optimizations were tested to improve the n-type MWT cell and module efficiency. A module made using MWT cells of 19.6% average efficiency resulted in a power output of 279W. The cell and module results are analyzed and routes for improvements are discussed.

  13. Design of reactive distillation processes for the production of butyl acrylate:Impact of bio-based raw materials☆

    Institute of Scientific and Technical Information of China (English)

    Alexander Niesbach⁎; Natalia Fink; Philip Lutze; Andrzej Górak

    2015-01-01

    The chemical industry is nowadays predominantly using fossil raw materials, but the alternative use of bio-based resources is investigated to account for the foreseeable scarcity of fossil feedstocks. A main challenge of using bio-based feedstocks is the complexity of the impurity profile. For an economic production of bio-based chemicals, the use of intensified processes is inevitable and approaches are needed for the various process intensification techniques to identify their applicability to be used for the production of bio-based components. In the presented study, an approach is shown for the reactive distil ation (RD) technology to identify the most critical bio-based impurities and their impact on the reactive distillation process. The investigated case-study is the production of n-butyl acrylate from acrylic acid and n-butanol. Among al initially identified impurities, the key impurities, having the biggest impact on the product purity in the reactive distil ation process, are found. These impurities are then studied in more detail and an operating window depending on the impurity concentration is identified for the reactive distil ation column. Furthermore, an integrated design of upstream and downstream processes is facilitated, as the presented results can be used in the development of the fermentation processes for the produc-tion of the bio-based reactants by decreasing the concentration of the critical impurities.

  14. NC INCREMENTAL SHEET METAL FORMING PROCESS AND VERTICAL WALL SQUARE BOX FORMING

    Institute of Scientific and Technical Information of China (English)

    Zhou Liuru; Mo Jianhua; Xiao Xiangzhi

    2004-01-01

    The forming principle and deformation analysis of NC incremental sheet metal forming process as well as the process planning, experiment and key process parameters of vertical wall square box forming are presented. Because the deformation of sheet metal only occurs around the tool head and the deformed region is subjected to stretch deformation, the deformed region of sheet metal thins, and surface area increases. Sheet metal forming stepwise is to lead to the whole sheet metal deformation. The forming half-apex angle θ and corner radius R are the main process parameters in NC incremental forming of vertical wall square box. According to sine law, a vertical wall square box can't be formed by NC incremental sheet metal forming process in a single process, rather, it must be formed in multi processes. Thus, the parallel line type tool path process method is presented to form the vertical wall square box, and the experiment and analysis are made to verify it.

  15. Variability in proactive and reactive cognitive control processes across the adult lifespan

    Directory of Open Access Journals (Sweden)

    Frini eKarayanidis

    2011-11-01

    Full Text Available Task-switching paradigms produce a highly consistent age-related increase in mixing cost (longer RT on repeat trials in mixed-task than single task blocks but a less consistent age effect on switch cost (longer RT on switch than repeat trials in mixed-task blocks. We use two approaches to examine the adult lifespan trajectory of control processes contributing to mixing cost and switch cost: latent variables derived from an evidence accumulation model of choice, and event-related potentials (ERP that temporally differentiate proactive (cue-driven and reactive (target-driven control processes. Under highly practiced and prepared task conditions, ageing was associated with increasing RT mixing cost but reducing RT switch cost. Both effects were largely due to the same cause: an age effect for mixed-repeat trials. In terms of latent variables, increasing age was associated with slower non-decision processes, slower rate of evidence accumulation about the target, and higher response criterion. Age effects on mixing costs were evident only on response criterion, the amount of evidence required to trigger a decision, whereas age effects on switch cost were present for all three latent variables. ERPs showed age-related increases in preparation for mixed-repeat trials, anticipatory attention, and post-target interference. Cue-locked ERPs that are linked to proactive control were associated with early emergence of age differences in response criterion. These results are consistent with age effects on strategic processes controlling decision caution. Consistent with an age-related decline in cognitive flexibility, younger adults flexibly adjusted response criterion from trial-to-trial on mixed-task blocks, whereas older adults maintained a high criterion for all trials.

  16. Geochemical investigations into the retention of reactive carbon compounds for toxic heavy metals. Final report; Geochemische Untersuchungen zur Retention von reaktiven Kohlenstoffverbindungen fuer toxische Schwermetalle. Abschlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Kupsch, H.; Mansel, A.; Crustewitz, C.

    2003-03-01

    The composition, reactivity and stability of reactive organic carbon compounds adsorbed on geogenic matrices was investigated. The surface deposits of NOM and its dependence on geochemical parameters was investigated in selected geomatrices. The retention of toxic heavy metals on these surface deposits of NOM was investigated in consideration of the presence of hydroxy species and inorganic ligands. The investigations of the reactivity of the NOM species requires analyses of these compounds and of the heavy metals in the ultratracer region. This was possible by means of radiochemical methods that were further developed in the context of this project. Radioactive labeling of identified reactive carbon compounds, e.g. with radioactive iodine, on the one hand, and the use of radioactive Cu, Pb, Hg isotopes on the other hand enabled speciation analyses in the binary systems (heavy metal + geomatrix, heavy metal + reactive carbon compounds, reactive carbon compounds + geomatrix) and especially in the ternary system (heavy metal + geomatrix + reactive carbon compounds) in defined conditions. The special labelling techniques were a precondition for distribution measurements in the near-natural, low concentration range. (orig.) [German] Ziel des Projektes war es, mit der vorhandenen Analytik und Expertise die Zusammensetzung, die Reaktivitaet und die Stabilitaet der auf den geogenen Matrizes sorbierten reaktiven organischen Kohlenstoffverbindungen und die damit verbundenen Stoffumsaetze aufzuklaeren. An ausgewaehlten Geomatrizes wurde die Ausbildung von Oberflaechendepositen des NOM und deren Abhaengigkeit gegenueber geochemischen Parametern untersucht. Unter der Beruecksichtigung der Gegenwart von Hydroxyspezies und anorganischen Liganden wurde die Retention toxischer Schwermetalle an diesen Oberflaechendepositen des NOM untersucht. Die Untersuchungen zur Reaktivitaet der NOM-Spezies setzt eine Analytik dieser Verbindungen und der Schwermetalle im Ultraspurenbereich

  17. Modeling and Characterization of Damage Processes in Metallic Materials

    Science.gov (United States)

    Glaessgen, E. H.; Saether, E.; Smith, S. W.; Hochhalter, J. D.; Yamakov, V. I.; Gupta, V.

    2011-01-01

    This paper describes a broad effort that is aimed at understanding the fundamental mechanisms of crack growth and using that understanding as a basis for designing materials and enabling predictions of fracture in materials and structures that have small characteristic dimensions. This area of research, herein referred to as Damage Science, emphasizes the length scale regimes of the nanoscale and the microscale for which analysis and characterization tools are being developed to predict the formation, propagation, and interaction of fundamental damage mechanisms. Examination of nanoscale processes requires atomistic and discrete dislocation plasticity simulations, while microscale processes can be examined using strain gradient plasticity, crystal plasticity and microstructure modeling methods. Concurrent and sequential multiscale modeling methods are being developed to analytically bridge between these length scales. Experimental methods for characterization and quantification of near-crack tip damage are also being developed. This paper focuses on several new methodologies in these areas and their application to understanding damage processes in polycrystalline metals. On-going and potential applications are also discussed.

  18. Water recycle treatment system for use in metal processing

    Energy Technology Data Exchange (ETDEWEB)

    Hewitt, D.E.; Dando, T.J.

    1976-08-10

    A water recycle treatment system is described comprising two main treatment sub-systems for treatment of contaminated water from a plurality of concentrated solutions and rinse baths to separate out the impurities therein. A first sub-system treats less concentrated solutions used for the rinse baths by channeling the flow therefrom to a first neutralizing tank which provides for pH control to produce a mixed output solution having a substantially constant pH factor, which is filtered to remove gross particles, the filtered solution being cooled in a holding tank and passed through a reverse osmosis process and carbon bed to produce clean water. The second sub-system treats highly concentrated solutions obtained from a plurality of chemical processes, mixes them in a second neutralizing tank which is utilized to produce a substantially constant pH output, which is fed to an evaporator to precipitate the metals and salts in sludge and also forms a water vapor output. The reverse osmosis waste is fed back into the second neutralizing tank and processed as noted above.

  19. Entrenched metal lift-off using a novel bilayer process

    Science.gov (United States)

    Dubois, Thomas D.; Tranjan, Farid M.; Jones, Susan K.; Bobbio, Stephen M.; Kellam, Mark D.; Frieser, Rudolph G.; Jones, A. D.

    1990-01-01

    This paper will discuss the preparation and characterization of a modified photoresist and describe its use in a novel bilayer process. The modified photoresist solutions are prepared by dissolving enough cyclic phosphonitrilic chloride trimer, PNCT, in commercially available photoresist solutions to achieve phosphorus concentrations of 10 to 12 weight percent in the resulting films. FTNMR and FTIR data will be presented which demonstrate that the cyclic phosphonitrilic chloride trimer does not undergo chemical reaction with the components of the photoresist in the photoresist solutions or photoresist films. The exposure threshold of the PNCT modified photoresist films is 1.5 times greater than that of the unmodified films. Experimental data will be discussed which suggests the decrease in exposure threshold is the result of a relatively lower concentration of photoactive compound in the PNCT modified films. The PNCT modified films will be shown to provide resolution comparable to that of the unmodified photoresist films and yield a process window of better than 20%. A mechanism for the formation of the 02/N2 plasma resistant etch barrier formed during 02/N2 plasma etching will be discussed. Finally, a bilayer process which uses the PNCT modified photoresist in generating metal features entrenched in polyimide will be presented.

  20. Fabrication of metal suspending nanostructures by nanoimprint lithography(NIL) and isotropic reactive ion etching(RIE)

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    We report herein a rational approach for fabricating metal suspending nanostructures by nanoimprint lithography(NIL) and isotropic reactive ion etching(RIE).The approach comprises three principal steps:(1) mold fabrication,(2) structure replication by NIL,and(3) suspending nanostructures creation by isotropic RIE.Using this approach,suspending nanostructures with Au,Au/Ti or Ti/Au bilayers,and Au/Ti/Au sandwiched structures are demonstrated.For Au nanostructures,straight suspending nanostructures can be obtained when the thickness of Au film is up to 50 nm for nano-bridge and 90 nm for nano-finger patterns.When the thickness of Au is below 50 nm for nano-bridge and 90 nm for nano-finger,the Au suspending nanostructures bend upward as a result of the mismatch of thermal expansion between the thin Au films and Si substrate.This leads to residual stresses in the thin Au films.For Au/Ti or Ti/Au bilayers nanostructures,the cantilevers bend toward Au film,since Au has a larger thermal expansion coefficient than that of Ti.While in the case of sandwich structures,straight suspending nanostructures are obtained,this may be due to the balance of residual stress between the thin films.

  1. Unbound position II in MXCXXC metallochaperone model peptides impacts metal binding mode and reactivity: Distinct similarities to whole proteins.

    Science.gov (United States)

    Shoshan, Michal S; Dekel, Noa; Goch, Wojciech; Shalev, Deborah E; Danieli, Tsafi; Lebendiker, Mario; Bal, Wojciech; Tshuva, Edit Y

    2016-06-01

    The effect of position II in the binding sequence of copper metallochaperones, which varies between Thr and His, was investigated through structural analysis and affinity and oxidation kinetic studies of model peptides. A first Cys-Cu(I)-Cys model obtained for the His peptide at acidic and neutral pH, correlated with higher affinity and more rapid oxidation of its complex; in contrast, the Thr peptide with the Cys-Cu(I)-Met coordination under neutral conditions demonstrated weaker and pH dependent binding. Studies with human antioxidant protein 1 (Atox1) and three of its mutants where S residues were replaced with Ala suggested that (a) the binding affinity is influenced more by the binding sequence than by the protein fold (b) pH may play a role in binding reactivity, and (c) mutating the Met impacted the affinity and oxidation rate more drastically than did mutating one of the Cys, supporting its important role in protein function. Position II thus plays a dominant role in metal binding and transport.

  2. Biodecolorization of Reactive Black-5 by a metal and salt tolerant bacterial strain Pseudomonas sp. RA20 isolated from Paharang drain effluents in Pakistan.

    Science.gov (United States)

    Hussain, Sabir; Maqbool, Zahid; Ali, Shafaqat; Yasmeen, Tahira; Imran, Muhammad; Mahmood, Faisal; Abbas, Farhat

    2013-12-01

    Discharge of untreated azo dyes contaminated textile wastewater into soil and water bodies causes severe contamination. The present study was conducted to isolate dye degrading bacterial strains from a textile industry wastewater carrying drain in the neighborhood of Faisalabad, Pakistan. Seventy six bacterial strains were initially isolated and was screened using liquid mineral salts medium spiked with Reactive Black-5 azo dye. The strain RA20 was found to be the most efficient azo dye degrading bacterial isolate and was identified by amplifying and sequencing its 16S rRNA. Analysis indicated that this strain belonged to genus Pseudomonas and was designated as Pseudomonas sp. RA20. It had the highest decolorization activity at pH 8 and 25 °C incubation temperature under static conditions using yeast extract as an additional C source. This strain was also effective in decolorizing structurally related other reactive dyes including Reactive Orange 16, Reactive Yellow 2 and Reactive Red 120 but with varying efficacy. RA20 decolorized Reactive Black-5 significantly in the presence of up to 30 g L⁻¹ NaCl; however, the decolorization rate was significantly (p≤0.05) reduced beyond this salt concentration. Moreover, this bacterial strain also exhibited moderate tolerance to different heavy metals including zinc (Zn), cadmium (Cd), chromium (Cr), lead (Pb) and copper (Cu). RA20 also decolorized Reactive Black-5 in the presence of a mixture of the selected heavy metals depending upon their concentrations. This study highlights the importance of Pseudomonas sp. RA20 as a prospective biological resource for bioremediation of water and soils contaminated with azo dyes.

