Science.gov

Sample records for fuel reactivity formation

  1. Fuel Temperature Coefficient of Reactivity

    SciTech Connect

    Loewe, W.E.

    2001-07-31

    A method for measuring the fuel temperature coefficient of reactivity in a heterogeneous nuclear reactor is presented. The method, which is used during normal operation, requires that calibrated control rods be oscillated in a special way at a high reactor power level. The value of the fuel temperature coefficient of reactivity is found from the measured flux responses to these oscillations. Application of the method in a Savannah River reactor charged with natural uranium is discussed.

  2. Water reactive hydrogen fuel cell power system

    DOEpatents

    Wallace, Andrew P; Melack, John M; Lefenfeld, Michael

    2014-11-25

    A water reactive hydrogen fueled power system includes devices and methods to combine reactant fuel materials and aqueous solutions to generate hydrogen. The generated hydrogen is converted in a fuel cell to provide electricity. The water reactive hydrogen fueled power system includes a fuel cell, a water feed tray, and a fuel cartridge to generate power for portable power electronics. The removable fuel cartridge is encompassed by the water feed tray and fuel cell. The water feed tray is refillable with water by a user. The water is then transferred from the water feed tray into the fuel cartridge to generate hydrogen for the fuel cell which then produces power for the user.

  3. Water reactive hydrogen fuel cell power system

    DOEpatents

    Wallace, Andrew P; Melack, John M; Lefenfeld, Michael

    2014-01-21

    A water reactive hydrogen fueled power system includes devices and methods to combine reactant fuel materials and aqueous solutions to generate hydrogen. The generated hydrogen is converted in a fuel cell to provide electricity. The water reactive hydrogen fueled power system includes a fuel cell, a water feed tray, and a fuel cartridge to generate power for portable power electronics. The removable fuel cartridge is encompassed by the water feed tray and fuel cell. The water feed tray is refillable with water by a user. The water is then transferred from the water feed tray into a fuel cartridge to generate hydrogen for the fuel cell which then produces power for the user.

  4. Engine combustion control via fuel reactivity stratification

    SciTech Connect

    Reitz, Rolf Deneys; Hanson, Reed M.; Splitter, Derek A.; Kokjohn, Sage L.

    2015-07-14

    A compression ignition engine uses two or more fuel charges having two or more reactivities to control the timing and duration of combustion. In a preferred implementation, a lower-reactivity fuel charge is injected or otherwise introduced into the combustion chamber, preferably sufficiently early that it becomes at least substantially homogeneously dispersed within the chamber before a subsequent injection is made. One or more subsequent injections of higher-reactivity fuel charges are then made, and these preferably distribute the higher-reactivity matter within the lower-reactivity chamber space such that combustion begins in the higher-reactivity regions, and with the lower-reactivity regions following thereafter. By appropriately choosing the reactivities of the charges, their relative amounts, and their timing, combustion can be tailored to achieve optimal power output (and thus fuel efficiency), at controlled temperatures (and thus controlled NOx), and with controlled equivalence ratios (and thus controlled soot).

  5. Engine combustion control via fuel reactivity stratification

    SciTech Connect

    Reitz, Rolf Deneys; Hanson, Reed M; Splitter, Derek A; Kokjohn, Sage L

    2013-12-31

    A compression ignition engine uses two or more fuel charges having two or more reactivities to control the timing and duration of combustion. In a preferred implementation, a lower-reactivity fuel charge is injected or otherwise introduced into the combustion chamber, preferably sufficiently early that it becomes at least substantially homogeneously dispersed within the chamber before a subsequent injection is made. One or more subsequent injections of higher-reactivity fuel charges are then made, and these preferably distribute the higher-reactivity matter within the lower-reactivity chamber space such that combustion begins in the higher-reactivity regions, and with the lower-reactivity regions following thereafter. By appropriately choose the reactivities of the charges, their relative amounts, and their timing, combustion can be tailored to achieve optimal power output (and thus fuel efficiency), at controlled temperatures (and thus controlled NOx), and with controlled equivalence ratios (and thus controlled soot).

  6. Engine combustion control via fuel reactivity stratification

    DOEpatents

    Reitz, Rolf Deneys; Hanson, Reed M.; Splitter, Derek A.; Kokjohn, Sage L.

    2016-06-28

    A compression ignition engine uses two or more fuel charges having two or more reactivities to control the timing and duration of combustion. In a preferred implementation, a lower-reactivity fuel charge is injected or otherwise introduced into the combustion chamber, preferably sufficiently early that it becomes at least substantially homogeneously dispersed within the chamber before a subsequent injection is made. One or more subsequent injections of higher-reactivity fuel charges are then made, and these preferably distribute the higher-reactivity matter within the lower-reactivity chamber space such that combustion begins in the higher-reactivity regions, and with the lower-reactivity regions following thereafter. By appropriately choosing the reactivities of the charges, their relative amounts, and their timing, combustion can be tailored to achieve optimal power output (and thus fuel efficiency), at controlled temperatures (and thus controlled NOx), and with controlled equivalence ratios (and thus controlled soot).

  7. Formation and Reactivity of Biogenic Iron Microminerals

    SciTech Connect

    Beveridge, Terrance J.; Glasauer, Susan; Korenevsky, Anton; Ferris, F. Grant

    2000-08-08

    The overall purpose of the project is to explore and quantify the processes that control the formation and reactivity of biogenic iron microminerals and their impact on the solubility of metal contaminants. The research addresses how surface components of bacterial cells, extracellular organic material, and the aqueous geochemistry of the DIRB microenvironment impacts the mineralogy, chemical state and micromorphology of reduced iron phases.

  8. Biodiesel Fuel Property Effects on Particulate Matter Reactivity

    SciTech Connect

    Williams, A.; Black, S.; McCormick, R. L.

    2010-06-01

    Controlling diesel particulate emissions to meet the 2007 U.S. standard requires the use of a diesel particulate filter (DPF). The reactivity of soot, or the carbon fraction of particulate matter, in the DPF and the kinetics of soot oxidation are important in achieving better control of aftertreatment devices. Studies showed that biodiesel in the fuel can increase soot reactivity. This study therefore investigated which biodiesel fuel properties impact reactivity. Three fuel properties of interest included fuel oxygen content and functionality, fuel aromatic content, and the presence of alkali metals. To determine fuel effects on soot reactivity, the performance of a catalyzed DPF was measured with different test fuels through engine testing and thermo-gravimetric analysis. Results showed no dependence on the aromatic content or the presence of alkali metals in the fuel. The presence and form of fuel oxygen was the dominant contributor to faster DPF regeneration times and soot reactivity.

  9. Reactive spreading: Adsorption, ridging and compound formation

    SciTech Connect

    Saiz, E.; Cannon, R.M.; Tomsia, A.P.

    2000-09-11

    Reactive spreading, in which a chemically active element is added to promote wetting of noble metals on nonmetallic materials, is evaluated. Theories for the energetics and kinetics of the necessary steps involved in spreading are outlined and compared to the steps in compound formation that typically accompany reactive wetting. These include: fluid flow, active metal adsorption, including nonequilibrium effects, and triple line ridging. All of these can be faster than compound nucleation under certain conditions. Analysis and assessment of recently reported experiments on metal/ceramic systems lead to a focus on those conditions under which spreading proceeds ahead of the actual formation of a new phase at the interface. This scenario may be more typical than believed, and perhaps the most effective situation leading to enhanced spreading. A rationale for the pervasive variability and hysteresis observed during high temperature wetting also emerges.

  10. Assessment of reactivity transient experiments with high burnup fuel

    SciTech Connect

    Ozer, O.; Yang, R.L.; Rashid, Y.R.; Montgomery, R.O.

    1996-03-01

    A few recent experiments aimed at determining the response of high-burnup LWR fuel during a reactivity initiated accident (RIA) have raised concerns that existing failure criteria may be inappropriate for such fuel. In particular, three experiments (SPERT CDC-859, NSRR HBO-1 and CABRI REP Na-1) appear to have resulted in fuel failures at only a fraction of the anticipated enthalpy levels. In evaluating the results of such RIA simulation experiments, however, it is necessary that the following two key considerations be taken into account: (1) Are the experiments representative of conditions that LWR fuel would experience during an in-reactor RIA event? (2) Is the fuel that is being utilized in the tests representative of the present (or anticipated) population of LWR fuel? Conducting experiments under conditions that can not occur in-reactor can trigger response modes that could not take place during in-reactor operation. Similarly, using unrepresentative fuel samples for the tests will produce failure information that is of limited relevance to commercial LWR fuel. This is particularly important for high-burnup fuel since the manner under which the test samples are base-irradiated prior to the test will impact the mechanical properties of the cladding and will therefore affect the RIA response. A good example of this effect can be seen in the results of the SPERT CDC-859 test and in the NSRR JM-4 and JM-5 tests. The conditions under which the fuel used for these tests was fabricated and/or base-irradiated prior to the RIA pulse resulted in the formation of multiple cladding defects in the form of hydride blisters. When this fuel was subjected to the RIA power pulse, it failed by developing multiple cracks that were closely correlated with the locations of the pre-existing hydride blisters. In the case of the JM tests, many of the cracks formed within the blisters themselves and did not propagate beyond the heavily hydrided regions.

  11. Heating subsurface formations by oxidizing fuel on a fuel carrier

    DOEpatents

    Costello, Michael; Vinegar, Harold J.