  3. Co-occurring anxiety and disruptive behavior disorders: the roles of anxious symptoms, reactive aggression, and shared risk processes.

    Science.gov (United States)

    Bubier, Jennifer L; Drabick, Deborah A G

    2009-11-01

    The current review uses a developmental perspective to examine processes that may underlie and partially account for the association between anxiety disorders and disruptive behavior disorders among children and adolescents. We propose that one way to understand development of comorbid anxiety and disruptive behavior disorders is to examine symptoms that are precursors for or part of these syndromes, such as anxious symptoms and reactive aggression. We use a framework that considers these issues first at the syndrome or disorder level (e.g., anxiety disorders, disruptive behavior disorders), then at the symptom level (e.g., anxious symptoms and reactive aggression), and finally at the risk factor level (e.g., factors associated with anxious symptoms and/or reactive aggression). We apply various frameworks that have been put forth for understanding comorbidity of psychological syndromes to the co-occurrence of anxiety and disruptive behavior disorders and to the co-occurrence of reactive aggression and anxious symptoms where possible. We then identify gaps in the literature with regard to anxiety and reactive aggression, as well as anxiety and disruptive behavior disorders more generally. Finally, we provide a conceptual model describing how the relation of anxiety and reactive aggression may develop into clinically identifiable, comorbid anxiety and disruptive behavior disorders.

  4. System and process for aluminization of metal-containing substrates

    Energy Technology Data Exchange (ETDEWEB)

    Chou, Yeong-Shyung; Stevenson, Jeffry W

    2015-11-03

    A system and method are detailed for aluminizing surfaces of metallic substrates, parts, and components with a protective alumina layer in-situ. Aluminum (Al) foil sandwiched between the metallic components and a refractory material when heated in an oxidizing gas under a compression load at a selected temperature forms the protective alumina coating on the surface of the metallic components. The alumina coating minimizes evaporation of volatile metals from the metallic substrates, parts, and components in assembled devices during operation at high temperature that can degrade performance.

  5. High Throughput Atomic Layer Deposition Processes: High Pressure Operations, New Reactor Designs, and Novel Metal Processing

    Science.gov (United States)

    Mousa, MoatazBellah Mahmoud

    Atomic Layer Deposition (ALD) is a vapor phase nano-coating process that deposits very uniform and conformal thin film materials with sub-angstrom level thickness control on various substrates. These unique properties made ALD a platform technology for numerous products and applications. However, most of these applications are limited to the lab scale due to the low process throughput relative to the other deposition techniques, which hinders its industrial adoption. In addition to the low throughput, the process development for certain applications usually faces other obstacles, such as: a required new processing mode (e.g., batch vs continuous) or process conditions (e.g., low temperature), absence of an appropriate reactor design for a specific substrate and sometimes the lack of a suitable chemistry. This dissertation studies different aspects of ALD process development for prospect applications in the semiconductor, textiles, and battery industries, as well as novel organic-inorganic hybrid materials. The investigation of a high pressure, low temperature ALD process for metal oxides deposition using multiple process chemistry revealed the vital importance of the gas velocity over the substrate to achieve fast depositions at these challenging processing conditions. Also in this work, two unique high throughput ALD reactor designs are reported. The first is a continuous roll-to-roll ALD reactor for ultra-fast coatings on porous, flexible substrates with very high surface area. While the second reactor is an ALD delivery head that allows for in loco ALD coatings that can be executed under ambient conditions (even outdoors) on large surfaces while still maintaining very high deposition rates. As a proof of concept, part of a parked automobile window was coated using the ALD delivery head. Another process development shown herein is the improvement achieved in the selective synthesis of organic-inorganic materials using an ALD based process called sequential vapor

  6. Antibiotic effect of amoxicillin on the feces composting process and reactivation of bacteria by intermittent feeding of feces.

    Science.gov (United States)

    Kakimoto, Takashi; Osawa, Teruma; Funamizu, Naoyuki

    2007-12-01

    The aim of this work was to investigate the single exposure effect of amoxicillin on the feces composting process and the possibility of its bacterial reactivation by intermittent feeding of feces. The respiratory activity of the bacteria during the process after receiving exposure to several dosages of amoxicillin indicated a decrement of treatment performance, which was caused by the reduction of the initial viable bacterial count and activity brought about by the amoxicillin dosage. The amount of remaining feces was proportional to the initial concentration of amoxicillin, and even though no amoxicillin was detected, no automatic reactivation was observed, either. An intermittent feces feeding test was conducted to reactivate the bacteria. For the 10 and 100microg-amoxicillin/g dry systems, reactivation was observed, but for the 1000microg/g dry, no reactivation was seen. Finally, an intermittent feces feeding test was conducted with sterilized sawdust and the result indicated that the feces acted as a substrate rather than as a bacterial carrier.

  7. Numerical Tools for Multicomponent, Multiphase, Reactive Processes: Flow of CO{sub 2} in Porous Medium

    Energy Technology Data Exchange (ETDEWEB)

    Khattri, Sanjay Kumar

    2006-07-01

    The thesis is concerned with numerically simulating multicomponent, multiphase, reactive transport in heterogeneous porous medium. Such processes are ubiquitous, for example, deposition of green house gases, flow of hydrocarbons and groundwater remediation. Understanding such processes is important from social and economic point of view. For the success of geological sequestration, an accurate estimation of migration patterns of green-house gases is essential. Due to an ever increasing computer power, computational mathematics has become an important tool for predicting dynamics of porous media fluids. Numerical and mathematical modelling of processes in a domain requires grid generation in the domain, discretization of the continuum equations on the generated grid, solution of the formed linear or nonlinear system of discrete equations and finally visualization of the results. The thesis is composed of three chapters and eight papers. Chapter 2 presents two techniques for generating structured quadrilateral and hexahedral meshes. These techniques are called algebraic and elliptic methods. Algebraic techniques are by far the most simple and computationally efficient method for grid generation. Transfinite interpolation operators are a kind of algebraic grid generation technique. In this chapter, many transfinite interpolation operators for grid generation are derived from 1D projection operators. In this chapter, some important properties of hexahedral elements are also mentioned. These properties are useful in discretization of partial differential equations on hexahedral mesh, improving quality of the hexahedral mesh, mesh generation and visualization. Chapter 3 is about CO{sub 2} flow in porous media. In this chapter, we present the mathematical models and their discretization for capturing major physical processes associated with CO{sub 2} deposition in geological formations. Some important simulations of practical applications in 2D and 3D are presented

  8. Numerical Tools for Multicomponent, Multiphase, Reactive Processes: Flow of CO{sub 2} in Porous Medium

    Energy Technology Data Exchange (ETDEWEB)

    Khattri, Sanjay Kumar

    2006-07-01

    The thesis is concerned with numerically simulating multicomponent, multiphase, reactive transport in heterogeneous porous medium. Such processes are ubiquitous, for example, deposition of green house gases, flow of hydrocarbons and groundwater remediation. Understanding such processes is important from social and economic point of view. For the success of geological sequestration, an accurate estimation of migration patterns of green-house gases is essential. Due to an ever increasing computer power, computational mathematics has become an important tool for predicting dynamics of porous media fluids. Numerical and mathematical modelling of processes in a domain requires grid generation in the domain, discretization of the continuum equations on the generated grid, solution of the formed linear or nonlinear system of discrete equations and finally visualization of the results. The thesis is composed of three chapters and eight papers. Chapter 2 presents two techniques for generating structured quadrilateral and hexahedral meshes. These techniques are called algebraic and elliptic methods. Algebraic techniques are by far the most simple and computationally efficient method for grid generation. Transfinite interpolation operators are a kind of algebraic grid generation technique. In this chapter, many transfinite interpolation operators for grid generation are derived from 1D projection operators. In this chapter, some important properties of hexahedral elements are also mentioned. These properties are useful in discretization of partial differential equations on hexahedral mesh, improving quality of the hexahedral mesh, mesh generation and visualization. Chapter 3 is about CO{sub 2} flow in porous media. In this chapter, we present the mathematical models and their discretization for capturing major physical processes associated with CO{sub 2} deposition in geological formations. Some important simulations of practical applications in 2D and 3D are presented

  9. A lubricant for cold processing of metals by pressure

    Energy Technology Data Exchange (ETDEWEB)

    Postolov, Yu.M.; Breskina, A.I.; Kalinin, Yu.G.; Kosenko, I.T.; Kutuyeva, Ye.P.; Osadchuk, Ye.S.; Proskuryakov, V.A.; Syroyezhko, A.M.; Vikhorev, A.A.; Zekin, V.L.

    1982-01-01

    In the lubricant (Sm) for cold processing of metals through pressure, which contains fatty acids from pyrolysis of castor oil (ZhK), in order to increase its antifriction properties and the quality of the processed surface, asphalts from distillation of fatty acids, isolated from soapstocks of vegetable oil or industrial fat (Gd), neutralization products, isolated from the oxidate obtained during oxidation of methylcyclohexane by atmospheric O/sub 2/ (NP) and petroleum oil (NM) are additionally introduced with the following component content in percent: fatty acids from pyrolysis of castor oil, 10 to 30; asphalts from the distillation of fatty acids isolated from vegetable oil or industrial fat soapstocks, 10 to 30; neutral products from the oxidate produced during oxidation of methylcyclohexane by atmospheric O/sub 2/, 10 to 50 and petroleum oil, the remainder. Axle grease or transformer oil may be used as the petroleum lubricant. The lubricant is made by simple mixing of the components at 20 to 40 degrees C.

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

    Science.gov (United States)

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

    2016-12-13

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

  11. Semisolid metal forming by novel sloping plate process

    Institute of Scientific and Technical Information of China (English)

    GUAN Ren-guo; WANG Chao; SHANG Jian-hong; XING Zhen-huan

    2006-01-01

    Semisolid metal forming by a novel sloping plate process was studied. A sloping plate with wavelike surface was used to prepare semisolid alloy. Semisolid billets and slurries with good microstructures and excellent property were prepared by cooling or preheating the sloping plate. During preparing semisolid alloy by the proposed process, the co-action of burst nucleation and dendrite fragmentation causes fine spherical microstructure formation, and casting temperature, cooling strength and sloping angle are the main factors influencing the alloy microstructure. Under the current experimental conditions, in order to prepare good quality semisolid billets, proper casting temperature ranges of 660-690 ℃ for AlMg3 alloy and 660-680 ℃ for AlSi6Mg2 alloy are suggested. A small car hub wheel of AlSi6Mg2 alloy was thixoformed, and its pattern and inner microstructure are fine. The reasonable technological conditions for preparing AlSi6Mg2 slurry are also proposed: the sloping plate preheating temperature is 300 ℃, and the casting temperature is 680 ℃.

  12. Control of the Chemoselectivity of Metal N-Aryl Nitrene Reactivity: C-H Bond Amination versus Electrocyclization.

    Science.gov (United States)

    Kong, Chen; Jana, Navendu; Jones, Crystalann; Driver, Tom G

    2016-10-04

    A mechanism study to identify the elements that control the chemoselectivity of metal-catalyzed N-atom transfer reactions of styryl azides is presented. Our studies show that the proclivity of the metal N-aryl nitrene to participate in sp(3)-C-H bond amination or electrocyclization reactions can be controlled by either the substrate or the catalyst. Electrocyclization is favored for mono-β-substituted and sterically noncongested styryl azides, whereas sp(3)-C-H bond amination through an H-atom abstraction-radical recombination mechanism is preferred when a tertiary allylic reaction center is present. Even when a weakened allylic C-H bond is present, our data suggest that the indole is still formed through an electrocyclization instead of a common allyl radical intermediate. The site selectivity of metal N-aryl nitrenes was found to be controlled by the choice of catalyst: Ir(I)-alkene complexes trigger electrocyclization processes while Fe(III) porphyrin complexes catalyze sp(3)-C-H bond amination in substrates where Rh2(II) carboxylate catalysts provide both products.

  13. DECOLORIZATION AND BIOLOGICAL DEGRADATION OF AZO DYE REACTIVE RED2 BY ANAEROBIC/AEROBIC SEQUENTIAL PROCESS

    Directory of Open Access Journals (Sweden)

    A. Naimabadi ، H. Movahedian Attar ، A. Shahsavani

    2009-04-01

    Full Text Available This study investigates the anaerobic treatability of reactive Red2 in an anaerobic/aerobic sequential process. Laboratory scale anaerobic baffled reactor and fixed activated sludge reactor were operated at different organic loadings and hydraulic retention times. The effects of shock dye concentration on the chemical oxygen demand and color removal efficiencies were investigated in the anaerobic baffled reactor. The effect of hydraulic retention time on the color and chemical oxygen demand removal efficiencies were also investigated in the aerobic reactor. The studies were carried out in continuous mode and the effluent of the anaerobic baffled reactor was used as feed for the fixed activated sludge reactor. Chemical oxygen demand removal efficiency of 54.5% was obtained at HRT =1 day in the anaerobic reactor. The average color removal was 89.5%. Chemical oxygen demand removal efficiency of 69% was obtained at HRT =7 h in the aerobic fixed activated sludge reactor. A slight decrease of the color was also observed in the aerobic reactor. This investigation has shown that successful treatment of a highly colored wastewater is possible in the anaerobic baffled reactor. Also the results showed that, anaerobic biological system has higher efficiency in dye removal than fixed activated sludge system, while aerobic system has higher efficiency in chemical oxygen demand removal comparing with the anaerobic baffled reactor.