    2012-10-02

    A method of heating a portion of a subsurface formation includes drawing fuel on a fuel carrier through an opening formed in the formation. Oxidant is supplied to the fuel at one or more locations in the opening. The fuel is combusted with the oxidant to provide heat to the formation.

  12. Formate Formation and Formate Conversion in Biological Fuels Production

    PubMed Central

    Crable, Bryan R.; Plugge, Caroline M.; McInerney, Michael J.; Stams, Alfons J. M.

    2011-01-01

    Biomethanation is a mature technology for fuel production. Fourth generation biofuels research will focus on sequestering CO2 and providing carbon-neutral or carbon-negative strategies to cope with dwindling fossil fuel supplies and environmental impact. Formate is an important intermediate in the methanogenic breakdown of complex organic material and serves as an important precursor for biological fuels production in the form of methane, hydrogen, and potentially methanol. Formate is produced by either CoA-dependent cleavage of pyruvate or enzymatic reduction of CO2 in an NADH- or ferredoxin-dependent manner. Formate is consumed through oxidation to CO2 and H2 or can be further reduced via the Wood-Ljungdahl pathway for carbon fixation or industrially for the production of methanol. Here, we review the enzymes involved in the interconversion of formate and discuss potential applications for biofuels production. PMID:21687599

  13. Critical Role of Water Content in the Formation and Reactivity of Uraniu, Neptunium, and Plutonium Iodates Under Hydrothermal Conditions: Implications for the Oxidative Dissolution of Spent Nuclear Fuel

    SciTech Connect

    Bray, T. H.; Ling, Jie; Choi, E- Sang; Brooks, James S.; Beitz, James V.; Sykora, Richard E.; Haire, Richard {Dick} G; Stanbury, David M.; Albrecht-Schmitt, Thomas E.

    2007-01-01

    The reactions of {sup 237}NpO{sub 2} with excess iodate under acidic hydrothermal conditions result in the isolation of the neptunium(IV), neptunium(V), and neptunium(VI) iodates, Np(IO{sub 3}){sub 4}, Np(IO{sub 3}){sub 4}{center_dot}nH{sub 2}O{center_dot}nHIO{sub 3}, NpO2(IO3), NpO2(IO3)2(H2O), and NpO{sub 2}(IO{sub 3}){sub 2}{center_dot}H{sub 2}O, depending on both the pH and the amount of water present in the reactions. Reactions with less water and lower pH favor reduced products. Although the initial redox processes involved in the reactions between {sup 237}NpO{sub 2} or {sup 242}PuO{sub 2} and iodate are similar, the low solubility of Pu(IO{sub 3}){sub 4} dominates product formation in plutonium iodate reactions to a much greater extent than does Np(IO{sub 3}){sub 4} in the neptunium iodate system. UO{sub 2} reacts with iodate under these conditions to yield uranium(VI) iodates solely. The isotypic structures of the actinide(IV) iodates, An(IO{sub 3}){sub 4} (An = Np, Pu), are reported and consist of one-dimensional chains of dodecahedral An(IV) cations bridged by iodate anions. The structure of Np(IO3)4{center_dot}nH2O{center_dot}nHIO3 is constructed from NpO9 tricapped-trigonal prisms that are bridged by iodate into a polar three-dimensional framework structure. Second-harmonic-generation measurements on a polycrystalline sample of the Th analogue of Np(IO{sub 3}){sub 4}{center_dot}nH{sub 2}O{center_dot}nHIO{sub 3} reveal a response of approximately 12x that of {alpha}-SiO{sub 2}. Single-crystal magnetic susceptibility measurements of Np(IO{sub 3}){sub 4} show magnetically isolated Np(IV) ions.

  14. Effects of poison panel shrinkage and gaps on fuel storage rack reactivity

    SciTech Connect

    Boyd, W.A.; Mueller, D.E.

    1988-01-01

    Fixed poison panels are used in spent fuel rack designs to increase enrichment limits and reduce cell spacing; therefore, assurances that the maximum rack reactivity will meet the design limit (0.95) throughout the lifetime of the racks depend on the continued effectiveness of the poison with time. Industry data have shown that poison panels will shrink under irradiated conditions. From recent data, however, poison panels have been found to have gaps spanning their width after relatively short operating periods. This paper presents results of studies showing the fuel rack reactivity changes associated with poison panel shrinkage and formation of gaps. The discovery of gaps in the fuel rack poison panels at an operating plant raises concerns regarding the effectiveness of the poison over the lifetime of the fuel racks. Studies performed to evaluate the effect of the poison panel shrinkage on reactivity show that reactivity changes from zero to several percent are possible depending on the initial panel size. Results of recent studies show that some gaps can be accommodated in the fuel rack poison panels at the fuel midplane without causing the fuel rack K{sub eff} limit to be exceeded. With worst-case assumptions concerning gap size and the number of panels affected, other actions will likely be required to show that the rack K{sub eff} design limit will not be exceeded.

  15. Reactive flash volatilization of fluid fuels

    DOEpatents

    Schmidt, Lanny D.; Dauenhauer, Paul J.; Dreyer, Bradon J.; Salge, James R.

    2013-01-08

    The invention provides methods for the production of synthesis gas. More particularly, various embodiments of the invention relate to systems and methods for volatilizing fluid fuel to produce synthesis gas by using a metal catalyst on a solid support matrix.

  16. Gasification reactivities of solid biomass fuels

    SciTech Connect

    Moilanen, A.; Kurkela, E.

    1995-12-31

    The design and operation of the biomass based gasification processes require knowledge about the biomass feedstocks characteristics and their typical gasification behaviour in the process. In this study, the gasification reactivities of various biomasses were investigated in laboratory scale Pressurized Thermogravimetric apparatus (PTG) and in the PDU-scale (Process Development Unit) Pressurized Fluidized-Bed (PFB) gasification test facility of VTT.

  17. Formation and Detoxification of Reactive Oxygen Species

    ERIC Educational Resources Information Center

    Kuciel, Radoslawa; Mazurkiewicz, Aleksandra

    2004-01-01

    A model of reactive oxygen species metabolism is proposed as a laboratory exercise for students. The superoxide ion in this model is generated during the reaction of oxidation of xanthine, catalyzed by xanthine oxidase. The effect of catalase, superoxide dismutase, and allopurinol on superoxide ion generation and removal in this system is also…

  18. Innovative Fast Reactors: Impact of Fuel Composition on Reactivity Coefficients

    SciTech Connect

    G. Palmiotti; M. Salvatores; M. Asswaroongruengchot

    2009-12-01

    A major challenge for future Fast Reactors could be the recycling of minor actinides (MA) in the core fuel, in order to minimize wastes and contribute to meet both the sustainability objective and the reduction of the burden on a geological disposal. Although the most outstanding issues will be found in the development and validation of the appropriate fuels, the presence of MA in the core can potentially deteriorate the core reactivity coefficients. In the present paper we will show however that there is no physical limit to the amount of MA in the core fuel, but that a careful physics analysis can indicate the most appropriate measures to reduce the MA impact on the reactivity coefficients, and in particular, for Na cooled reactors, on the Na void reactivity coefficient.

  19. Fuel temperature reactivity coefficient calculation by Monte Carlo perturbation techniques

    SciTech Connect

    Shim, H. J.; Kim, C. H.

    2013-07-01

    We present an efficient method to estimate the fuel temperature reactivity coefficient (FTC) by the Monte Carlo adjoint-weighted correlated sampling method. In this method, a fuel temperature change is regarded as variations of the microscopic cross sections and the temperature in the free gas model which is adopted to correct the asymptotic double differential scattering kernel. The effectiveness of the new method is examined through the continuous energy MC neutronics calculations for PWR pin cell problems. The isotope-wise and reaction-type-wise contributions to the FTCs are investigated for two free gas models - the constant scattering cross section model and the exact model. It is shown that the proposed method can efficiently predict the reactivity change due to the fuel temperature variation. (authors)

  20. Engine combustion control at low loads via fuel reactivity stratification

    SciTech Connect

    Reitz, Rolf Deneys; Hanson, Reed M; Splitter, Derek A; Kokjohn, Sage L

    2014-10-07

    A compression ignition (diesel) engine uses two or more fuel charges during a combustion cycle, with the fuel charges having two or more reactivities (e.g., different cetane numbers), in order to control the timing and duration of combustion. By appropriately choosing the reactivities of the charges, their relative amounts, and their timing, combustion can be tailored to achieve optimal power output (and thus fuel efficiency), at controlled temperatures (and thus controlled NOx), and with controlled equivalence ratios (and thus controlled soot). At low load and no load (idling) conditions, the aforementioned results are attained by restricting airflow to the combustion chamber during the intake stroke (as by throttling the incoming air at or prior to the combustion chamber's intake port) so that the cylinder air pressure is below ambient pressure at the start of the compression stroke.

  1. Deposit formation in hydrocarbon rocket fuels

    NASA Technical Reports Server (NTRS)

    Roback, R.; Szetela, E. J.; Spadaccini, L. J.

    1981-01-01

    An experimental program was conducted to study deposit formation in hydrocarbon fuels under flow conditions that exist in high-pressure, rocket engine cooling systems. A high pressure fuel coking test apparatus was designed and developed and was used to evaluate thermal decomposition (coking) limits and carbon deposition rates in heated copper tubes for two hydrocarbon rocket fuels, RP-1 and commercial-grade propane. Tests were also conducted using JP-7 and chemically-pure propane as being representative of more refined cuts of the baseline fuels. A parametric evaluation of fuel thermal stability was performed at pressures of 136 atm to 340 atm, bulk fuel velocities in the range 6 to 30 m/sec, and tube wall temperatures in the range 422 to 811 K. Results indicated that substantial deposit formation occurs with RP-1 fuel at wall temperatures between 600 and 800 K, with peak deposit formation occurring near 700 K. No improvements were obtained when deoxygenated JP-7 fuel was substituted for RP-1. The carbon deposition rates for the propane fuels were generally higher than those obtained for either of the kerosene fuels at any given wall temperature. There appeared to be little difference between commercial-grade and chemically-pure propane with regard to type and quantity of deposit. Results of tests conducted with RP-1 indicated that the rate of deposit formation increased slightly with pressure over the range 136 atm to 340 atm. Finally, lating the inside wall of the tubes with nickel was found to significantly reduce carbon deposition rates for RP-1 fuel.

  2. Direct formate fuel cells: A review

    NASA Astrophysics Data System (ADS)

    An, L.; Chen, R.

    2016-07-01

    Direct formate fuel cells (DFFC), which convert the chemical energy stored in formate directly into electricity, are recently attracting more attention, primarily because of the use of the carbon-neutral fuel and the low-cost electrocatalytic and membrane materials. As an emerging energy technology, the DFFC has made a rapid progress in recent years (currently, the state-of-the-art power density is 591 mW cm-2 at 60 °C). This article provides a review of past research on the development of this type of fuel cell, including the working principle, mechanisms and materials of the electrocatalytic oxidation of formate, singe-cell designs and performance, as well as innovative system designs. In addition, future perspectives with regard to the development of this fuel cell system are also highlighted.

  3. Cerium Oxyhydroxide Clusters: Formation, Structure and Reactivity

    SciTech Connect

    Aubriet, F.; Gaumet, Jean-Jacques; De Jong, Wibe A.; Groenewold, G. S.; Gianotto, Anita K.; McIIwain, Michael E.; Van Stipdonk, Michael J.; Leavitt, Christopher M.

    2009-05-11

    Cerium oxyhydroxide cluster anions were produced by irradiating ceric oxide particles using 355 nm laser pulses that were synchronized with pulses of nitrogen gas admitted to the irradiation chamber. The gas pulse stabilized the nascent clusters that are largely anhydrous [CexOy] ions and neutrals. These initially-formed species react with water, principally forming closed-shell (c-s) oxohydroxy species that are described by the general formula [CexOy(OH)z]-. In general, the extent of hydroxylation varies from a value of 3 OH per Ce atom when x = 1 to a value slightly greater than 1 for x > 8. The Ce3 and Ce6 species deviate significantly from this trend: the x = 3 cluster accommodates more hydroxyl moieties compared to neighboring congeners at x = 2 and x = 4. Conversely, the x = 6 cluster is significantly less hydroxylated. Density functional theory (DFT) modeling of the cluster structures show that the hydrated clusters are hydrolyzed, and contain one-to-multiple hydroxide moieties, but not datively bound water. DFT also predicts an energetic preference for formation of highly symmetric structures as the size of the clusters increases. The calculated structures indicate that the ability of the Ce3 oxyhydroxide to accommodate more extensive hydroxylation is due to a more open, hexagonal structure in which the Ce atoms can participate in multiple hydrolysis reactions. Conversely the Ce6 oxyhydroxide has an octahedral structure that is not conducive to hydrolysis. In addition to the c-s clusters, open-shell (o-s) oxyhydroxides and superoxides are also formed, and they become more prominent as the size of the clusters increases, suggesting that the larger ceria clusters have an increased ability to stabilize a non-bonding electron. The overall intensity of the clusters tends to monotonically decrease as the cluster size increases, however this trend is interrupted at Ce13, which is significantly more stable compared to neighboring congeners, suggesting formation of

  4. Cerium Oxyhydroxide Clusters: Formation, Structure and Reactivity

    SciTech Connect

    Frederic Aubriet; Jean-Jacques Gaumet; Wibe A de Jong; Groenewold, Gary S; Gianotto, Anita K; McIlwain, Michael E; Michael J. Van Stipdonk; Christopher M. Leavitt

    2009-06-01

    Cerium oxyhydroxide cluster anions were produced by irradiating ceric oxide particles using 355 nm laser pulses that were synchronized with pulses of nitrogen gas admitted to the irradiation chamber. The gas pulse stabilized the nascent clusters that are largely anhydrous [CexOy] ions and neutrals. These initially-formed species react with water, principally forming closed-shell (c-s) oxohydroxy species that are described by the general formula [CexOy(OH)z]-. In general, the extent of hydroxylation varies from a value of 3 OH per Ce atom when x = 1 to a value slightly greater than 1 for x > 8. The Ce3 and Ce6 species deviate significantly from this trend: the x = 3 cluster accommodates more hydroxyl moieties compared to neighboring congeners at x = 2 and x = 4. Conversely, the x = 6 cluster is significantly less hydroxylated. Density functional theory (DFT) modeling of the cluster structures show that the hydrated clusters are hydrolyzed, and contain one-to-multiple hydroxide moieties, but not datively bound water. DFT also predicts an energetic preference for formation of highly symmetric structures as the size of the clusters increases. The calculated structures indicate that the ability of the Ce3 oxyhydroxide to accommodate more extensive hydroxylation is due to a more open, hexagonal structure in which the Ce atoms can participate in multiple hydrolysis reactions. Conversely the Ce6 oxyhydroxide has an octahedral structure that is not conducive to hydrolysis. In addition to the c-s clusters, open-shell (o-s) oxyhydroxides and superoxides are also formed, and they become more prominent as the size of the clusters increases, suggesting that the larger ceria clusters have an increased ability to stabilize a non-bonding electron. The overall intensity of the clusters tends to monotonically decrease as the cluster size increases, however this trend is interrupted at Ce13, which is significantly more stable compared to neighboring congeners, suggesting formation of

  5. Reactive vaporization of oxides in solid oxide fuel cell systems

    NASA Astrophysics Data System (ADS)

    Key, Camas Fought

    Metals such as chromium, aluminum and silicon are of extreme technological and industrial importance due to the corrosion resistance they offer in oxidizing environments at high temperature. Much of this robustness is based on the formation of a thin, well-adhered metal-oxide (MO) layer on the surface of the metal. In particularly corrosive environments or at high-enough temperatures and or pressures, the MO will chemically react with constituents in the surrounding gas, removing atoms from the solid. For many systems, material loss and subsequent mechanical failure is the foremost concern. However, in solid oxide fuel cell (SOFC) systems, the presence of gaseous metal species leads to severe degradation in electrochemical performance well before mechanical limits are reached. Reactive vaporization from ferritic stainless steels, chromia, aluminosilicates and a candidate electrode material (Sr2VMoO6), was investigated using the transpiration method. Two novel collection methods were employed: condensation of vapors on wafer collectors analyzed with Rutherford backscattering spectrometry (RBS); and, condensation of vapors on quartz wool analyzed via inductively coupled plasma mass spectroscopy (ICP-MS). Identification and quantification of vapor species provided assessment of material performance in SOFC environments. Experiments demonstrated that Cr vapor species from ferritic stainless steels used for SOFC interconnect applications could be reduced by as much as one order of magnitude through the application of barrier coatings. Base alloys were compared and exhibited a variety of Cr vaporization rates despite being similar in composition, thus illustrating the importance of minor elemental constituents in the alloy. Measurements identified Si as the primary volatile element in aluminosilicate materials when Si concentrations in the bulk material were as low as one percent. Aluminosilicate materials demonstrated a burn out phase during the first hundred hours at

  6. Experimental study of fuel cloud formation inside aircraft fuel tank

    NASA Astrophysics Data System (ADS)

    Putthawong, Panu

    The design of fuel tank flammability has relied on the flammability envelope of a homogeneous mixture. There are researches indicated that the presence of droplets could cause such mixture to be flammable even the fuel-to-air ratio was below the Lower Flammability Limit. This research aims to investigate the formation of fuel cloud/droplets by a condensation process and its effect on tank flammability. The center-wing tank is the main interest because the fuel vapor in the ullage space can condense when its temperature and pressure are changed. The Fuel Tank Test Facility has proven that a cloud or group of droplets is produced under normal operating condition of the center-wing tank. Results from the experiments show the number densities of droplets on the order of 103--105 and the maximum drop size being recorded is 18 mum. The experiments also indicate that Jet A vapor and droplets must have different properties from its liquid form because of the volatility difference among species in fuel. The new parameter for droplets flammability, i.e., non-dimensional droplet spacing, suggested by Hayashi et al. (1984) is employed for a flammability assessment. The non-dimensional droplet spacings from the experiments have found to be in the vicinity of the critical value. It points toward the high possibility of having flammable center-wing tank. The explosion strength calculation of droplets-vapor-air mixture implies the sufficient explosive condition if an ignition source is introduced.

  7. Formation, structure, and reactivity of palladium superoxo complexes

    SciTech Connect

    Talsi, E.P.; Babenko, V.P.; Shubin, A.A.; Chinakov, V.D.; Nekipelov, V.M.; Zamaraev, K.I.