  14. Heterogeneous fenton process using the mineral hematite for the discolouration of a reactive dye solution

    Directory of Open Access Journals (Sweden)

    F. V. F. Araujo

    2011-12-01

    Full Text Available This work reports a study on the heterogeneous Fenton reaction using hematite powder (Fe2O3 in suspension for the discolouration of the reactive dye Drimarene Red X-6BN in aqueous solutions. The efficiency of the process was studied as a function of the experimental conditions: initial pH; H2O2 dose; and hematite powder concentration; all of which showed a strong effect on the reaction kinetics. Under the best experimental conditions: pH = 2.5; H2O2 dose = 800 mg/L; and [Hematite] = 20 g/L, it was possible to remove about 99% of the initial colour in 120 minutes in a batch reaction at 25ºC. The analysis of the kinetic results suggests that the reaction is initiated by heterogeneous generation of free radicals on the hematite surface, but as soluble iron (III and iron (II species are released into the solution during the course of the reaction, a simultaneous homogeneous Fenton reaction step propagates and contributes to the overall reaction.

  15. Control of a reactive batch distillation process using an iterative learning technique

    Energy Technology Data Exchange (ETDEWEB)

    Ahn, Hyunsoo; Lee, Kwang Soon [Sogang University, Seoul (Korea, Republic of); Kim, Mansuk; Lee, Juhyun [Samsung Cheil Industries Inc., Uiwang (Korea, Republic of)

    2014-01-15

    Quadratic criterion-based iterative learning control (QILC) was applied to a numerical reactive batch distillation process, in which methacrylic anhydride (MAN) is produced through the reaction of methacrylic acid with acetic anhydride. The role of distillation is to shift the equilibrium conversion toward the direction of the product by removing acetic acid (AcH), a by-product of the reaction. Two temperatures at both ends of the column were controlled by individual control loops. A nonlinear PID controller manipulating the reflux ratio was employed to regulate the top temperature at the boiling point of AcH. A constrained QILC was used for the tracking of the reactor temperature. A time-varying reference trajectory for the reactor temperature that satisfies the target conversion and purity of MAN was obtained through repeated simulations and confirmation experiments in the pilot plant. The QILC achieved satisfactory tracking in several batch runs with gentle control movements, while the PID control as a substitute of the QILC in a comparative study exhibited unacceptable performance.

  16. Purification of radioactive decontamination liquids from NPP Paks with reactive adsorption and ion-exchange process

    Energy Technology Data Exchange (ETDEWEB)

    Szaanya, T.; Hanaak, L.; Marton, Gy.; Salamon, T. [University of Veszprem, Veszprem (Hungary); Tilky, P. [Nuclear Power Plant, Paks (Hungary)

    1999-07-01

    In nuclear power plant Paks, Hungary, alkaline oxidative (NaOH, KMnO{sub 4}, H{sub 2}O) and acidic reductive (citric- and oxalic acid, water) liquids are using for the decontamination of primary circuit equipment (main liquid circulating pumps, steam generators, pipelines etc). The above mentioned decontamination liquids are containing {sup 110m}Ag, {sup 95}Nb, {sup 54}Mn, {sup 58} Co, {sup 60}Co, {sup 51} Cr, {sup 124} Sb radioisotopes, summarized radioactivity is between 10{sup 3}-8x10{sup 4} kBq/dm{sup 3} liquid. The decontamination liquid can be cleaned with reactive adsorption (active carbon) and ion-exchange process at elevated temperature (333-368 K) in multilayered columns. After purification the summarized radioactivity for {sup 54}Mn, {sup 60}Co, and {sup 110m}Ag are in the outlet liquid below 1 kBq/dm{sup 3}. Decontamination factor DF{approx_equal}10{sup 3}-10{sup 4}, volumetric reduction factor VRF{approx_equal}50-500.

  17. Using fluorescence-based microplate assay to assess DOM-metal binding in reactive materials for treatment of acid mine drainage

    Institute of Scientific and Technical Information of China (English)

    Carmen Mihaela Neculita; Yves Dudal; Gerald J Zagury

    2011-01-01

    One potential drawback of compost-based passive bioreactors, which is a promising biotechnology for acid mine drainage (AMD) treatment, is the transport of dissolved organic matter (DOM)-metal complexes in surface waters.To address this problem, the objective of this study was to assess the maximum capacity of organic substrates to release soluble DOM-metal complexes in treated water.The reactivities of DOM in maple wood chips and sawdust, composted poultry manure, and leaf compost were quantified toward Cd2+, Ni2+, Fe2+, and Cu2+ using fluorescence quenching.The DOM showed the highest reactivity toward Fe, but a limited number of available sites for sorption, whereas DOM-Cd complexes exhibited the lowest fluorescence quenching.Overall, the DOM from a mixture of wastes formed higher concentrations of DOM-metal complexes relative to sole substrates.Among DOM-metal complexes, the concentrations of DOM-Ni complexes were the highest.After reaching steady-state, low concentrations of DOM-metal complexes were released in treated water, which is in agreement with theoretical predictions based on geochemical modeling.Therefore, in addition to physicochemical characterization, fluorescence quenching technique is recommended for the substrate selection of bioreactors.

  18. Process stabilization by peak current regulation in reactive high-power impulse magnetron sputtering of hafnium nitride

    Science.gov (United States)

    Shimizu, T.; Villamayor, M.; Lundin, D.; Helmersson, U.

    2016-02-01

    A simple and cost effective approach to stabilize the sputtering process in the transition zone during reactive high-power impulse magnetron sputtering (HiPIMS) is proposed. The method is based on real-time monitoring and control of the discharge current waveforms. To stabilize the process conditions at a given set point, a feedback control system was implemented that automatically regulates the pulse frequency, and thereby the average sputtering power, to maintain a constant maximum discharge current. In the present study, the variation of the pulse current waveforms over a wide range of reactive gas flows and pulse frequencies during a reactive HiPIMS process of Hf-N in an Ar-N2 atmosphere illustrates that the discharge current waveform is a an excellent indicator of the process conditions. Activating the reactive HiPIMS peak current regulation, stable process conditions were maintained when varying the N2 flow from 2.1 to 3.5 sccm by an automatic adjustment of the pulse frequency from 600 Hz to 1150 Hz and consequently an increase of the average power from 110 to 270 W. Hf-N films deposited using peak current regulation exhibited a stable stoichiometry, a nearly constant power-normalized deposition rate, and a polycrystalline cubic phase Hf-N with (1 1 1)-preferred orientation over the entire reactive gas flow range investigated. The physical reasons for the change in the current pulse waveform for different process conditions are discussed in some detail.

  19. Structure and reactivity studies of transition metals ligated by tBuSi3X (X = O, NH, N, S, and CC).

    Science.gov (United States)

    Wolczanski, Peter T

    2009-02-21

    Use of the (t)Bu(3)Si group can sterically protect O, N, S, and acetylide donors, enabling chemistry at low-coordinate transition metal centers. This article provides examples from these laboratories on the utilization of (t)Bu(3)SiO(-), (t)Bu(3)SiNH(-), (t)Bu(3)SiN(2-), (t)Bu(3)SiS(-) and (t)Bu(3)SiCC(-) as ligands in exploratory synthesis and reactivity studies of transition metal complexes.

  20. Electrophilic acid gas-reactive fluid, proppant, and process for enhanced fracturing and recovery of energy producing materials

    Science.gov (United States)

    Fernandez, Carlos A.; Heldebrant, David J.; Bonneville, Alain H. R.; Jung, Hun Bok; Carroll, Kenneth

    2016-09-20

    An electrophilic acid gas-reactive fracturing and recovery fluid, proppant, and process are detailed. The fluid expands in volume to provide rapid and controlled increases in pressure that enhances fracturing in subterranean bedrock for recovery of energy-producing materials. Proppants stabilize openings in fractures and fissures following fracturing.

  1. Blending of NR/BR/EPDM by reactive processing for tire sidewall applications. I. Preparation, cure characteristics and mechanical properties

    NARCIS (Netherlands)

    Sahakaro, Kannika; Naskar, Nityananda; Datta, Rabin N.; Noordermeer, Jacques W.M.

    2007-01-01

    EPDM incorporated into blends of natural rubber/butadiene rubber (NR/BR) improves ozone resistance. In this work, the inferior mechanical properties of NR/BR/EPDM blends generally obtained by conventional straight mixing are overcome by utilizing a reactive processing technique. The entire amount of

  2. Evaluation of reactive oxygen species generating AirOcare system for reducing airborne microbial populations in a meat processing plant

    Science.gov (United States)

    The microbial contamination of meat and meat products is of continuing concern to the meat industry and regulatory agencies. Air has been established as a source of microbial contamination in slaughter and processing facilities. The objective of this research was to determine the efficacy of reactiv...

  3. A simultaneous modulation of reactive and proactive inhibition processes by anodal tDCS on the right inferior frontal cortex.

    Directory of Open Access Journals (Sweden)

    Toni Cunillera

    Full Text Available Proactive and reactive inhibitory processes are a fundamental part of executive functions, allowing a person to stop inappropriate responses when necessary and to adjust performance in in a long term in accordance to the goals of a task. In the current study, we manipulate, in a single task, both reactive and proactive inhibition mechanisms, and we investigate the within-subjects effect of increasing, by means of anodal transcranial direct current stimulation (tDCS, the involvement of the right inferior frontal cortex (rIFC. Our results show a simultaneous enhancement of these two cognitive mechanisms when modulating the neural activity of rIFC. Thus, the application of anodal tDCS increased reaction times on Go trials, indicating a possible increase in proactive inhibition. Concurrently, the stop-signal reaction time, as a covert index of the inhibitory process, was reduced, demonstrating an improvement in reactive inhibition. In summary, the current pattern of results validates the engagement of the rIFC in these two forms of inhibitory processes, proactive and reactive inhibition and it provides evidence that both processes can operate concurrently in the brain.

  4. Effect of reactive oxygen species (ROS) generating system for control of airborne microorganisms in meat processing environment

    Science.gov (United States)

    The effectiveness of reactive oxygen species (ROS) generating AirOcare equipment on the reduction of airborne bacteria in a meat processing environment was determined. Serratia marcescens and lactic acid bacteria (Lactococcus lactis subsp. lactis and Lactobacillus plantarum) were used to artificiall...

  5. The development of the super-biodiesel production continuously from Sunan pecan oil through the process of reactive distillation

    Science.gov (United States)

    Yohana, Eflita; Yulianto, Moh. Endy; Ikhsan, Diyono; Nanta, Aditya Marga; Puspitasari, Ristiyanti

    2016-06-01

    In general, a vegetable oil-based biodiesel production commercially operates a batch process with high investments and operational costs. Thus, it is necessary to develop super-biodiesel production from sunan pecan oil continuously through the process of reactive distillation. There are four advantages of the reactive distillation process for the biodiesel production, as follows: (i) it incorporates the process of transesterification reaction, and product separation of residual reactants become one stage of the process, so it saves the investment and operation costs, (ii) it reduces the need for raw materials because the methanol needed corresponds to the stoichiometry, so it also reduces the operation costs, (iii) the holdup time in the column is relatively short (5±0,5 minutes) compared to the batch process (1-2 hours), so it will reduce the operational production costs, and (iv) it is able to shift the reaction equilibrium, because the products and reactants that do not react are instantly separated (based on Le Chatelier's principles) so the conversion will be increased. However, the very crucial problem is determining the design tools and process conditions in order to maximize the conversion of the transesterification reaction in both phases. Thus, the purpose of this research was to design a continuous reactive distillation process by using a recycled condensate to increase the productivity of the super-biodiesel from sunan pecan oil. The research was carried out in three stages including (i) designing and fabricating the reactive distillation equipment, (ii) testing the tool performance and the optimization of the biodiesel production, and (iii) biodiesel testing on the diesel engine. These three stages were needed in designing and scaling-up the process tools and the process operation commercially. The reactive distillation process tools were designed and manufactured with reference to the design system tower by Kitzer, et.al. (2008). The manufactured

  6. Enhanced tunability of the composition in silicon oxynitride thin films by the reactive gas pulsing process

    Science.gov (United States)

    Aubry, Eric; Weber, Sylvain; Billard, Alain; Martin, Nicolas

    2014-01-01

    Silicon oxynitride thin films were sputter deposited by the reactive gas pulsing process. Pure silicon target was sputtered in Ar, N2 and O2 mixture atmosphere. Oxygen gas was periodically and solely introduced using exponential signals. In order to vary the injected O2 quantity in the deposition chamber during one pulse at constant injection time (TON), the tau mounting time τmou of the exponential signals was systematically changed for each deposition. Taking into account the real-time measurements of the discharge voltage and the I(O*)/I(Ar*) emission lines ratio, it is shown that the oscillations of the discharge voltage during the TON and TOFF times (injection of O2 stopped) are attributed to the preferential adsorption of the oxygen compared to that of the nitrogen. The sputtering mode alternates from a fully nitrided mode (TOFF time) to a mixed mode (nitrided and oxidized mode) during the TON time. For the highest injected O2 quantities, the mixed mode tends toward a fully oxidized mode due to an increase of the trapped oxygen on the target. The oxygen (nitrogen) concentration in the SiOxNy films similarly (inversely) varies as the oxygen is trapped. Moreover, measurements of the contamination speed of the Si target surface are connected to different behaviors of the process. At low injected O2 quantities, the nitrided mode predominates over the oxidized one during the TON time. It leads to the formation of Si3N4-yOy-like films. Inversely, the mixed mode takes place for high injected O2 quantities and the oxidized mode prevails against the nitrided one producing SiO2-xNx-like films.