    1987-11-18

    The mechanism of formation of palladium superoxo complexes, their structure, and their reactivity are discussed. The formation of the palladium superoxo complexes in the reaction of palladium(II) acetate, propionate, trifluororacetate, and bis(acetylacetonate) and palladium(0) tetrakis(triphenylphosphine) with hydrogen peroxide and potassium superoxide has been detected in solution by electron proton resonance. The oxidation of olefins and carbon monoxide by these complexes is considered. Reaction mechanisms and reaction kinetics for these oxidations are reported using the palladium superoxo complexes. 44 references, 8 figures, 2 tables.

  8. Reactivity effects of void formations in a solution critical assembly

    SciTech Connect

    Walters, S.G.

    1994-01-01

    SHEBA II (Solution High Energy Burst Assembly) was constructed in order to better understand the neutronics of solutions of fissile materials. In order to estimate the effect on criticality from the formation of bubbles, models were devised in MCNP (Monte Carlo Neutron Photon transport code) and THREEDANT (THREE dimensional, Diffusion-Accelerated, Neutral-Particle Transport). It was found that the formation of voids in all but the outside bottom edge of the assembly cylinder tend to act as a negative insertion of reactivity. Also, an experiment has been designed which will verify the results of the codes.

  9. Fuels for fuel cells: Fuel and catalyst effects on carbon formation

    SciTech Connect

    Borup, R. L.; Inbody, M. A.; Perry, W. L.; Parkinson, W. J. ,

    2002-01-01

    The goal of this research is to explore the effects of fuels, fuel constituents, additives and impurities on the performance of on-board hydrogen generation devices and consequently on the overall performance of fuel cell systems using reformed hydrocarbon fuels. Different fuels and components have been tested in automotive scale, adiabatic autothermal reactors to observe their relative reforming characteristics with various operating conditions. Carbon formation has been modeled and was experimentally monitored in situ during operation by laser measurements of the effluent reformate. Ammonia formation was monitored, and conditions varied to observe under what conditions N H 3 is made.

  10. FORMATION PROCESSES AND CONSEQUENCES OF REACTIVE AND NON-REACTIVE MINERAL PRECIPITATES IN PERMEABLE REACTIVE BARRIERS

    EPA Science Inventory

    Mineral precipitates in zero-valent iron PRBs can be classified by formation processes into three groups: 1) those that result from changes in chemical conditions (i.e., change in pH, e.g., calcite); 2) those that are a consequence of microbial activity (i.e., sulfate reduction, ...

  11. On mechanisms of reactive metabolite formation from drugs.

    PubMed

    Claesson, Alf; Spjuth, Ola

    2013-04-01

    Idiosyncratic adverse drug reactions (IADRs) cause a broad range of clinically severe conditions of which drug induced liver injury (DILI) in particular is one of the most frequent causes of safety-related drug withdrawals. The underlying cause is almost invariably formation of reactive metabolites (RM) which by attacking macromolecules induc eorgan injuries. Attempts are being made in the pharmaceutical industry to lower the risk of selecting unfit compounds as clinical candidates. Approaches vary but do not seem to be overly successful at the initial design/synthesis stage. We review here the most frequent categories of mechanisms for RM formation and propose that many cases of RMs encountered within early ADME screening can be foreseen by applying chemical and metabolic knowledge. We also mention a web tool, SpotRM, which can be used for efficient look-up and learning about drugs that have recognized IADRs likely caused by RM formation. PMID:23035789

  12. Pollutant Formation in Monodisperse Fuel Spray Combustion

    NASA Technical Reports Server (NTRS)

    Cernansky, N. P.; Sarv, H.

    1983-01-01

    The combustion of liquid sprays represents an extremely important class of combustion processes. In the transition region, encompassing droplet sizes in the range of 25-80 micron diameter, the mixing and evaporation processes are both incomplete at the flame front and burning occurs in a combined diffusive and premixed fashion. Under these conditions, the relative importance of heterogeneous and homogeneous effects in dominating the combustion process is switched and gives rise to a number of interesting phenomena. NO (sub x) formation in monodisperse spray combustion was investigated with the following specific objectives: (1) to quantitatively determine the effect of droplet size, number density, etc. on NO sub x formation in monodisperse fuel spray combustion; and (2) to isolate the important physical and chemical phenomena in NO sub x formation in these combustion systems.

  13. Molten salt extraction of transuranic and reactive fission products from used uranium oxide fuel

    SciTech Connect

    Herrmann, Steven Douglas

    2014-05-27

    Used uranium oxide fuel is detoxified by extracting transuranic and reactive fission products into molten salt. By contacting declad and crushed used uranium oxide fuel with a molten halide salt containing a minor fraction of the respective uranium trihalide, transuranic and reactive fission products partition from the fuel to the molten salt phase, while uranium oxide and non-reactive, or noble metal, fission products remain in an insoluble solid phase. The salt is then separated from the fuel via draining and distillation. By this method, the bulk of the decay heat, fission poisoning capacity, and radiotoxicity are removed from the used fuel. The remaining radioactivity from the noble metal fission products in the detoxified fuel is primarily limited to soft beta emitters. The extracted transuranic and reactive fission products are amenable to existing technologies for group uranium/transuranic product recovery and fission product immobilization in engineered waste forms.

  14. Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product

    NASA Technical Reports Server (NTRS)

    David, Dennis D.; Dee, Louis A.; Beeson, Harold D.

    1997-01-01

    Fuel-oxidizer reaction product (FORP), the product of incomplete reaction of monomethylhydrazine and nitrogen tetroxide propellants prepared under laboratory conditions and from firings of Shuttle Reaction Control System thrusters, has been characterized by chemical and thermal analysis. The composition of FORP is variable but falls within a limited range of compositions that depend on three factors: the fuel-oxidizer ratio at the time of formation; whether the composition of the post-formation atmosphere is reducing or oxidizing; and the reaction or post-reaction temperature. A typical composition contains methylhydrazinium nitrate, ammonium nitrate, methylammonium nitrate, and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. Thermal decomposition reactions of the FORP compositions used in this study were unremarkable. Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid monomethylhydrazine and liquid nitrogen tetroxide in a confined space. These tests demonstrated that monomethylhydrazine, methylhydrazinium nitrate, ammonium nitrate, or Inconel corrosion products can induce a mixture of monomethylhydrazine and nitrogen tetroxide to produce component-damaging energies. Damaging events required FORP or metal salts to be present at the initial mixing of monomethylhydrazine and nitrogen tetroxide.

  15. Formation, stability, and reactivity studies of neutral iron sulfide clusters

    NASA Astrophysics Data System (ADS)

    Yin, Shi; Wang, Zhechen; Bernstein, Elliot

    2014-03-01

    Different methods are used to generate neutral iron sulfide clusters to study their formation, stability, and reactivity, employing a time of flight mass spectrometer (TOFMS) with VUV (118 nm) radiation single photon ionization (SPI). Neutral FemSn (m = 1-4, n = 1-6), and hydrogen containing FemSnHx (x >0, n > m) clusters are generated by the reaction of seeded H2S in a helium carrier gas with laser ablated iron metal within a supersonic nozzle. The observed strong signal of association products Fe2S2(SH)0,1 M (M = CO, C2H4, C3H6) suggest that the Fe2S2(SH)0,1 clusters have the high activity for interactions with these small molecules. In order to avoid the effect for reactivity from hydrogen containing clusters, pure FemSnclusters are generated through laser ablation of a mixed iron/sulfur target in the presence of a pure helium carrier gas. (FeS)m (m = 1-4) is observed to be the most stable series. Reaction of CO and H2 on neutral (FeS)1,2clusters is farther investigated both experimentally and theoretically. A size dependent reactivity of iron sulfide clusters toward CO is characterized. The reaction FeS + CO --> Fe + OCS is found for the FeS cluster. Products Fe2S 213COH2 and Fe2S 213COH4 are identified for reactions of 13CO and H2 on Fe2S2 clusters: this suggests that the Fe2S2 cluster has a high catalytic activity for hydrogenation reactions of CO to form formaldehyde and methanol. DFT calculations are performed to explore the potential energy surfaces for the two reactions: Fe2S2 + CO + 2H2 --> Fe2S2 + CH3OH; and Fe2S2 + CO + H2 --> Fe2S2 + CH2O.

  16. Reactive oxygen species promote raft formation in T lymphocytes.

    PubMed

    Lu, Shu-Ping; Lin Feng, Ming-Hsien; Huang, Huey-Lan; Huang, Ya-Ching; Tsou, Wen-I; Lai, Ming-Zong

    2007-04-01

    Lipid rafts are involved in many cell biology events, yet the molecular mechanisms on how rafts are formed are poorly understood. In this study we probed the possible requirement of reactive oxygen species (ROS) for T-cell receptor (TCR)-induced lipid raft formation. Microscopy and biochemical analyses illustrated that blockage of ROS production, by superoxide dismutase-mimic MnTBAP, significantly reduced partitioning of LAT, phospho-LAT, and PLC-gamma in lipid rafts. Another antioxidant N-acetylcysteine (NAC) displayed a similar suppressive effect on the entry of phospho-LAT into raft microdomains. The involvement of ROS in TCR-mediated raft assembly was observed in T-cell hybridomas, T leukemia cells, and normal T cells. Removal of ROS was accompanied by an attenuated activation of LAT and PKCtheta, with reduced production of IL-2. Consistently, treating T cells with the ROS-producer tert-butyl hydrogen peroxide (TBHP) greatly enhanced membrane raft formation, distribution of phospho-LAT into lipid rafts, and increased IL-2 production. Our results indicate for the first time that ROS contribute to TCR-induced membrane raft formation. PMID:17349922

  17. Black Silicon Formation in Cryogenic Reactive Ion Etching

    NASA Astrophysics Data System (ADS)

    Abi Saab, David; Basset, Philippe; Pierotti, Matthew J.; Trawick, Matthew L.; Angelescu, Dan E.

    2015-03-01

    We present both experimental data and computational modeling that explain some aspects of the formation of black silicon during cryogenic reactive ion etching (RIE) processes. We generate a phase diagram that predicts combinations of RIE parameters that lead to different black silicon geometries. We also show that the combination of needle- and hole-like features of various heights and depths in black silicon creates a uniquely smooth transition in refractive index that is responsible for the material's low optical reflectivity. These details are captured by our model and confirmed by focused ion beam (FIB) nanotomography and scanning electron microscopy of black silicon surfaces during various stages of development. The model also correctly describes dynamical characteristics such as the dependence of aspect ratio on process time, and the prediction of new etching fronts appearing at topographical saddle points.

  18. Sensitivity and uncertainty analysis of reactivities for UO2 and MOX fueled PWR cells

    SciTech Connect

    Foad, Basma; Takeda, Toshikazu

    2015-12-31

    The purpose of this paper is to apply our improved method for calculating sensitivities and uncertainties of reactivity responses for UO{sub 2} and MOX fueled pressurized water reactor cells. The improved method has been used to calculate sensitivity coefficients relative to infinite dilution cross-sections, where the self-shielding effect is taken into account. Two types of reactivities are considered: Doppler reactivity and coolant void reactivity, for each type of reactivity, the sensitivities are calculated for small and large perturbations. The results have demonstrated that the reactivity responses have larger relative uncertainty than eigenvalue responses. In addition, the uncertainty of coolant void reactivity is much greater than Doppler reactivity especially for large perturbations. The sensitivity coefficients and uncertainties of both reactivities were verified by comparing with SCALE code results using ENDF/B-VII library and good agreements have been found.

  19. Two-Dimensional Diffusion Theory Analysis of Reactivity Effects of a Fuel-Plate-Removal Experiment

    NASA Technical Reports Server (NTRS)

    Gotsky, Edward R.; Cusick, James P.; Bogart, Donald

    1959-01-01

    Two-dimensional two-group diffusion calculations were performed on the NASA reactor simulator in order to evaluate the reactivity effects of fuel plates removed successively from the center experimental fuel element of a seven- by three-element core loading at the Oak Ridge Bulk Shielding Facility. The reactivity calculations were performed by two methods: In the first, the slowing-down properties of the experimental fuel element were represented by its infinite media parameters; and, in the second, the finite size of the experimental fuel element was recognized, and the slowing-down properties of the surrounding core were attributed to this small region. The latter calculation method agreed very well with the experimented reactivity effects; the former method underestimated the experimental reactivity effects.

  20. Reactivity-controlled compression ignition drive cycle emissions and fuel economy estimations using vehicle system simulations

    DOE PAGESBeta

    Curran, Scott J.; Gao, Zhiming; Wagner, Robert M.

    2014-12-22

    In-cylinder blending of gasoline and diesel to achieve reactivity-controlled compression ignition has been shown to reduce NOX and soot emissions while maintaining or improving brake thermal efficiency as compared with conventional diesel combustion. The reactivity-controlled compression ignition concept has an advantage over many advanced combustion strategies in that the fuel reactivity can be tailored to the engine speed and load, allowing stable low-temperature combustion to be extended over more of the light-duty drive cycle load range. In this paper, a multi-mode reactivity-controlled compression ignition strategy is employed where the engine switches from reactivity-controlled compression ignition to conventional diesel combustion whenmore » speed and load demand are outside of the experimentally determined reactivity-controlled compression ignition range. The potential for reactivity-controlled compression ignition to reduce drive cycle fuel economy and emissions is not clearly understood and is explored here by simulating the fuel economy and emissions for a multi-mode reactivity-controlled compression ignition–enabled vehicle operating over a variety of US drive cycles using experimental engine maps for multi-mode reactivity-controlled compression ignition, conventional diesel combustion, and a 2009 port-fuel injected gasoline engine. Drive cycle simulations are completed assuming a conventional mid-size passenger vehicle with an automatic transmission. Multi-mode reactivity-controlled compression ignition fuel economy simulation results are compared with the same vehicle powered by a representative 2009 port-fuel injected gasoline engine over multiple drive cycles. Finally, engine-out drive cycle emissions are compared with conventional diesel combustion, and observations regarding relative gasoline and diesel tank sizes needed for the various drive cycles are also summarized.« less

  1. Reactivity-controlled compression ignition drive cycle emissions and fuel economy estimations using vehicle system simulations

    SciTech Connect

    Curran, Scott J.; Gao, Zhiming; Wagner, Robert M.

    2014-12-22

    In-cylinder blending of gasoline and diesel to achieve reactivity-controlled compression ignition has been shown to reduce NOX and soot emissions while maintaining or improving brake thermal efficiency as compared with conventional diesel combustion. The reactivity-controlled compression ignition concept has an advantage over many advanced combustion strategies in that the fuel reactivity can be tailored to the engine speed and load, allowing stable low-temperature combustion to be extended over more of the light-duty drive cycle load range. In this paper, a multi-mode reactivity-controlled compression ignition strategy is employed where the engine switches from reactivity-controlled compression ignition to conventional diesel combustion when speed and load demand are outside of the experimentally determined reactivity-controlled compression ignition range. The potential for reactivity-controlled compression ignition to reduce drive cycle fuel economy and emissions is not clearly understood and is explored here by simulating the fuel economy and emissions for a multi-mode reactivity-controlled compression ignition–enabled vehicle operating over a variety of US drive cycles using experimental engine maps for multi-mode reactivity-controlled compression ignition, conventional diesel combustion, and a 2009 port-fuel injected gasoline engine. Drive cycle simulations are completed assuming a conventional mid-size passenger vehicle with an automatic transmission. Multi-mode reactivity-controlled compression ignition fuel economy simulation results are compared with the same vehicle powered by a representative 2009 port-fuel injected gasoline engine over multiple drive cycles. Finally, engine-out drive cycle emissions are compared with conventional diesel combustion, and observations regarding relative gasoline and diesel tank sizes needed for the various drive cycles are also summarized.

  2. Reactive thrust cruise for a geosynchronous satellite with minimum fuel consumption

    NASA Astrophysics Data System (ADS)

    Sidi, Marcel

    1993-02-01

    A simple control concept utilizing product of inertia is used to provide active nutation control of a reactive thrust control system of a geosynchronous momentum-based satellite. The reactive thrust control system itself is immune to sensor noise and thus prevents unnecessary thrust firings. Any nutation excitation is damped in a small number of nutational periods, with no fuel consumption.

  3. Premixed direct injection nozzle for highly reactive fuels

    SciTech Connect

    Ziminsky, Willy Steve; Johnson, Thomas Edward; Lacy, Benjamin Paul; York, William David; Uhm, Jong Ho; Zuo, Baifang

    2013-09-24

    A fuel/air mixing tube for use in a fuel/air mixing tube bundle is provided. The fuel/air mixing tube includes an outer tube wall extending axially along a tube axis between an inlet end and an exit end, the outer tube wall having a thickness extending between an inner tube surface having a inner diameter and an outer tube surface having an outer tube diameter. The tube further includes at least one fuel injection hole having a fuel injection hole diameter extending through the outer tube wall, the fuel injection hole having an injection angle relative to the tube axis. The invention provides good fuel air mixing with low combustion generated NOx and low flow pressure loss translating to a high gas turbine efficiency, that is durable, and resistant to flame holding and flash back.

  4. Low-Toxicity Reactive Hypergolic Fuels for Use with Hydrogen Peroxide

    NASA Astrophysics Data System (ADS)

    Palmer, R. K.; Rusek, J. J.

    2004-10-01

    The need for low toxicity hypergolic fuels has brought rocket grade hydrogen peroxide (RGHP) to the forefront as the oxidizer of choice for future hypergolic systems. The search for a hypergolic mate for RGHP has been primarily focused on using transition metal salts dissolved in energetic liquids to create hypergolic fuels. These dissolved salts catalytically decompose RGHP on contact, producing heated oxygen and steam which ignite the remainder of the fuel. The use of transition metal salts in these fuels is therefore necessary to induce hypergolicity, but these compounds reduce the specific impulse of these fuels due to the presence of high molecular weight transition metal oxides in the exhaust. Reactive hypergolic fuels can eliminate this problem by using light metal hydrides dissolved in energetic liquids for fuels. These metal hydrides combust directly with RGHP upon contact and ignite the remainder of the fuel. Due to the low atomic weights of the metals used, these metal hydrides can enhance the specific impulse of such fuels instead of degrading the performance as transitional metal salts do. Tests of such reactive fuels are promising and indicate that fuels of this type can be successful hypergolic fuels for use with hydrogen peroxide.