  7. Air Stripping Designs and Reactive Water Purification Processes for the Lunar Surface

    Science.gov (United States)

    Boul, Peter J.; Lange, Kevin; Conger, Bruce; Anderson, Molly

    2010-01-01

    Air stripping designs are considered to reduce the presence of volatile organic compounds in the purified water. Components of the wastewater streams are ranked by Henry's Law Constant and the suitability of air stripping in the purification of wastewater in terms of component removal is evaluated. Distillation processes are modeled in tandem with air stripping to demonstrate the potential effectiveness and utility of these methods in recycling wastewater on the Moon. Scaling factors for distillation and air stripping columns are presented to account for the difference in the lunar gravitation environment. Commercially available distillation and air stripping units which are considered suitable for Exploration Life Support are presented. The advantages to the various designs are summarized with respect to water purity levels, power consumption, and processing rates. An evaluation of reactive distillation and air stripping is presented with regards to the reduction of volatile organic compounds in the contaminated water and air. Among the methods presented, an architecture is presented for the evaluation of the simultaneous oxidation of organics in air and water. These and other designs are presented in light of potential improvements in power consumptions and air and water purities for architectures which include catalytic activity integrated into the water processor. In particular, catalytic oxidation of organics may be useful as a tool to remove contaminants that more traditional distillation and/or air stripping columns may not remove. A review of the current leading edge at the commercial level and at the research frontier in catalytically active materials is presented. Themes and directions from the engineering developments in catalyst design are presented conceptually in light of developments in the nanoscale chemistry of a variety of catalyst materials.

  8. Reactive control processes contributing to residual switch cost and mixing cost in young and old adults

    Directory of Open Access Journals (Sweden)

    Lisa Rebecca Whitson

    2014-04-01

    Full Text Available In task-switching paradigms, performance is better when repeating the same task than when alternating between tasks (switch cost and when repeating a task alone rather than intermixed with another task (mixing cost. These costs remain even after extensive practice and when task cues enable advanced preparation (residual costs. Moreover, residual RT mixing cost has been consistently shown to increase with age. Residual switch and mixing costs modulate the amplitude of the stimulus-locked P3b. This mixing effect is disproportionately larger in older adults who also prepare more for and respond more cautiously on these ‘mixed’ repeat trials (Karayanidis et al., 2011. In this study, we examine stimulus-locked and response-locked P3 and lateralized readiness potentials to identify whether residual switch and mixing cost arise from the need to control interference at the level of stimulus processing or response processing. Residual mixing cost was associated with control of stimulus-level interference, whereas residual switch cost was also associated with a delay in response selection. In older adults, the disproportionate increase in mixing cost was associated with greater interference at the level of decision-response mapping and response programming for repeat trials in mixed-task blocks. We argue that, together with evidence of greater proactive control and more cautious responding for these trials, these findings suggest that older adults strategically recruit greater proactive and reactive control to overcome increased susceptibility to post-stimulus interference. This interpretation is consistent with recruitment of compensatory strategies to compensate for reduced repetition benefit rather than an overall decline on cognitive flexibility.

  9. A RISK MANAGEMENT METHODOLOGY FOR NON-METALLIC PROCESS EQUIPMENT

    Directory of Open Access Journals (Sweden)

    J.J. Viviers

    2012-01-01

    Full Text Available

    ENGLISH ABSTRACT: Many companies in South Africa have implemented the risk-based inspection (RBI methodology as a maintenance strategy. The risk involved in operating a piece of equipment, past history, non-destructive examination techniques, failure modes, and many other aspects determine the frequency of inspections required to meet legislation. The main purpose of the RBI methodology is to prevent failures of process equipment. The methodology for risk-based inspection for metal equipment is well-established and has been proven in industry, becoming the norm nationally and internationally. However, it is not possible to apply all the techniques to nonmetallic equipment owing to vast differences between the two types of materials. This paper discusses the results of data gathered on the RBI methodology for nonmetallic equipment, and proposes a risk-based model that can be used to perform a risk assessment for non-metallic equipment in a process plant. The risk assessment can be used to formulate the next inspection interval for the asset.

    AFRIKAANSE OPSOMMING: Verskeie maatskappye in Suid-Afrika het reeds die metodologie van risikogebaseeerde inspeksie (RBI geïmplementeer as deel van ‘n omvattende instandhoudingstrategie. Die risiko betrokke by ‘n fisiese item, bedryfsgeskiedenis, nie-vernietigende toetstegnieke, falingsmodusse, en vele ander aspekte bepaal die frekwensie van inspeksies wat benodig word om aan wetlike vereistes te voldoen. Die hoofdoel van die risiko-gebaseerde metodologie is om faling van prosestoerusting te verhinder. Die metodologie vir risiko-gebaseerde inspeksie van metaaltoerusting is goed bekend en word suksesvol toegepas in die industrie. Dis is egter nie moontlik om al die tegnieke toe te pas op nie-metaaltoerusting nie weens die groot verskeidenheid van materiaaltipes. Hierdie artikel bespreek die data wat ingewin is op die risiko-gebaseerde metodologie vir nie-metaaltipeprosestoerusting, en stel

  10. Cobalt,a reactive metal in releasing hydrogen from sodium borohydride by hydrolysis:A short review and a research perspective

    Institute of Scientific and Technical Information of China (English)

    DEMIRCI; Umit; B; AKDIM; Ouardia; HANNAUER; Julien; CHAMOUN; Rita; MIELE; Philippe

    2010-01-01

    Cobalt is commonly admitted as being a promising catalyst in accelerating NaBH4 hydrolysis,being as reactive as noble metals and much more cost-effective.This is the topic of the present paper.Herein,we survey(i) the NaBH4-devoted literature while especially focusing on the Co catalysts and(ii) our work on the same topic.Finally,we report(iii) reactivity results of newly developed Co-based catalysts.From both surveys,it mainly stands out that Co has been investigated as catalysts in various forms:namely,as chlorides,reduced nanoparticles(metal Co,Co boride,Co-B alloy),supported over supports and shaped.In doing so the reactivity can be easily varied achieving H2 generation rates from few to >1000 L(H2)/min·g(metal).Nevertheless,our work can be distinguished from the NaBH4 literature.Indeed,we are working on strategies that focus on making alternative Co-based catalysts.One of these strategies is illustrated here as we report new reactivity data of Co-based bimetallic supported catalysts.For example,we show that 20 wt% Co90Y10/γAl2O3-20 wt% Co95Hf5/γAl2O3 > 20 wt% Co99Zr1/γAl2O3 > 20 wt% Co/γAl2O3,the best catalysts showing HGRs of about 245 mL(H2)/min or 123 L(H2) /min·g(metals).

  11. Amyloid-β and α-synuclein decrease the level of metal-catalyzed reactive oxygen species by radical scavenging and redox silencing

    DEFF Research Database (Denmark)

    Pedersen, Jeppe Trudslev; Chen, Serene W.; Borg, Christian Bernsen;

    2016-01-01

    The formation of reactive oxygen species (ROS) is linked to the pathogenesis of Alzheimer's and Parkinson's diseases. Here we have investigated the effect of soluble and aggregated Aβ and α-synuclein, associated with Alzheimer's and Parkinson's disease respectively, on the Cu2+-catalyzed formation......-active metal ions in the aggregates or as a downstream consequence of the formation of the patho-logical amyloid structures....

  12. Periodic regularities in bonding, coordination modes and reactivity of sulfur oxides on transition metal surfaces: Combined BOC-MP and ab initio results

    Energy Technology Data Exchange (ETDEWEB)

    Shustorovich, E. [Blue Planet Technologies Co., New York, NY (United States); Sellers, H. [South Dakota State Univ., Brookings, SD (United States)

    1995-12-01

    A combination of theoretical methods (BOC-MP and high quality ab initio calculations) has been employed to understand the nature of bonding, coordination modes and reactivity of sulfur oxides on metal fcc (111), (100), (110) surfaces along the periodic series Cu, Pt, Pd and Ni. The emphasis was on the molecular chemisorption of SO{sub 2} and its dissociative pathways: S + 20 <--- SO + O <--- SO{sub 2} --- > SO{sub 3} --- > SO{sub 4}. M

  13. Reactivity of ionic oxides through water molecules adsorption process; MgO-V sub 2 O sub 5 behaviour

    Energy Technology Data Exchange (ETDEWEB)

    Goni-Elizalde, S. (Consejo Superior de Investigaciones Cientificas, Madrid (Spain). Instituto de Ciencias de la Construccion Eduardo Torroja); Garcia-Clavel, M.E. (Consejo Superior de Investigaciones Cientificas, Madrid (Spain). Instituto de Edafologia)

    1991-03-01

    Crystalline V{sub 2}O{sub 5} reactivity is strongly dependent on both particle size and relative humidity surrounding the sample. To study the increase of reactivity of crystalline V{sub 2}O{sub 5} (grain size<0.05 mm), a mixture of MgO-V{sub 2}O{sub 5} (1:1) has been kept in a watervapour saturated atmosphere for different periods of time. X-ray diffraction is employed to follow the structural evolution of the mixture, the adsorption process of water molecules has been studied by infrared spectroscopy as well as by thermogravimetry. (author). 11 refs.; 5 figs.; 1 tab.

  14. Heavy metal removal from MSWI fly ash by electrokinetic remediation coupled with a permeable activated charcoal reactive barrier

    Science.gov (United States)

    Huang, Tao; Li, Dongwei; Kexiang, Liu; Zhang, Yuewei

    2015-10-01

    This paper presents the investigations into the feasibility of the application of a remediation system that couples electrokinetic remediation (EKR) with the permeable reactive barrier (PRB) concept for municipal solid waste incineration (MSWI) fly ash with activated charcoal as the PRB material. The experimental results of this study showed that the proposed combined method can effectively improve the remediation efficiency and that the addition of the oxalic acid to the PRB media before the coupled system can further enhance the remediation process. In the optimization tests, the maximum removals of Zn, Pb, Cu and Cd were achieved under different experimental conditions. The voltage gradient and processing time were shown to have significant effects on the removal of Cu and Cd, whereas the addition of the oxalic acid had a more significant influence on the removal of Pb. Generally, the processing time is the most significant factor in changing the removal rates of HMs in the enhanced coupled system. In terms of the leaching toxicity, the specimen remediated by ENEKR + PRB showed the lowest leaching value for each HM in the S2 and S3 regions.

  15. Effect of metal oxides on the reactivity of persulfate/Fe(II) in the remediation of diesel-contaminated soil and sand.

    Science.gov (United States)

    Do, Si-Hyun; Kwon, Yong-Jae; Kong, Sung-Ho

    2010-10-15

    The effect of metal oxides on the ability of persulfate (PS) with Fe(II) to remediate diesel-contaminated soil was investigated. In both natural soil and purchased sand, the highest diesel degradation occurred at pH 3 and the optimum molar ratio of PS/Fe(II) was 100:1 (i.e. 500 mM PS to 5 mM Fe(II)). Moreover, adding Fe(II) increased PS reactivity more in soil than it did in sand, indicating the involvement of metal oxides in the soil matrix. Evaluating the effects of metal oxides (i.e. goethite, hematite, magnetite, and manganese oxide) on the reactivity of PS with/without Fe(II) in a system containing diesel-contaminated sand revealed that manganese oxide increased PS activity the most and that the highest diesel degradation by PS occurred when both manganese oxide and Fe(II) were used as activators. XRD did not show the transformation of manganese oxide in the presence of Fe(II). SEM-EDS showed the association of Fe(II) on the surface of manganese oxide, and ICP analysis revealed that almost all the added Fe(II) adsorbed to manganese oxide but almost none adsorbed to iron oxides under acidic conditions. Therefore, the high reactivity of PS could be due to the high density of Fe(II) over the surface of manganese oxide. 2010 Elsevier B.V. All rights reserved.

  16. Redox-inactive metal ions modulate the reactivity and oxygen release of mononuclear non-haem iron(III)-peroxo complexes.

    Science.gov (United States)

    Bang, Suhee; Lee, Yong-Min; Hong, Seungwoo; Cho, Kyung-Bin; Nishida, Yusuke; Seo, Mi Sook; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

    2014-10-01

    Redox-inactive metal ions that function as Lewis acids play pivotal roles in modulating the reactivity of oxygen-containing metal complexes and metalloenzymes, such as the oxygen-evolving complex in photosystem II and its small-molecule mimics. Here we report the synthesis and characterization of non-haem iron(III)-peroxo complexes that bind redox-inactive metal ions, (TMC)Fe(III)-(μ,η(2):η(2)-O2)-M(n+) (M(n+) = Sr(2+), Ca(2+), Zn(2+), Lu(3+), Y(3+) and Sc(3+); TMC, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). We demonstrate that the Ca(2+) and Sr(2+) complexes showed similar electrochemical properties and reactivities in one-electron oxidation or reduction reactions. However, the properties and reactivities of complexes formed with stronger Lewis acidities were found to be markedly different. Complexes that contain Ca(2+) or Sr(2+) ions were oxidized by an electron acceptor to release O2, whereas the release of O2 did not occur for complexes that bind stronger Lewis acids. We discuss these results in the light of the functional role of the Ca(2+) ion in the oxidation of water to dioxygen by the oxygen-evolving complex.