  5. Reactivity Descriptors for Direct Methanol Fuel Cell Anode Catalysts

    SciTech Connect

    Ferrin, Peter; Nilekar, Anand U.; Greeley, Jeffrey P.; Mavrikakis, Manos; Rossmeisl, Jan

    2008-11-01

    We have investigated the anode reaction in direct methanol fuel cells using a database of adsorption free energies for 16 intermediates on 12 close-packed transition metal surfaces calculated with periodic, selfconsistent, density functional theory (DFT–GGA). This database, combined with a simple electrokinetic model of the methanol electrooxidation reaction, yields mechanistic insights that are consistent with previous experimental and theoretical studies on Pt, and extends these insights to a broad spectrum of other transition metals. In addition, by using linear scaling relations between the adsorption free energies of various intermediates in the reaction network, we find that the results determined with the full database of adsorption energies can be estimated by knowing only two key descriptors for each metal surface: the free energies of OH and CO on the surface. Two mechanisms for methanol oxidation to CO₂ are investigated: an indirect mechanism that goes through a CO intermediate and a direct mechanism where methanol is oxidized to CO₂ without the formation of a CO intermediate. For the direct mechanism, we find that, because of CO poisoning, only a small current will result on all non-group 11 transition metals; of these metals, Pt is predicted to be the most active. For methanol decomposition via the indirect mechanism, we find that the onset potential is limited either by the ability to activate methanol, by the ability to activate water, or by surface poisoning by CO* or OH*/O*. Among pure metals, there is no obvious candidate for a good anode catalyst, and in order to design a better catalyst, one has to look for bi-functional surfaces such as the well-studied PtRu alloy.

  6. Mathematical modeling of biomass fuels formation process

    SciTech Connect

    Gaska, Krzysztof Wandrasz, Andrzej J.

    2008-07-01

    The increasing demand for thermal and electric energy in many branches of industry and municipal management accounts for a drastic diminishing of natural resources (fossil fuels). Meanwhile, in numerous technical processes, a huge mass of wastes is produced. A segregated and converted combustible fraction of the wastes, with relatively high calorific value, may be used as a component of formed fuels. The utilization of the formed fuel components from segregated groups of waste in associated processes of co-combustion with conventional fuels causes significant savings resulting from partial replacement of fossil fuels, and reduction of environmental pollution resulting directly from the limitation of waste migration to the environment (soil, atmospheric air, surface and underground water). The realization of technological processes with the utilization of formed fuel in associated thermal systems should be qualified by technical criteria, which means that elementary processes as well as factors of sustainable development, from a global viewpoint, must not be disturbed. The utilization of post-process waste should be preceded by detailed technical, ecological and economic analyses. In order to optimize the mixing process of fuel components, a mathematical model of the forming process was created. The model is defined as a group of data structures which uniquely identify a real process and conversion of this data in algorithms based on a problem of linear programming. The paper also presents the optimization of parameters in the process of forming fuels using a modified simplex algorithm with a polynomial worktime. This model is a datum-point in the numerical modeling of real processes, allowing a precise determination of the optimal elementary composition of formed fuels components, with assumed constraints and decision variables of the task.

  7. Deposit formation in hydrocarbon rocket fuels: Executive summary

    NASA Technical Reports Server (NTRS)

    Roback, R.; Szetela, E. J.; Spadaccini, L. J.

    1981-01-01

    An experimental program was conducted to study deposit formation in hydrocarbon fuels under flow conditions that exist in high-pressure, rocket engine cooling systems. A high pressure fuel coking test apparatus was designed and developed and was used to evaluate thermal decomposition (coking) limits and carbon deposition rates in heated copper tubes for two hydrocarbon rocket fuels, RP-1 and commercial-grade propane. Tests were also conducted using JP-7 and chemically-pure propane as being representative of more refined cuts of the baseline fuels. A parametric evaluation of fuel thermal stability was performed at pressures of 136 atm to 340 atm, bulk fuel velocities in the range 6 to 30 m/sec, and tube wall temperatures in the range 422 to 811K. In addition, the effect of the inside wall material on deposit formation was evaluated in selected tests which were conducted using nickel-plated tubes. The results of the tests indicated that substantial deposit formation occurs with RP-1 fuel at wall temperatures between 600 and 800K, with peak deposit formation occurring near 700K. No improvements were obtained when de-oxygenated JP-7 fuel was substituted for RP-1. The carbon deposition rates for the propane fuels were generally higher than those obtained for either of the kerosene fuels at any given wall temperature. There appeared to be little difference between commercial-grade and chemically-pure propane with regard to type and quantity of deposit. The results of tests conducted with RP-1 indicated that the rate of deposit formation increased slightly with pressure over the range 136 atm to 340 atm. Finally, plating the inside wall of the tubes with nickel was found to significantly reduce carbon deposition rates for RP-1 fuel.

  8. Assessment of light water reactor fuel damage during a reactivity initiated accident

    SciTech Connect

    MacDonald, P.E.; Seiffert, S.L.; Martinson, Z.R.; McCardell, R.K.; Owen, D.E.; Fukuda, S.K.

    1980-01-01

    This paper presents an assessment of LWR fuel damage during a reactivity initiated accident and comments on the adequacy of the present USNRC design requirements. Results from early SPERT tests are reviewed and compared with results from recent computer simulations and PBF tests. A progression of fuel rod and cladding damage events is presented. High strain rate deformation of relatively cool irradiated cladding early in the transient may result in fracture at a radial average peak fuel enthalpy of approximately 140 cal/g UO/sub 2/. Volume expansion of previously irradiated fuel upon melting may cause deformation and rupture of the cladding, and coolant channel blockage at higher peak enthalpies.

  9. Reactivity of NH{sub 3} and HCN during low-grade fuel combustion in a swirling flow burner

    SciTech Connect

    Chunyang Wu; Dale Tree; Larry Baxter

    2007-07-01

    The experimentally measured major gas species profiles in the near-burner region provide insight on flame structure and pollutant formation mechanisms during pilot-scale biomass, coal, and biomass-coal cofiring tests. All tests involved separately metered but jointly fed coal and biomass in a variable-swirl burner. Locally fuel-rich regions form under overall fuel-lean conditions, as is typical of such flames, although there are no regions of the combustor that indicate average oxygen concentration reaches zero. The data strongly suggest that instantaneous oxygen concentrations reach zero, so the average finite values are indicative of turbulent intermittency between fuel-rich and fuel-lean eddies. Such intermittency impacts the entire flame structure in these and many previously published flames, though this feature may not be widely appreciated. Detectable HCN concentrations appear in the fuel-rich eddies in the coal-dominated flames with little or no detectable NH{sub 3}, whereas NH{sub 3} appears in the biomass-dominated flames with little or no detectable HCN. These data indicate that biomass predominantly forms NH{sub 3} whereas coal predominantly forms HCN as stable, fuel-rich, gas-phase compounds. Kinetics calculations demonstrate that NH{sub 3} has higher thermal stability and is more reactive within the flame front than HCN. Both species have similar conversion to NO at the same temperatures. The results confirm that NOx precursor formation depends on the parent fuel and form of nitrogen, at least for the coal and biomass fuels investigated here. 24 refs., 11 figs., 3 tabs.

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

    EPA Science Inventory

    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...

  11. Impact investigation of reactor fuel operating parameters on reactivity for use in burnup credit applications

    NASA Astrophysics Data System (ADS)

    Sloma, Tanya Noel

    When representing the behavior of commercial spent nuclear fuel (SNF), credit is sought for the reduced reactivity associated with the net depletion of fissile isotopes and the creation of neutron-absorbing isotopes, a process that begins when a commercial nuclear reactor is first operated at power. Burnup credit accounts for the reduced reactivity potential of a fuel assembly and varies with the fuel burnup, cooling time, and the initial enrichment of fissile material in the fuel. With regard to long-term SNF disposal and transportation, tremendous benefits, such as increased capacity, flexibility of design and system operations, and reduced overall costs, provide an incentive to seek burnup credit for criticality safety evaluations. The Nuclear Regulatory Commission issued Interim Staff Guidance 8, Revision 2 in 2002, endorsing burnup credit of actinide composition changes only; credit due to actinides encompasses approximately 30% of exiting pressurized water reactor SNF inventory and could potentially be increased to 90% if fission product credit were accepted. However, one significant issue for utilizing full burnup credit, compensating for actinide and fission product composition changes, is establishing a set of depletion parameters that produce an adequately conservative representation of the fuel's isotopic inventory. Depletion parameters can have a significant effect on the isotopic inventory of the fuel, and thus the residual reactivity. This research seeks to quantify the reactivity impact on a system from dominant depletion parameters (i.e., fuel temperature, moderator density, burnable poison rod, burnable poison rod history, and soluble boron concentration). Bounding depletion parameters were developed by statistical evaluation of a database containing reactor operating histories. The database was generated from summary reports of commercial reactor criticality data. Through depletion calculations, utilizing the SCALE 6 code package, several light

  12. Fuel composition and secondary organic aerosol formation: gas-turbine exhaust and alternative aviation fuels.

    PubMed

    Miracolo, Marissa A; Drozd, Greg T; Jathar, Shantanu H; Presto, Albert A; Lipsky, Eric M; Corporan, Edwin; Robinson, Allen L

    2012-08-01

    A series of smog chamber experiments were performed to investigate the effects of fuel composition on secondary particulate matter (PM) formation from dilute exhaust from a T63 gas-turbine engine. Tests were performed at idle and cruise loads with the engine fueled on conventional military jet fuel (JP-8), Fischer-Tropsch synthetic jet fuel (FT), and a 50/50 blend of the two fuels. Emissions were sampled into a portable smog chamber and exposed to sunlight or artificial UV light to initiate photo-oxidation. Similar to previous studies, neat FT fuel and a 50/50 FT/JP-8 blend reduced the primary particulate matter emissions compared to neat JP-8. After only one hour of photo-oxidation at typical atmospheric OH levels, the secondary PM production in dilute exhaust exceeded primary PM emissions, except when operating the engine at high load on FT fuel. Therefore, accounting for secondary PM production should be considered when assessing the contribution of gas-turbine engine emissions to ambient PM levels. FT fuel substantially reduced secondary PM formation in dilute exhaust compared to neat JP-8 at both idle and cruise loads. At idle load, the secondary PM formation was reduced by a factor of 20 with the use of neat FT fuel, and a factor of 2 with the use of the blend fuel. At cruise load, the use of FT fuel resulted in no measured formation of secondary PM. In every experiment, the secondary PM was dominated by organics with minor contributions from sulfate when the engine was operated on JP-8 fuel. At both loads, FT fuel produces less secondary organic aerosol than JP-8 because of differences in the composition of the fuels and the resultant emissions. This work indicates that fuel reformulation may be a viable strategy to reduce the contribution of emissions from combustion systems to secondary organic aerosol production and ultimately ambient PM levels. PMID:22732009

  13. Ceramic-metal composite formation by reactive metal penetration

    SciTech Connect

    Loehman, R.E.; Ewsuk, K.G.; Fahrenholtz, W.G.; Lakshman, B.B.

    1996-11-01

    Ceramic-metal composites can be made to near-net-shape by reactive penetration of dense ceramic preforms by molten metals. Reactive metal penetration is driven by a strongly negative Gibbs energy for reaction. For Al, the general form of the reaction is (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 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] degree(927 degrees C) of -338 per mole of mullite and, for fully dense mullite, the theoretical volume change on reaction is less than 1%. Experiments with commercial mullite containing a silicate grain boundary phase average less than 2% volume change on reaction. In the Al/mullite system, reactive metal penetration produces a fine-grained alumina skeleton with an interspersed metal phase. With > or =15 vol.% excess aluminum, mutually interpenetrating ceramic-metal composites are produced. Properties measurements show that ceramic-metal composites produced by reactive metal penetration of mullite by Al have a Young`s modulus and hardness similar to that of Al[sub 2]O[sub 3], with improved fracture toughness. Other compositions also are candidates for in- situ reaction synthesis, but they exhibit differences in reaction kinetics, most probably due to different wetting behavior.

  14. Deposit formation and heat transfer in hydrocarbon rocket fuels

    NASA Technical Reports Server (NTRS)

    Giovanetti, A. J.; Spadaccini, L. J.; Szetela, E. J.

    1983-01-01

    An experimental research program was undertaken to investigate the thermal stability and heat transfer characteristics of several hydrocarbon fuels under conditions that simulate high-pressure, rocket engine cooling systems. The rates of carbon deposition in heated copper and nickel-plated copper tubes were determined for RP-1, propane, and natural gas using a continuous flow test apparatus which permitted independent variation and evaluation of the effect on deposit formation of wall temperature, fuel pressure, and fuel velocity. In addition, the effects of fuel additives and contaminants, cryogenic fuel temperatures, and extended duration testing with intermittent operation were examined. Parametric tests to map the thermal stability characteristics of RP-1, commercial-grade propane, and natural gas were conducted at pressures of 6.9 to 13.8 MPa, bulk fuel velocities of 30 to 90 m/s, and tube wall temperatures in the range of 230 to 810 K. Also, tests were run in which propane and natural gas fuels were chilled to 230 and 160 K, respectively. Corrosion of the copper tube surface was detected for all fuels tested. Plating the inside of the copper tubes with nickel reduced deposit formation and eliminated tube corrosion in most cases. The lowest rates of carbon deposition were obtained for natural gas, and the highest rates were obtained for propane. For all fuels tested, the forced-convection heat transfer film coefficients were satisfactorily correlated using a Nusselt-Reynolds-Prandtl number equation.

  15. NOx formation in combustion of gaseous fuel in ejection burner

    NASA Astrophysics Data System (ADS)

    Rimár, Miroslav; Kulikov, Andrii

    2016-06-01

    The aim of this work is to prepare model for researching of the formation in combustion of gaseous fuels. NOx formation is one of the main ecological problems nowadays as nitrogen oxides is one of main reasons of acid rains. The ANSYS model was designed according to the calculation to provide full combustion and good mixing of the fuel and air. The current model is appropriate to research NOx formation and the influence of the different principles of NOx reduction method. Applying of designed model should spare both time of calculations and research and also money as you do not need to measure the burner characteristics.

  16. Incremental Reactivity Effects of Anthropogenic and Biogenic Volatile Organic Compounds on Secondary Organic Aerosol Formation

    NASA Astrophysics Data System (ADS)

    Kacarab, M.; Li, L.; Carter, W. P. L.; Cocker, D. R., III

    2015-12-01

    Two surrogate reactive organic gas (ROG) mixtures were developed to create a controlled reactivity environment simulating different urban atmospheres with varying levels of anthropogenic (e.g. Los Angeles reactivity) and biogenic (e.g. Atlanta reactivity) influences. Traditional chamber experiments focus on the oxidation of one or two volatile organic compound (VOC) precursors, allowing the reactivity of the system to be dictated by those compounds. Surrogate ROG mixtures control the overall reactivity of the system, allowing for the incremental aerosol formation from an added VOC to be observed. The surrogate ROG mixtures were developed based on that used to determine maximum incremental reactivity (MIR) scales for O3 formation from VOC precursors in a Los Angeles smog environment. Environmental chamber experiments were designed to highlight the incremental aerosol formation in the simulated environment due to the addition of an added anthropogenic (aromatic) or biogenic (terpene) VOC. All experiments were conducted in the UC Riverside/CE-CERT dual 90m3 environmental chambers. It was found that the aerosol precursors behaved differently under the two altered reactivity conditions, with more incremental aerosol being formed in the anthropogenic ROG system than in the biogenic ROG system. Further, the biogenic reactivity condition inhibited the oxidation of added anthropogenic aerosol precursors, such as m-xylene. Data will be presented on aerosol properties (density, volatility, hygroscopicity) and bulk chemical composition in the gas and particle phases (from a SYFT Technologies selected ion flow tube mass spectrometer, SIFT-MS, and Aerodyne high resolution time of flight aerosol mass spectrometer, HR-ToF-AMS, respectively) comparing the two controlled reactivity systems and single precursor VOC/NOx studies. Incremental aerosol yield data at different controlled reactivities provide a novel and valuable insight in the attempt to extrapolate environmental chamber

  17. Testing to determine chemical stability, handling characteristics, and reactivity of energetic-fuel mixtures: Final report

    SciTech Connect

    Lackey, M.E.

    1988-04-01

    The US Army generates approximately 2.5 million pounds of waste explosives each year as a result of explosives production and the loading of ordnance. In addition, the US Army currently stores >200,000 tons of obsolete munitions. The current alternative to storage is open-air burning, open-air detonation, or incineration. The US Army Toxic and Hazardous Materials Agency is currently developing methods and procedures for the utilization of energetic materials blended with fuel oil as supplemental fuel in Army industrial combustors. A series of tests were conducted to evaluate the chemical compatibility, reactivity, and handling characteristics of energetic-fuel mixtures. The energetics studied were TNT, RDX, and Composition B. Results indicated that under specific conditions of energetic content, energetic/fuel oil preparation, and system design, energetic/fuel oil mixtures can successfully be used as supplemental fuel in Army industrial combustors. 9 refs., 2 figs., 8 tabs.

  18. A Critical Review of Practice of Equating the Reactivity of Spent Fuel to Fresh Fuel in Burnup Credit Criticality Safety Analyses for PWR Spent Fuel Pool Storage

    SciTech Connect

    Wagner, J.C.; Parks, C.V.

    2000-09-01

    This research examines the practice of equating the reactivity of spent fuel to that of fresh fuel for the purpose of performing burnup credit criticality safety analyses for PWR spent fuel pool (SFP) storage conditions. The investigation consists of comparing k{sub inf} estimates based on reactivity equivalent fresh fuel enrichment (REFFE) to k{sub inf} estimates using the actual spent fuel isotopics. Analyses of selected storage configurations common in PWR SFPs show that this practice yields nonconservative results (on the order of a few tenths of a percent) in configurations in which the spent fuel is adjacent to higher-reactivity assemblies (e.g., fresh or lower-burned assemblies) and yields conservative results in configurations in which spent fuel is adjacent to lower-reactivity assemblies (e.g., higher-burned fuel or empty cells). When the REFFE is determined based on unborated water moderation, analyses for storage conditions with soluble boron present reveal significant nonconservative results associated with the use of the REFFE. This observation is considered to be important, especially considering the recent allowance of credit for soluble boron up to 5% in reactivity. Finally, it is shown that the practice of equating the reactivity of spent fuel to fresh fuel is acceptable, provided the conditions for which the REFFE was determined remain unchanged. Determination of the REFFE for a reference configuration and subsequent use of the REFFE for different configurations violates the basis used for the determination of the REFFE and, thus, may lead to inaccurate, and possibly, nonconservative estimates of reactivity. A significant concentration ({approximately}2000 ppm) of soluble boron is typically (but not necessarily required to be) present in PWR SFPs, of which only a portion ({le} 500 ppm) may be credited in safety analyses. Thus, a large subcritical margin currently exists that more than accounts for errors or uncertainties associated with the use of

  19. Formation of tetragonal hydrogen tungsten bronze by reactive mechanical alloying

    SciTech Connect

    Urretavizcaya, G. Tonus, F.; Gaudin, E.; Bobet, J.-L.; Castro, F.J.