  17. Reactive Distillation and Air Stripping Processes for Water Recycling and Trace Contaminant Control

    Science.gov (United States)

    Boul, Peter J.; Lange, Kevin E.; Conger, Bruce; Anderson, Molly

    2009-01-01

    Reactive distillation designs are considered to reduce the presence of volatile organic compounds in the purified water. Reactive distillation integrates a reactor with a distillation column. A review of the literature in this field has revealed a variety of functional reactive columns in industry. Wastewater may be purified by a combination of a reactor and a distiller (e.g., the EWRS or VPCAR concepts) or, in principle, through a design which integrates the reactor with the distiller. A review of the literature in reactive distillation has identified some different designs in such combinations of reactor and distiller. An evaluation of reactive distillation and reactive air stripping is presented with regards to the reduction of volatile organic compounds in the contaminated water and air. Among the methods presented, an architecture is presented for the evaluation of the simultaneous oxidation of organics in air and water. These and other designs are presented in light of potential improvements in power consumptions and air and water purities for architectures which include catalytic activity integrated into the water processor. In particular, catalytic oxidation of organics may be useful as a tool to remove contaminants that more traditional distillation and/or air stripping columns may not remove. A review of the current leading edge at the commercial level and at the research frontier in catalytically active materials is presented. Themes and directions from the engineering developments in catalyst design are presented conceptually in light of developments in the nanoscale chemistry of a variety of catalyst materials.

  18. Reactive Distillation and Air Stripping Processes for Water Recycling and Trace Contaminant Control

    Science.gov (United States)

    Boul, Peter J.; Lange, Kevin E.; Conger, Bruce; Anderson, Molly

    2009-01-01

    Reactive distillation designs are considered to reduce the presence of volatile organic compounds in the purified water. Reactive distillation integrates a reactor with a distillation column. A review of the literature in this field has revealed a variety of functional reactive columns in industry. Wastewater may be purified by a combination of a reactor and a distiller (e.g., the EWRS or VPCAR concepts) or, in principle, through a design which integrates the reactor with the distiller. A review of the literature in reactive distillation has identified some different designs in such combinations of reactor and distiller. An evaluation of reactive distillation and reactive air stripping is presented with regards to the reduction of volatile organic compounds in the contaminated water and air. Among the methods presented, an architecture is presented for the evaluation of the simultaneous oxidation of organics in air and water. These and other designs are presented in light of potential improvements in power consumptions and air and water purities for architectures which include catalytic activity integrated into the water processor. In particular, catalytic oxidation of organics may be useful as a tool to remove contaminants that more traditional distillation and/or air stripping columns may not remove. A review of the current leading edge at the commercial level and at the research frontier in catalytically active materials is presented. Themes and directions from the engineering developments in catalyst design are presented conceptually in light of developments in the nanoscale chemistry of a variety of catalyst materials.

  19. Role of metal-induced reactive oxygen species generation in lung responses caused by residual oil fly ash

    Indian Academy of Sciences (India)

    Anthony B Lewis; Michael D Taylor; Jenny R Roberts; Stephen S Leonard; Xianglin Shi; James M Antonini

    2003-02-01

    Inhalation of residual oil fly ash (ROFA) increases pulmonary morbidity in exposed workers. We examined the role of reactive oxygen species (ROS) in ROFA-induced lung injury. ROFA was collected from a precipitator at Boston Edison Co., Everett, MA, USA. ROFA (ROFA-total) was suspended in saline, incubated for 24 h at 37°C, centrifuged, and separated into its soluble (ROFA-sol.) and insoluble (ROFA-insol.) fractions. Sprague-Dawley rats were intratracheally instilled with saline or ROFA-total or ROFA-sol. or ROFA-insol. (1 mg/100 g body wt.). Lung tissue and bronchoalveolar lavage cells were harvested at 4, 24, and 72 h after instillation. Chemiluminescence (CL) of recovered cells was measured as an index of ROS production, and tissue-lipid-peroxidation was assessed to determine oxidative injury. Significant amounts of Al, Fe, and Ni were present in ROFA-sol., whereas ROFA-insol. contained Fe, V, and Al. Using electron spin resonance (ESR), significantly more hydroxyl radicals were measured in ROFA-sol. as compared to ROFA-insol. None of the ROFA samples had an effect on CL or lipid peroxidation at 4 h. Treatment with ROFA-total and ROFA-insol. caused significant increases in both CL (at 24 h) and lipid peroxidation (at 24 and 72 h) when compared to saline control value. ROFA-sol. significantly reduced CL production at 72 h after treatment and had no effect on lipid peroxidation at any time point. In summary, ROFA, particularly its soluble fraction, generated a metal-dependent hydroxyl radical as measured by a cell-free ESR assay. However, cellular oxidant production and tissue injury were observed mostly with the ROFA-total and ROFA-insol. particulate forms. ROS generated by ROFA-sol. as measured by ESR appear not to play a major role in the lung injury caused after ROFA exposure.

  20. Optimization of the Parameters Influencing the Photo-Fenton Process for the Decolorization of Reactive Red 198 (RR198

    Directory of Open Access Journals (Sweden)

    Dehghani

    2015-04-01

    Full Text Available Background Reactive dyes, anionic compounds with high water solubility, are widely used in textile industries. Objectives The present study aimed to assess the feasibility of the photo-Fenton process in removing Reactive Red 198 dye from aqueous solutions and determine the optimal conditions for maximum removal. Materials and Methods This study was performed on a laboratory scale using a 4-liter photochemical reactor. The spectrophotometer DR5000 (wavelength 520 nm was used to determine the dye concentration. The effect of the influencing parameters, including pH (3–9, Fe (II concentration (10–200 mg/L, H2O2 concentration (25 - 150 mg/L, initial dye concentration (50–200 mg/L, and reaction time (15 - 120 minutes were studied. Results According to the results, the photo-Fenton (UV/ H2O2/Fe (II process significantly removed dye from the aqueous solution. The Reactive Red 198 dye removal efficiency from aqueous solutions was more than 99% at optimal conditions (pH = 3, Fe (II = 10 mg/L, H2O2 = 75 mg/L, initial dye concentration = 50 mg/L, and reaction time = 120 minutes. Conclusions The present study demonstrated that the UV/ H2O2/Fe (II process could be used as an efficient, reliable method for removing Reactive Red 198 dye from textile wastewater.

  1. Metal (Pb, Cd, and Cu)-induced reactive oxygen species accumulations in aerial root cells of the Chinese banyan (Ficus microcarpa).

    Science.gov (United States)

    Liu, Nan; Lin, Zhifang; Mo, Hui

    2012-10-01

    The current study evaluated the toxicity of three heavy metals to aerial roots of the Chinese banyan (Ficus microcarpa), which is a tree species native to China. In a laboratory experiment, segments of aerial roots cut from trees were treated with 0, 25, 50, 100, and 200 μM of lead, cadmium, or copper (Cu). The contents of these heavy metals in cells increased and root cell viability decreased with increases in treatment concentration. High levels of reactive oxygen species accumulated in the aerial root sections after heavy metal treatment. Both biochemical assay and histochemical localization showed that O(2) (•-), which is a precursor of H(2)O(2) accumulated in root sections and that the amount accumulated was positively related to heavy metal concentration, especially for Cu-treated samples. Histochemical staining with diaminobenzidine (DAB) and a fluorometric scopoletin oxidation assay indicated that the amount of H(2)O(2) accumulated was positively related to heavy metal concentration in the treatments; the scopoletin fluorescence assay was more sensitive and efficient than DAB staining for detection and quantification of H(2)O(2). The results indicate that aerial roots are sensitive to heavy metal-induced oxidative damage and that aerial roots have the potential to be used as indicators of heavy metal pollution in urban areas.

  2. Hydrodynamics of heavy liquid metal coolant processes and filtering apparatus

    Energy Technology Data Exchange (ETDEWEB)

    Albert K Papovyants; Yuri I Orlov; Pyotr N Martynov; Yuri D Boltoev [Institute for Physics and Power Engineering named after A.I. Leypunsky Bondarenko sq. 1, 249033, Obninsk, Kaluga region (Russian Federation)

    2005-07-01

    forces at a distance from the wall equal to S {<=} 0,2 d{sub p}. It is demonstrated that the filtration efficiency can be significantly influenced by the properties of the capillary-porous structure of the filter material: the fiber diameter, type of braiding providing the availability of stagnant zones, porosity and wetting angle. With some simplifying prerequisites, the evaluation of the dynamics of the sedimentation growth on the porous partition has been performed as a function of time. Analysis of the conditions of the hydrodynamic separation of filter entrained particles (d{sub p} {approx_equal} 2 {mu}m) by the coolant flow revealed that to realize this process, it is necessary that the wall flow velocity be about V = 0,2 m/s. The object of investigations was a broad class of filter materials, including metallo-ceramics, metallic grids, carbon cloth, glass-fibers, needle-pierced cloth made of metallic fibers, grainy materials (made of aluminium oxides). By the complex of technical characteristics, with the thermal stability, cleaning efficiency (fineness), impurity retention capacity and hydraulic resistance considered, the multi-layer siliceous textured cloth (SiO{sub 2}>95%, t 400 deg. C) and needle-pierced cloth made of 40 {mu}m-d. metallic fibers (X18H10T steel, t {<=} 400-550 deg. C) are recommended for HLMC cleaning. The routine monitoring of the filter operation is implemented based on its resistance and the reduction of the flow rate through the filter, induced by its clogging by impurities, the clogging being dependent on the concentration of suspensions in coolant. The investigations as conducted made it possible to construct high temperature filter specimens, including those for an output capacity of 900 m{sup 3}/h, in reference to operation and maintenance conditions of heavy liquid metal cooled nuclear power installations. (authors)

  3. Development of Replacements for Phoscoating Used in Forging, Extrusion and Metal Forming Processes

    Energy Technology Data Exchange (ETDEWEB)

    Kerry Barnett

    2003-03-01

    Many forging, extrusion, heading and other metal forming processes use graphite-based lubricants, phosphate coatings, and other potentially hazardous or harmful substances to improve the tribology of the metal forming process. The application of phosphate-based coatings has long been studied to determine if other synthetic ''clean'' lubricants could provide the same degree of protection afforded by phoscoatings and its formulations. So far, none meets the cost and performance objectives provided by phoscoatings as a general aid to the metal forming industry. In as much as phoscoatings and graphite have replaced lead-based lubricants, the metal forming industry has had previous experience with a legislated requirement to change processes. However, without a proactive approach to phoscoating replacement, many metal forming processes could find themselves without a cost effective tribology material necessary for the metal forming process

  4. Titanium Metal Powder Production by the Plasma Quench Process

    Energy Technology Data Exchange (ETDEWEB)

    R. A. Cordes; A. Donaldson

    2000-09-01

    The goals of this project included the scale-up of the titanium hydride production process to a production rate of 50 kg/hr at a purity level of 99+%. This goal was to be achieved by incrementally increasing the production capability of a series of reactor systems. This methodic approach was designed to allow Idaho Titanium Technologies to systematically address the engineering issues associated with plasma system performance, and powder collection system design and performance. With quality powder available, actual fabrication with the titanium hydride was to be pursued. Finally, with a successful titanium production system in place, the production of titanium aluminide was to be pursued by the simultaneously injection of titanium and aluminum precursors into the reactor system. Some significant accomplishments of the project are: A unique and revolutionary torch/reactor capable of withstanding temperatures up to 5000 C with high thermal efficiency has been operated. The dissociation of titanium tetrachloride into titanium powder and HC1 has been demonstrated, and a one-megawatt reactor potentially capable of producing 100 pounds per hour has been built, but not yet operated at the powder level. The removal of residual subchlorides and adsorbed HC1 and the sintering of powder to form solid bodies have been demonstrated. The production system has been operated at production rates up to 40 pounds per hour. Subsequent to the end of the project, Idaho Titanium Technologies demonstrated that titanium hydride powder can indeed be sintered into solid titanium metal at 1500 C without sintering aids.

  5. Multiscale processing of loss of metal: a machine learning approach

    Science.gov (United States)

    De Masi, G.; Gentile, M.; Vichi, R.; Bruschi, R.; Gabetta, G.

    2017-07-01

    Corrosion is one of the principal causes of degradation to failure of marine structures. In practice, localized corrosion is the most dangerous mode of attack and can result in serious failures, in particular in marine flowlines and inter-field lines, arousing serious concerns relatively to environmental impact. The progress in time of internal corrosion, the location along the route and across the pipe section, the development pattern and the depth of the loss of metal are a very complex issue: the most important factors are products characteristics, transport conditions over the operating lifespan, process fluid-dynamics, and pipeline geometrical configuration. Understanding which factors among them play the most important role is a key step to develop a model able to predict with enough accuracy the sections more exposed to risk of failure. Some factors play a crucial role at certain spatial scales while other factors at other scales. The Mutual Information Theory, intimately related to the concept of Shannon Entropy in Information theory, has been applied to detect the most important variables at each scale. Finally, the variables emerged from this analysis at each scale have been integrated in a predicting data driven model sensibly improving its performance.

  6. Hot-rolled Process of Multilayered Composite Metal Plate

    Directory of Open Access Journals (Sweden)

    YU Wei

    2017-02-01

    Full Text Available For multi-layer plate, it is a difficult problem to increase product yield rate and improve bonding interface quality. A high yield hot-rolled method of multilayered plate was proposed. The raw strips and plate were fixed by argon arc welding. The combined billet was put into a metal box and vacuum pumped, and then heated and rolled by multi passes at the temperature of 1000-1200℃. The 67 layered plate with the thickness of 2.5mm was successfully produced. The interfacial microstructures and diffusion behavior were investigated and analyzed by optical microscopy and scan electronic microscopy. The tensile and shear strength were tested,and the shear fractures were analyzed. The results show that the multilayered plate yield rate is more than 90% by two steps billet combination method and rolling process optimization. The good bonding interface quality is obtained, the shear strength of multilayered plate reaches 241 MPa. Nickel interlayer between 9Cr18 and 1Cr17 can not only prevent the diffusion of carbon, but also improve the microstructure characteristics.

  7. A Process for Making Bulk Heavy Metal Fluoride Glasses.

    Science.gov (United States)

    This invention relates to the preparation of glasses, and, in particular, relates to the preparation of heavy metal fluoride glasses with...reproducible high optical qualities. Considerable effort has been expended to develop heavy metal fluoride glasses ( HMFG ) as a viable family of infrared

  8. Process for forming a metal compound coating on a substrate

    Science.gov (United States)

    Sharp, D.J.; Vernon, M.E.; Wright, S.A.

    1988-06-29

    A method of coating a substrate with a thin layer of a metal compound by forming a dispersion of an electrophoretically active organic colloid and a precursor of the metal compound in an electrolytic cell in which the substrate is an electrode. Upon application of an electric potential, the electrode is coated with a mixture of the organic colloid and the precursor to the metal compound, and the coated substrate is then heated in the presence of an atmosphere or vacuum to decompose the organic colloid and form a coating of either a combination of metal compound and carbon, or optionally forming a porous metal compound coating by heating to a temperature high enough to chemically react the carbon.

  9. Interconnection of reactive oxygen species chemistry across the interfaces of atmospheric, environmental, and biological processes.

    Science.gov (United States)

    Anglada, Josep M; Martins-Costa, Marilia; Francisco, Joseph S; Ruiz-López, Manuel F

    2015-03-17

    Oxidation reactions are ubiquitous and play key roles in the chemistry of the atmosphere, in water treatment processes, and in aerobic organisms. Ozone (O3), hydrogen peroxide (H2O2), hydrogen polyoxides (H2Ox, x > 2), associated hydroxyl and hydroperoxyl radicals (HOx = OH and HO2), and superoxide and ozonide anions (O2(-) and O3(-), respectively) are the primary oxidants in these systems. They are commonly classified as reactive oxygen species (ROS). Atmospheric chemistry is driven by a complex system of chain reactions of species, including nitrogen oxides, hydroxyl and hydroperoxide radicals, alkoxy and peroxy radicals, and ozone. HOx radicals contribute to keeping air clean, but in polluted areas, the ozone concentration increases and creates a negative impact on plants and animals. Indeed, ozone concentration is used to assess air quality worldwide. Clouds have a direct effect on the chemical composition of the atmosphere. On one hand, cloud droplets absorb many trace atmospheric gases, which can be scavenged by rain and fog. On the other hand, ionic species can form in this medium, which makes the chemistry of the atmosphere richer and more complex. Furthermore, recent studies have suggested that air-cloud interfaces might have a significant impact on the overall chemistry of the troposphere. Despite the large differences in molecular composition, concentration, and thermodynamic conditions among atmospheric, environmental, and biological systems, the underlying chemistry involving ROS has many similarities. In this Account, we examine ROS and discuss the chemical characteristics common to all of these systems. In water treatment, ROS are key components of an important subset of advanced oxidation processes. Ozonation, peroxone chemistry, and Fenton reactions play important roles in generating sufficient amounts of hydroxyl radicals to purify wastewater. Biochemical processes within living organisms also involve ROS. These species can come from pollutants in

  10. Improved Reactive Dye-fixation in Pad-Steam Process of Dyeing Cotton Fabric Using Tetrasodium N, NBiscarboxylatomethyl- L-Glutamate

    OpenAIRE

    Awais Khatri; Mazhar Hussain Peerzada

    2012-01-01

    Pad steam process of dyeing cotton with reactive dyes is known to give lower levels of dye-fixation on the fiber because of excessive dye-hydrolysis. This research presents improved reactive dye-fixation in padsteam process of dyeing cotton found in an effort of using biodegradable organic salts to improve the effluent quality. The CI Reactive Blue 250, a bissulphatoethylsulphone dye and the Tetrasodium N, Nbiscarboxylatomethyl- L-Glutamate, a biodegradable organic salt, were used...

  11. Spectroscopic capture and reactivity of a low-spin cobalt(IV)-oxo complex stabilized by binding redox-inactive metal ions.

    Science.gov (United States)

    Hong, Seungwoo; Pfaff, Florian F; Kwon, Eunji; Wang, Yong; Seo, Mi-Sook; Bill, Eckhard; Ray, Kallol; Nam, Wonwoo

    2014-09-22

    High-valent cobalt-oxo intermediates are proposed as reactive intermediates in a number of cobalt-complex-mediated oxidation reactions. Herein we report the spectroscopic capture of low-spin (S=1/2) Co(IV)-oxo species in the presence of redox-inactive metal ions, such as Sc(3+), Ce(3+), Y(3+), and Zn(2+), and the investigation of their reactivity in C-H bond activation and sulfoxidation reactions. Theoretical calculations predict that the binding of Lewis acidic metal ions to the cobalt-oxo core increases the electrophilicity of the oxygen atom, resulting in the redox tautomerism of a highly unstable [(TAML)Co(III)(O˙)](2-) species to a more stable [(TAML)Co(IV)(O)(M(n+))] core. The present report supports the proposed role of the redox-inactive metal ions in facilitating the formation of high-valent metal-oxo cores as a necessary step for oxygen evolution in chemistry and biology.

  12. Soluble and particulate Co-Cr-Mo alloy implant metals activate the inflammasome danger signaling pathway in human macrophages: a novel mechanism for implant debris reactivity.

    Science.gov (United States)

    Caicedo, Marco S; Desai, Ronak; McAllister, Kyron; Reddy, Anand; Jacobs, Joshua J; Hallab, Nadim J

    2009-07-01

    Immune reactivity to soluble and particulate implant debris remains the primary cause of aseptic inflammation and implant loosening. However, the intracellular mechanisms that trigger immune cells to sense and respond to exogenous nonbiological agents such as metal particles or metal ions released from orthopedic implants remain unknown. Recent studies in immunology have outlined the importance of the intracellular inflammasome complex of proteins in sensing danger/stress signals triggered by nonbiological agents in the cytosol of macrophages. We hypothesized that metal implant debris can activate the inflammasome pathway in macrophages that causes caspase-1-induced cleavage of intracellular pro-IL-1beta into its mature form, resulting in IL-1beta secretion and induction of a broader proinflammatory response. We tested this hypothesis by examining whether soluble cobalt, chromium, molybdenum, and nickel ions and Co-Cr-Mo alloy particles induce inflammasome- mediated macrophage reactivity. Our results demonstrate that these agents stimulate IL-1beta secretion in human macrophages that is inflammasome mediated (i.e., NADPH-, caspase-1-, Nalp3-, and ASC-dependent). Thus, metal ion- and particle-induced activation of the inflammasome in human macrophages provides evidence of a novel pathway of implant debris-induced inflammation, where contact with implant debris is sensed and transduced by macrophages into a proinflammatory response.

  13. Fires in Operating or Abandoned Coal Mines or Heaps of Reactive Materials and the Governing Transport and Reaction Processes

    Science.gov (United States)

    Wuttke, M. W.; Kessels, W.; Wessling, S.; Han, J.

    2007-05-01

    Spontaneous combustion is a world wide problem for technical operations in mining, waste disposal and power plant facilities. The principle driving the combustion is every where the same independent of the different reactive materials: Fresh air with the common oxygen content is getting in contact with the reactive material by human operations. The following reaction process produces heat at a usually low but constant rate. The reactive material in operating or abandoned coal mines, heaps of coal, waste or reactive minerals is most times strongly broken or fractured, such that the atmospheric oxygen can deeply penetrate into the porous or fractured media. Because the strongly broken or fractured medium with air filled pores and fractures is often combined with a low thermal conductivity of the bulk material the produced heat accumulates and the temperature increases with time. If the reactivity strongly increases with temperature, the temperature rise accelerates up to the "combustion temperature". Once the temperature is high enough the combustion process is determined by the oxygen transport to the combustion center rather than the chemical reactivity. Spontaneous combustion is thus a self- amplifying process where an initial small variation in the parameters and the starting conditions can create exploding combustion hot spots in an apparently homogenous material. The phenomenon will be discussed by various examples in the context of the German - Sino coal fire project. A temperature monitoring in hot fracture systems documents the strong influence of the weather conditions on the combustion process. Numerical calculations show the sensitivity of the combustion to the model geometries, the boundary conditions and mainly the permeability. The most used fire fighting operations like covering and water injection are discussed. A new method of using saltwater for fire fighting is presented and discussed. References: Kessels, W., Wessling, S., Li, X., and Wuttke, M

  14. A process model of adolescents' triangulation into parents' marital conflict: the role of emotional reactivity.

    Science.gov (United States)

    Buehler, Cheryl; Welsh, Deborah P

    2009-04-01

    This study examined adolescents' emotional reactivity to parents' marital conflict as a mediator of the association between triangulation and adolescents' internalizing problems in a sample of 2-parent families (N = 416)[corrected]. Four waves of annual, multiple-informant data were analyzed (youth ages 11-15 years). The authors used structural equation modeling and found that triangulation was associated with increases in adolescents' internalizing problems, controlling for marital hostility and adolescent externalizing problems. There also was an indirect pathway from triangulation to internalizing problems across time through youths' emotional reactivity. Moderating analyses indicated that the 2nd half of the pathway, the association between emotional reactivity and increased internalizing problems, characterized youth with lower levels of hopefulness and attachment to parents. The findings help detail why triangulation is a risk factor for adolescents' development and which youth will profit most from interventions focused on emotional regulation.

  15. Electronic Relaxation Processes of Transition Metal Atoms in Helium Nanodroplets

    Science.gov (United States)

    Kautsch, Andreas; Lindebner, Friedrich; Koch, Markus; Ernst, Wolfgang E.

    2014-06-01

    Spectroscopy of doped superfluid helium nanodroplets (He_N) gives information about the influence of this cold, chemically inert, and least interacting matrix environment on the excitation and relaxation dynamics of dopant atoms and molecules. We present the results from laser induced fluorescence (LIF), photoionization (PI), and mass spectroscopy of Cr and Cu doped He_N. From these results, we can draw a comprehensive picture of the complex behavior of such transition metal atoms in He_N upon photo-excitation. The strong Cr and Cu ground state transitions show an excitation blueshift and broadening with respect to the bare atom transitions which can be taken as indication for the solvation inside the droplet. From the originally excited states the atoms relax to energetically lower states and are ejected from the He_N. The relaxation processes include bare atom spin-forbidden transitions, which clearly bears the signature of the He_N influence. Two-color resonant two-photon ionization (2CR2PI) also shows the formation of bare atoms and small Cr-He_n and Cu-He_n clusters in their ground and metastable states ^c. Currently, Cr dimer excitation studies are in progress and a brief outlook on the available results will be given. C. Callegari and W. E. Ernst, Helium Droplets as Nanocryostats for Molecular Spectroscopy - from the Vacuum Ultraviolet to the Microwave Regime, in Handbook of High-Resolution Spectroscopy, eds. M. Quack and F. Merkt, John Wiley & Sons, Chichester, 2011. A. Kautsch, M. Koch, and W. E. Ernst, J. Phys. Chem. A, 117 (2013) 9621-9625, DOI: 10.1021/jp312336m F. Lindebner, A. Kautsch, M. Koch, and W. E. Ernst, Int. J. Mass Spectrom. (2014) in press, DOI: 10.1016/j.ijms.2013.12.022 M. Koch, A. Kautsch, F. Lackner, and W. E. Ernst, submitted to J. Phys. Chem. A

  16. Bioleaching of metal ions from low grade sulphide ore: Process ...

    African Journals Online (AJOL)

    STORAGESEVER

    2010-05-10

    May 10, 2010 ... copper, gold, silver, platinum, chromium, iron, lead and zinc in various ... metal compounds into their water-soluble forms and are biocatalysts of this .... whose column elements represent the low, medium and high levels.

  17. Phycoremediation of Wastewater: Heavy Metal and Nutrient Removal Processes

    Directory of Open Access Journals (Sweden)

    Kwarciak-Kozłowska Anna

    2014-12-01

    Full Text Available Phycoremediation is the use of algae for the removal or biotrans-formation of pollutants from wastewater. The study is a novel at-tempt to integrate nutrient (N and P removal and some heavy met-als (iron, manganese and zinc bioaccumulation from municipal wastewater using two microalgae species: Chlorella vulgaris and Scenedesmus armatus. The Chlorella vulgaris showed higher re-moval of total nitrogen (TN both in influent and effluent waste water than Scenedesmus armatus. Nevertheless, more than 51% of total phosphorus (TP in effluent and 36% in influent wastewaters were removed by Scenedesmus armatus. More efficient microalga in heavy metal removal in influent wastewater was Scenedesmus armatus. The results showed that Chlorella vulgaris was appropriate for TN removal and bioaccumulation of heavy metals from effluent wastewater. Nevertheless, Scenedesmus armatus was highly pref-erable for heavy metals removal from influent wastewater.

  18. Metal ion exchange process by natural and modified clinoptilolite

    Energy Technology Data Exchange (ETDEWEB)

    Athanasiadis, K.; Petter, C.; Hilliges, R.; Helmreich, B.; Wilderer, P.A. [TU Muenchen (Germany). Lehrstuhl fuer Wasserguete- und Abfallwirtschaft

    2003-07-01

    Clinoptilolite, one of the most frequently studied natural zeolites, was shown to have high selectivity for certain heavy metals such as lead, cadmium and nickel. The aim of this study is to present equilibrium and kinetic data for Pb{sup 2+}, Cu{sup 2+} and Zn{sup 2+} exchange on natural and modified clinoptilolite for two different pH values. Selectivity series and kinetic data from these three heavy metals are presented. (orig.)

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

    OpenAIRE

    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 durin...

  20. Development of Highly Durable and Reactive Regenerable Magnesium-Based Sorbents for CO2 Separation in Coal Gasification Process

    Energy Technology Data Exchange (ETDEWEB)

    Javad Abbasian; Armin Hassanzadeh Khayyat; Rachid B. Slimane

    2005-06-01

    The specific objective of this project was to develop physically durable and chemically regenerable MgO-based sorbents that can remove carbon dioxide from raw coal gas at operating condition prevailing in IGCC processes. A total of sixty two (62) different sorbents were prepared in this project. The sorbents were prepared either by various sol-gel techniques (22 formulations) or modification of dolomite (40 formulations). The sorbents were prepared in the form of pellets and in granular forms. The solgel based sorbents had very high physical strength, relatively high surface area, and very low average pore diameter. The magnesium content of the sorbents was estimated to be 4-6 % w/w. To improve the reactivity of the sorbents toward CO{sub 2}, The sorbents were impregnated with potassium salts. The potassium content of the sorbents was about 5%. The dolomite-based sorbents were prepared by calcination of dolomite at various temperature and calcination environment (CO{sub 2} partial pressure and moisture). Potassium carbonate was added to the half-calcined dolomite through wet impregnation method. The estimated potassium content of the impregnated sorbents was in the range of 1-6% w/w. In general, the modified dolomite sorbents have significantly higher magnesium content, larger pore diameter and lower surface area, resulting in significantly higher reactivity compared to the sol-gel sorbents. The reactivities of a number of sorbents toward CO{sub 2} were determined in a Thermogravimetric Analyzer (TGA) unit. The results indicated that at the low CO{sub 2} partial pressures (i.e., 1 atm), the reactivities of the sorbents toward CO{sub 2} are very low. At elevated pressures (i.e., CO{sub 2} partial pressure of 10 bar) the maximum conversion of MgO obtained with the sol-gel based sorbents was about 5%, which corresponds to a maximum CO{sub 2} absorption capacity of less than 1%. The overall capacity of modified dolomite sorbents were at least one order of magnitude

  1. Process for the displacement of cyanide ions from metal-cyanide complexes

    Science.gov (United States)

    Smith, Barbara F.; Robinson, Thomas W.

    1997-01-01

    The present invention relates to water-soluble polymers and the use of such water-soluble polymers in a process for the displacement of the cyanide ions from the metal ions within metal-cyanide complexes. The process waste streams can include metal-cyanide containing electroplating waste streams, mining leach waste streams, mineral processing waste streams, and related metal-cyanide containing waste streams. The metal ions of interest are metals that give very strong complexes with cyanide, mostly iron, nickel, and copper. The physical separation of the water-soluble polymer-metal complex from the cyanide ions can be accomplished through the use of ultrafiltration. Once the metal-cyanide complex is disrupted, the freed cyanide ions can be recovered for reuse or destroyed using available oxidative processes rendering the cyanide nonhazardous. The metal ions are released from the polymer, using dilute acid, metal ion oxidation state adjustment, or competing chelating agents, and collected and recovered or disposed of by appropriate waste management techniques. The water-soluble polymer can then be recycled. Preferred water-soluble polymers include polyethyleneimine and polyethyleneimine having a catechol or hydroxamate group.

  2. Glass-to-metal bonding process improves stability and performance of semiconductor devices

    Science.gov (United States)

    Trent, R. L.

    1970-01-01

    Anodic bonding of glass coverslips to photodiodes and photovoltaic devices eliminates the need for adhesive. The process requires relatively low temperatures /less than 560 degrees C/ and the metals and glass remain solid throughout the bonding process.

  3. Analysis of Al diffusion processes in TiN barrier layers for the application in silicon solar cell metallization

    Science.gov (United States)

    Kumm, J.; Samadi, H.; Chacko, R. V.; Hartmann, P.; Wolf, A.

    2016-07-01

    An evaporated Al layer is known as an excellent rear metallization for highly efficient solar cells, but suffers from incompatibility with a common solder process. To enable solar cell-interconnection and module integration, in this work the Al layer is complemented with a solder stack of TiN/Ti/Ag or TiN/NiV/Ag, in which the TiN layer acts as an Al diffusion barrier. X-ray photoelectron spectroscopy measurements prove that diffusion of Al through the stack and the formation of an Al2O3 layer on the stack's surface are responsible for a loss of solderability after a strong post-metallization anneal, which is often mandatory to improve contact resistance and passivation quality. An optimization of the reactive TiN sputter process results in a densification of the TiN layer, which improves its barrier quality against Al diffusion. However, measurements with X-ray diffraction and scanning electron microscopy show that small grains with vertical grain boundaries persist, which still offer fast diffusion paths. Therefore, the concept of stuffing is introduced. By incorporating oxygen into the grain boundaries of the sputtered TiN layer, Al diffusion is strongly reduced as confirmed by secondary ion mass spectroscopy profiles. A quantitative analysis reveals a one order of magnitude lower Al diffusion coefficient for stuffed TiN layers. This metallization system maintains its solderability even after strong post-metallization annealing at 425 °C for 15 min. This paper thus presents an industrially feasible, conventionally solderable, and long-term stable metallization scheme for highly efficient silicon solar cells.

  4. Correlation between the oxidation state of {alpha}-SiC and its wettability with non-reactive (Sn) or reactive (Ni) metallic components and their binary Si-alloys

    Energy Technology Data Exchange (ETDEWEB)

    Tsoga, A.; Ladas, S.; Nikolopoulos, P. [Univ. of Patras (Greece). Dept. of Chemical Engineering]|[Inst. of Chemical Engineering and High Temperature Chemical Processes, Patras (Greece)

    1997-09-01

    Wetting experiments were performed on {alpha}-SiC/Sn (505 K < T < 1873 K) and {alpha}-SiC/Ni (T = 1,773 K) in an argon atmosphere with 700 vpm moisture. Wettability and reactivity of {alpha}-SiC with both metallic components were affected by the oxidation state of {alpha}-SiC. Under the experimental conditions, passive to active transition of {alpha}-SiC occurs at {approximately}1,600 K. Up to 1,600 K, wettability between liquid Sn and {alpha}-SiC is governed by a passive SiO{sub 2}-film overlaying {alpha}-SiC, while at higher temperatures an increased carbon surface concentration, leads to higher contact angle values. Under the present experimental conditions the start of reactivity between Ni and {alpha}-SiC coincides with the passive to active transition of {alpha}-SiC. The presence of silicon at the ceramic-metal interface, in the form of alloying element into both Sn or Ni, was found to decrease the temperature of passive to active transition of {alpha}-SiC, to improve the wettability for both {alpha}-SiC/Sn and {alpha}-SiC/Ni, and to suppress the interfacial reaction between Ni and {alpha}-SiC.

  5. Renovation and Reuse of Reactive Dyeing Effluent by a Novel Heterogeneous Fenton System Based on Metal Modified PTFE Fibrous Catalyst/H2O2

    Directory of Open Access Journals (Sweden)

    Bing Li

    2013-01-01

    Full Text Available Cu-Fe bimetallic grafted polytetrafluoroethylene (PTFE fiber complexes were prepared and optimized as the novel heterogeneous Fenton catalysts for the degradation of reactive dyes under UV irradiation. Cotton fabrics were dyed with three reactive dyes, namely, Reactive Red 195, Reactive Yellow 145, and Reactive Blue 222, in tap fresh water using exhaustion process. The spent dyeing effluents were then collected and degraded with the optimized Cu-Fe bimetallic grafted PTFE fiber complex/H2O2 system. The treated dyeing effluents were characterized and reused for the dyeing of cotton fabrics through the same process. The effect of reuse process number on quality of the dyed cotton fabrics was examined. The results indicated that the Cu-Fe bimetallic modified PTFE fiber complex with a Cu/Fe molar ratio of 2.87 was found to be the most effective fibrous catalyst, which enhanced complete decolorization of the treated dyeing effluents with H2O2 in 4 h. However, the TOC removal for the treated dyeing effluents was below 80%. The dyeing quality was not affected for three successive cycles. The increase in residual TOC value influences fourth dyeing cycle. Further TOC reduction of the treated effluents is needed for its repeated reuse in more than three dyeing cycles.

  6. Co-occurring Anxiety and Disruptive Behavior Disorders: The Roles of Anxious Symptoms, Reactive Aggression, and Shared Risk Processes

    OpenAIRE

    Bubier, Jennifer L.; Drabick, Deborah A.G.

    2009-01-01

    The current review uses a developmental perspective to examine processes that may underlie and partially account for the association between anxiety disorders and disruptive behavior disorders among children and adolescents. We propose that one way to understand development of comorbid anxiety and disruptive behavior disorders is to examine symptoms that are precursors for or part of these syndromes, such as anxious symptoms and reactive aggression. We use a framework that considers these iss...

  7. Effects of Processing Variables on Tantalum Nitride by Reactive-Ion-Assisted Magnetron Sputtering Deposition

    Science.gov (United States)

    Wei, Chao‑Tsang; Shieh, Han‑Ping D.

    2006-08-01

    The binary compound tantalum nitride (TaN) and ternary compounds tantalum tungsten nitrides (Ta1-xWxNy) exhibit interesting properties such as high melting point, high hardness, and chemical inertness. Such nitrides were deposited on a tungsten carbide (WC) die and silicon wafers by ion-beam-sputter evaporation of the respective metal under nitrogen ion-assisted deposition (IAD). The effects of N2/Ar flux ratio, post annealing, ion-assisted deposition, deposition rate, and W doping in coating processing variables on hardness, load critical scratching, oxidation resistance, stress and surface roughness were investigated. The optimum N2/Ar flux ratios in view of the hardness and critical load of TaN and Ta1-xWxNy films were ranged from 0.9 to 1.0. Doping W into TaN to form Ta1-xWxNy films led significant increases in hardness, critical load, oxidation resistance, and reduced surface roughness. The optimum doping ratio was [W/(W+Ta)]=0.85. From the deposition rate and IAD experiments, the stress in the films is mainly contributed by sputtering atoms. The lower deposition rate at a high N2/Ar flux ratio resulted in a higher compressive stress. A high compressive residual stress accounts for a high hardness. The relatively high compressive stress was attributed primarily to peening by atoms, ions and electrons during film growth, the Ta1-xWxNy films showed excellent hardness and strength against a high temperature, and sticking phenomena can essentially be avoided through their use. Ta1-xWxNy films showed better performance than the TaN film in terms of mechanical properties and oxidation resistance.

  8. Cycloaddition reactivity studies of first-row transition metal-azide complexes and alkynes: an inorganic click reaction for metalloenzyme inhibitor synthesis.

    Science.gov (United States)

    Evangelio, Emi; Rath, Nigam P; Mirica, Liviu M

    2012-07-14

    The studies described herein focus on the 1,3-dipolar cycloaddition reaction between first-row transition metal-azide complexes and alkyne reagents, i.e. an inorganic variant of the extensively used "click reaction". The reaction between the azide complexes of biologically-relevant metals (e.g., Fe, Co and Ni) found in metalloenzyme active sites and alkyne reagents has been investigated as a proof-of-principle for a novel method of developing metalloenzyme triazole-based inhibitors. Six Fe, Co and Ni mono-azide complexes employing salen- and cyclam-type ligands have been synthesized and characterized. The scope of the targeted inorganic azide-alkyne click reaction was investigated using the electron-deficient alkyne dimethyl acetylenedicarboxylate. Of the six metal-azide complexes tested, the Co and Ni complexes of the 1,4,8,11-tetrametyl-1,4,8,11-tetraazacyclotetradecane (Me(4)cyclam) ligand showed a successful cycloaddition reaction and formation of the corresponding metal-triazolate products, which were crystallographically characterized. Moreover, use of less electron deficient alkynes resulted in a loss of cycloaddition reactivity. Analysis of the structural parameters of the investigated metal-azide complexes suggests that a more symmetric structure and charge distribution within the azide moiety is needed for the formation of a metal-triazolate product. Overall, these results suggest that a successful cycloaddition reaction between a metal-azide complex and an alkyne substrate is dependent both on the ligand and metal oxidation state, that determine the electronic properties of the bound azide, as well as the electron deficient nature of the alkyne employed.

  9. Scale up tools in reactive extrusion and compounding processes. Could 1D-computer modeling be helpful?

    Science.gov (United States)

    Pradel, J.-L.; David, C.; Quinebèche, S.; Blondel, P.

    2014-05-01

    Industrial scale-up (or scale down) in Compounding and Reactive Extrusion processes is one of the most critical R&D challenges. Indeed, most of High Performances Polymers are obtained within a reactive compounding involving chemistry: free radical grafting, in situ compatibilization, rheology control... but also side reactions: oxidation, branching, chain scission... As described by basic Arrhenius and kinetics laws, the competition between all chemical reactions depends on residence time distribution and temperature. Then, to ensure the best possible scale up methodology, we need tools to match thermal history of the formulation along the screws from a lab scale twin screw extruder to an industrial one. This paper proposes a comparison between standard scale-up laws and the use of Computer modeling Software such as Ludovic® applied and compared to experimental data. Scaling data from a compounding line to another one, applying general rules (for example at constant specific mechanical energy), shows differences between experimental and computed data, and error depends on the screw speed range. For more accurate prediction, 1D-Computer Modeling could be used to optimize the process conditions to ensure the best scale-up product, especially in temperature sensitive reactive extrusion processes. When the product temperature along the screws is the key, Ludovic® software could help to compute the temperature profile along the screws and extrapolate conditions, even screw profile, on industrial extruders.

  10. Optimization and/or acclimatization of activated sludge process under heavy metals stress.

    Science.gov (United States)

    El Bestawy, Ebtesam; Helmy, Shacker; Hussein, Hany; Fahmy, Mohamed

    2013-04-01

    The present study aimed to overcome the toxicity of the heavy metals load, discharged with the industrial effluents into Alexandria sewerage network, on the activated sludge treatment system through effective acclimation for organic matter and heavy metals removal. Optimization and/or acclimatization of the activated sludge process in the presence of Cu, Cd, Co and Cr contaminating mixed domestic-industrial wastewater was investigated. Acclimatization process was performed through abrupt and stepwise addition of tested metals using sequencing batch reactors treatment approach and evaluated as microbial oxygen uptake rate (OUR), dehydrogenase activity (DHA), organic matter (COD) and heavy metals removal. Abrupt addition of metals adversely affected sludge bioactivity leading to decline in the removal efficiency of the targeted contaminants and loss of floc structure. Metals IC50 confirmed that copper possessed the highest toxicity towards the OUR, DHA activity and COD removal with orders Cu > Cd > Cr > Co; Cu > Cd > Co = Cr and Cu > Cd > Cr > Co, respectively. The highest metal removal was recorded for Cd followed by Co, Cu and finally Cr, most of which was retained in the dissolved influent. However, controlled stepwise application of the tested metals exhibited high sensitivity of DHA and OUR activities only at the highest metal concentrations although enhanced at the lowest concentrations while COD removal was not significantly affected. In conclusion, this approach resulted in adaptation of the system where sludge microbes acquired and developed natural resistance to such metals leading to remarkable enhancement of both organic matter and heavy metals removal.

  11. Integrated fab process for metal oxide EUV photoresist

    Science.gov (United States)

    Grenville, Andrew; Anderson, Jeremy T.; Clark, Benjamin L.; De Schepper, Peter; Edson, Joseph; Greer, Michael; Jiang, Kai; Kocsis, Michael; Meyers, Stephen T.; Stowers, Jason K.; Telecky, Alan J.; De Simone, Danilo; Vandenberghe, Geert

    2015-03-01

    Inpria is developing directly patternable, metal oxide hardmasks as robust, high-resolution photoresists for EUV lithography. Targeted formulations have achieved 13nm half-pitch at 35 mJ/cm2 on an ASML's NXE:3300B scanner. Inpria's second-generation materials have an absorbance of 20/μm, thereby enabling an equivalent photon shot noise compared to conventional resists at a dose lower by a factor of 4X. These photoresists have ~40:1 etch selectivity into a typical carbon underlayer, so ultrathin 20nm films are possible, mitigating pattern collapse. In addition to lithographic performance, we review progress in parallel advances required to enable the transition from lab to fab for such a metal oxide photoresist. This includes considerations and data related to: solvent compatibility, metals cross-contamination, coat uniformity, stability, outgassing, and rework.

  12. Metal speciation in a complexing soft film layer: a theoretical dielectric relaxation study of coupled chemodynamic and electrodynamic interfacial processes.

    Science.gov (United States)

    Merlin, Jenny; Duval, Jérôme F L

    2012-04-07

    We report a comprehensive formalism for the dynamics of metal speciation across an interphase formed between a complexing soft film layer and an electrolyte solution containing indifferent ions and metal ions that form complexes with charged molecular ligands distributed throughout the film. The analysis integrates the intricate interplay between metal complexation kinetics and diffusive metal transfer from/toward the ligand film, together with the kinetics of metal electrostatic partitioning across the film/solution interphase. This partitioning is determined by the settling dynamics of the interfacial electric double layer (EDL), as governed by time-dependent conduction-diffusion transports of both indifferent and reactive metal ions. The coupling between such chemodynamic and electrodynamic processes is evaluated via derivation of the dielectric permittivity increment for the ligand film/electrolyte interphase that is perturbed upon application of an ac electric field (pulsation ω) between electrodes supporting the films. The dielectric response is obtained from the ω-dependent distributions of all ions across the ligand film, as ruled by coupled Poisson-Nernst-Planck equations amended for a chemical source term involving the intra-film complex formation and dissociation pulsations (ω(a) and ω(d) respectively). Dielectric spectra are discussed for bare and film coated-electrodes over a wide range of field pulsations and Deborah numbers De = ω(a,d)/ω(diff), where ω(diff) is the electric double layer relaxation pulsation. The frequency-dependent dynamic or inert character of the formed metal complexes is then addressed over a time window that ranges from transient to fully relaxed EDL. The shape and magnitude of the dielectric spectra are further shown to reflect the lability of dynamic complexes, i.e. whether the overall speciation process at a given pulsation ω is primarily rate-limited either by complexation kinetics or by ion-transport dynamics. The

  13. Sequential process test for metal pyro-processing using U, Pu, and Am

    Energy Technology Data Exchange (ETDEWEB)

    Masaki Kurata; Noboru Yahagi [Central research Institute of Electric Power Industry, Iwadokita 2-11-1, Komae, Tokyo 201-8511 (Japan); Shinichi Kitawaki; Akira Nakayoshi; Mineo Fukushima [Japan Atomic Energy Agency, Muramatsu 4-33, Tokai-mura, Naka-gun, Ibaraki 319-1194 (Japan)

    2008-07-01

    The Central Research Institute of Electric Power Industry (CRIEPI) and the Japan Atomic Energy Agency (JAEA) are continuing a collaboration study for metal pyro-processing, in which sequential process tests have been performed under practical conditions using {approx}1 kg of molten salt baths. Recent results on two kinds of sequential process test are reported. The former is the electro-chemical reduction test of MOX pellet in order to form U-Pu alloy ingots. The latter is the electrolysis test using a combination of U-Pu alloy anode and solid or liquid cadmium cathode to recover U-product or U-Pu-Am alloy product, respectively. Variation in electrode potentials, current efficiency, molten salt composition, Pu- or Am-impurity in the U-product, U/Pu or Am/Pu separation factor in the U-Pu alloy product, and etc. were measured. These tests reproduced practical operating conditions at a scale of {approx}1/1000 that of the actual process. (author)

  14. Bead and Process for Removing Dissolved Metal Contaminants

    Energy Technology Data Exchange (ETDEWEB)

    Summers, Bobby L., Jr.; Bennett, Karen L.; Foster, Scott A.

    2005-01-18

    A bead is provided which comprises or consists essentially of activated carbon immobilized by crosslinked poly (carboxylic acid) binder, sodium silicate binder, or polyamine binder. The bead is effective to remove metal and other ionic contaminants from dilute aqueous solutions. A method of making metal-ion sorbing beads is provided, comprising combining activated carbon, and binder solution (preferably in a pin mixer where it is whipped), forming wet beads, and heating and drying the beads. The binder solution is preferably poly(acrylic acid) and glycerol dissolved in water and the wet beads formed from such binder solution are preferably heated and crosslinked in a convection oven.

  15. Characterization of a salt resistant bacterial strain Proteus sp. NA6 capable of decolorizing reactive dyes in presence of multi-metal stress.

    Science.gov (United States)

    Abbas, Naila; Hussain, Sabir; Azeem, Farrukh; Shahzad, Tanvir; Bhatti, Sajjad Haider; Imran, Muhammad; Ahmad, Zulfiqar; Maqbool, Zahid; Abid, Muhammad

    2016-11-01

    Microbial biotechnologies for the decolorization of textile wastewaters have attracted worldwide attention because of their economic suitability and easiness in handling. However, the presence of high amounts of salts and metal ions in textile wastewaters adversely affects the decolorization efficiency of the microbial bioresources. In this regard, the present study was conducted to isolate salt tolerant bacterial strains which might have the potential to decolorize azo dyes even in the presence of multi-metal ion mixtures. Out of the tested 48 bacteria that were isolated from an effluent drain, the strain NA6 was found relatively more efficient in decolorizing the reactive yellow-2 (RY2) dye in the presence of 50 g L(-1) NaCl. Based on the similarity of its 16S rRNA gene sequence and its position in a phylogenetic tree, this strain was designated as Proteus sp. NA6. The strain NA6 showed efficient decolorization (>90 %) of RY2 at pH 7.5 in the presence of 50 g L(-1) NaCl under static incubation at 30 °C. This strain also had the potential to efficiently decolorize other structurally related azo dyes in the presence of 50 g L(-1) NaCl. Moreover, Proteus sp. NA6 was found to resist the presence of different metal ions (Co(+2), Cr(+6), Zn(+2), Pb(+2), Cu(+2), Cd(+2)) and was capable of decolorizing reactive dyes in the presence of different levels of the mixtures of these metal ions along with 50 g L(-1) NaCl. Based on the findings of this study, it can be suggested that Proteus sp. NA6 might serve as a potential bioresource for the biotechnologies involving bioremediation of textile wastewaters containing the metal ions and salts.

  16. Reactive magnetron co-sputtering of Cu(In,Ga)Se{sub 2} absorber layers by a 2-stage process: Role of substrate type and Na-doping

    Energy Technology Data Exchange (ETDEWEB)

    Schulte, Jonas; Harbauer, Karsten; Ellmer, Klaus, E-mail: ellmer@helmholtz-berlin.de

    2015-05-01

    By simultaneous sputtering from metallic CuGa and In targets in an Ar:H{sub 2}Se atmosphere onto heated substrates, single phase and well crystallized Cu(In,Ga)Se{sub 2} thin films can be directly deposited in a single process step. However, the preparation of Cu-poor films, which are needed for high solar cell efficiencies, is impeded by the re-evaporation of excess indium, which occurs readily at moderate substrate temperatures in the range of 400 °C to 500 °C. Therefore, a significant In-excess is necessary during the second deposition stage in order to transform the final film composition into the desired Cu-poor regime ([Cu]/([In] + [Ga]) < 0.95). Higher open circuit voltages and efficiencies are achieved for absorbers produced with an intermediate Cu-rich composition and/or by using Na containing precursor films (NaF or Mo:Na). A best cell efficiency of 12.9% is achieved, which demonstrates the high potential of the investigated reactive magnetron sputtering process for solar cell manufacturing, as it is well suited for large-area, industrial applications. - Highlights: • Reactive sputtering in Ar:H{sub 2}Se allows the use of easy to fabricate targets. • Absorber quality can be improved by a 2-stage process. • The best cell has an efficiency of 12.9%. • Na-doping by NaF or Mo:Na precursors enhances the V{sub oc}.

  17. Memcapacitive characteristics in reactive-metal (Mo, Al)/HfO{sub X}/n-Si structures through migration of oxygen by applied voltage

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Paul; Noh, Young Jun; Baek, Yoon-Jae; Zheng, Hong; Yoon, Tae-Sik, E-mail: tsyoon@mju.ac.kr [Department of Materials Science and Engineering, Myongji University, Gyeonggi-do 449-728 (Korea, Republic of); Kang, Chi Jung [Department of Physics, Myongji University, Gyeonggi-do 449-728 (Korea, Republic of); Lee, Hyun Ho [Department of Chemical Engineering, Myongji University, Gyeonggi-do 449-728 (Korea, Republic of)

    2016-02-01

    Memcapacitive characteristics were investigated in metal-oxide-semiconductor (MOS) structure of reactive electrode (Mo, Al) and hafnium oxide (HfO{sub X}) on n-type Si substrate. The capacitance-voltage curves exhibited sequentially changing capacitance with memory function as repeating voltage sweeps, featured the memcapacitive behaviors. The saturation capacitance was decreased by repeating +V sweeps, while barely changed by −V sweeps. Also, the capacitance-time curves disclosed the same tendency. However, the MOS structure with inert Pt electrode did not show the capacitance change. The memcapacitive behaviors were induced by the migration of oxygen ions from HfO{sub X} to reactive electrodes by applied voltage, which altered the permittivity of HfO{sub X}.

  18. Reactivity of Metal e B (Boro in the Estuarine System of Cananéia –Iguapé (South Coast of São Paulo, Brazil

    Directory of Open Access Journals (Sweden)

    Vitor Rossi Victor

    2012-12-01

    Full Text Available Dissolved elements reactivity in water column directly influences their chemical and toxic behavior, and in their bioavailability, therefore, in their environmental profile in estuarine systems, important for their great biological productivity and location in zones with potential anthropic impacts. In this context, this study evaluated the behavior of metals (Ba, Fe, Li, Mn and Zn and  the semimetal B throughout the estuarine mixture in the Estuarine System of Cananéia-Iguape. It was observed that B and Li presented conservative behavior as they are not reactive, Ba, Fe and Zn presented not conservative behavior with removal in low salinities, and Mn presented mixed behavior, with addition in low salinities and approximately conservative behavior in high salinities.

  19. Rheology at the Interface and the Role of the Interphase in Reactive Functionalized Multilayer Polymers in Coextrusion Process

    Science.gov (United States)

    Lamnawar, Khalid; Maazouz, Abderrahim

    2008-07-01

    Coextrusion technologies are commonly used to produce multilayered composite sheets or films for a large range of applications from food packaging to optics. The contrast of rheological properties between layers can lead to interfacial instabilities during flow. Importa