    2007-10-15

    Hydrogen tungsten bronzes have been synthesized by reactive mechanical alloying monoclinic tungsten (VI) oxide under hydrogen atmosphere. Two milling devices with different energy ranges were used. Regardless of the distinct reaction times, a similar phase evolution was observed with both apparatus. The characterization of the materials was performed by XRD, SEM, DSC and total hydrogen content determination. The final product obtained was a mixture of tetragonal H{sub 0.33}WO{sub 3} and H{sub 0.23}WO{sub 3} bronzes. - Graphical abstract: Hydrogen tungsten bronzes have been synthesized by reactive mechanical alloying (RMA) monoclinic WO{sub 3} under H{sub 2} atmosphere. By using two milling devices with different energy ranges a similar phase evolution with distinct reaction times was observed. The materials were characterized by XRD, SEM, DSC and total hydrogen content determination. The final product obtained was a mixture of tetragonal H{sub 0.33}WO{sub 3} and H{sub 0.23}WO{sub 3} bronzes. Display Omitted.

  20. Characterization of the sodium void reactivity effect for advanced liquid metal reactor fuels

    SciTech Connect

    Kessler, S.F.

    1993-12-01

    This report discusses the problems of a large positive sodium void reactivity effect in liquid metal reactors which have received increased attention following the accident at Chernobyl, a light water reactor with a positive coolant void coefficient. While the probability of voiding sodium is small, a large positive sodium void reactivity effect is, in many minds, unacceptable. Analyses were performed on models of an advanced liquid metal reactors to determine the effects fuel type have on the sodium void reactivity effect. Three fuel types were considered; metal, oxide, and nitride. Calculations were performed using three-dimensional, multigroup diffusion theory. Two programs were developed to aid the analyses. One calculated the capture-to-fission ratio and the other calculated reaction rates of selected materials. A one-group equation was derived to determine a theoretical basis for the sodium void reactivity effect. An option was presented for a shortened core having a near-zero sodium-void worth. The effect on the sodium void reactivity effect of using actinides as fuel is also considered.

  1. ReaxFF Reactive Force-Field Modeling of the Triple-Phase Boundary in a Solid Oxide Fuel Cell.

    PubMed

    Merinov, Boris V; Mueller, Jonathan E; van Duin, Adri C T; An, Qi; Goddard, William A

    2014-11-20

    In our study, the Ni/YSZ ReaxFF reactive force field was developed by combining the YSZ and Ni/C/H descriptions. ReaxFF reactive molecular dynamics (RMD) were applied to model chemical reactions, diffusion, and other physicochemical processes at the fuel/Ni/YSZ interface. The ReaxFF RMD simulations were performed on the H2/Ni/YSZ and C4H10/Ni/YSZ triple-phase boundary (TPB) systems at 1250 and 2000 K, respectively. The simulations indicate amorphization of the Ni surface, partial decohesion (delamination) at the interface, and coking, which have indeed all been observed experimentally. They also allowed us to derive the mechanism of the butane conversion at the Ni/YSZ interface. Many steps of this mechanism are similar to the pyrolysis of butane. The products obtained in our simulations are the same as those in experiment, which indicates that the developed ReaxFF potential properly describes complex physicochemical processes, such as the oxide-ion diffusion, fuel conversion, water formation reaction, coking, and delamination, occurring at the TPB and can be recommended for further computational studies of the fuel/electrode/electrolyte interfaces in a SOFC. PMID:26276491

  2. Deposit formation and heat transfer in hydrocarbon rocket fuels

    NASA Technical Reports Server (NTRS)

    Giovanetti, A. J.; Spadaccini, L. J.; Szetela, E. J.

    1984-01-01

    An experimental research program was undertaken to investigate the thermal stability and heat transfer characteristics of several hydrocarbon fuels under conditions that simulate high-pressure, rocket engine cooling systems. The rates of carbon deposition in heated copper and nickel-plated copper tubes were determined for RP-1, propane, and natural gas using a continuous flow test apparatus which permitted independent variation and evaluation of the effect on deposit formation of wall temperature, fuel pressure, and fuel velocity. In addition, the effects of fuel additives and contaminants, cryogenic fuel temperatures, and extended duration testing with intermittent operation were examined. Corrosion of the copper tube surface was detected for all fuels tested; however, plating the insides of the tubes with nickel reduced deposit formation and eliminated corrosion in most cases. The lowest rates of carbon deposition were obtained for natural gas, and the highest rates were obtained for propane. Forced-convection heat transfer film coefficients were satisfactorily correlated using a Nusselt-Reynolds-Prandtl number equation for all the fuels tested.

  3. Formation and control of aldehydes in alcohol fueled engines

    SciTech Connect

    Ayyasamy, R.; Nagalingam, B.; Ganesan, V.; Gopalakrishnan, K.V.; Murthy, B.S.

    1981-01-01

    Aldehyde formation and emissions from alcohol fueled engines are presented in this paper. Several chemical kinetic models on the mechanism leading to aldehyde formation have been examined to explore the appropriate control methods to reduce exhaust aldehyde emissions. Control of aldehydes in exhaust emissions by suitable alteration of engine operating parameters, by in cylinder treatment with additives like aniline and water, by external treatment like airpreheating, secondary air injection cooling water rate and exhaust treatment are examined. The concept of surface ignition for alcohol fuels is briefly presented as a long range objective for using alcohols with minimal aldehyde emissions. 27 refs.

  4. Strategies and chemical design approaches to reduce the potential for formation of reactive metabolic species.

    PubMed

    Argikar, Upendra A; Mangold, James B; Harriman, Shawn P

    2011-01-01

    Metabolic activation of new chemical entities to reactive intermediates is routinely monitored in drug discovery and development. Reactive intermediates may bind to cellular macromolecules such as proteins, DNA and may eventually lead to cell death via necrosis, apoptosis or oxidative stress. The evidence that the ultimate outcome of metabolic activation is an adverse drug reaction manifested as in vivo toxicity, is at best circumstantial. However, understanding the process of bioactivation of structural alerts by trapping the reactive intermediates is critical to guide medicinal chemistry efforts in quest for safer and potent molecules. This commentary provides a brief introduction to adverse drug reactions and mechanisms of reactive intermediate formation for various functional groups, followed by a review of chemical design approaches, examples of such strategies, possible isosteric replacements for structural alerts and rationalization of laboratory approaches to determine reactive intermediates, as a guide to today's medicinal chemist. PMID:21320068

  5. Formation Processes and Impacts of Reactive and Nonreactive Minerals in Permeable Reactive Barriers

    EPA Science Inventory

    Mineral precipitates in zero-valent iron PRBs can be classified by formation processes into three groups: 1) those that result from changes in chemical conditions (i.e., changes in pH, e.g., calcite); 2) those that are a consequence of microbial activity (i.e., sulfate reduction,...

  6. Performance of direct formate-peroxide fuel cells

    NASA Astrophysics Data System (ADS)

    Li, Yinshi; Wu, Hao; He, Yaling; Liu, Yue; Jin, Lei

    2015-08-01

    We report the high-performance direct formate-peroxide fuel cells (DFPFCs) that consist of a cation-exchange membrane sandwiched between an alkaline formate anode and an acid peroxide cathode. Much attention has been paid to investigate the effects of different composite parameters and operating parameters, including catalyst loadings at both anode and cathode electrodes, operating temperatures, as well as the concentrations of both formate and electrolyte solutions. It is demonstrated that the optimization of both the electrode composition (anode 2.0 mgPd cm-2, cathode 2.0 mgPt cm-2) and the solution concentration (1.0 M HCOONa-3.0 M NaOH) enables the DFPFC to yield a peak power density as high as 591 mW cm-2 at 60 °C, which is about one times higher than that of state-of-the-art anion-exchange membrane direct formate fuel cells.

  7. CASMO5/TSUNAMI-3D spent nuclear fuel reactivity uncertainty analysis

    SciTech Connect

    Ferrer, R.; Rhodes, J.; Smith, K.

    2012-07-01

    The CASMO5 lattice physics code is used in conjunction with the TSUNAMI-3D sequence in ORNL's SCALE 6 code system to estimate the uncertainties in hot-to-cold reactivity changes due to cross-section uncertainty for PWR assemblies at various burnup points. The goal of the analysis is to establish the multiplication factor uncertainty similarity between various fuel assemblies at different conditions in a quantifiable manner and to obtain a bound on the hot-to-cold reactivity uncertainty over the various assembly types and burnup attributed to fundamental cross-section data uncertainty. (authors)

  8. Impacts of fuel formulation and engine operating parameters on the nanostructure and reactivity of diesel soot

    NASA Astrophysics Data System (ADS)

    Yehliu, Kuen

    This study focuses on the impacts of fuel formulations on the reactivity and nanostructure of diesel soot. A 2.5L, 4-cylinder, turbocharged, common rail, direct injection light-duty diesel engine was used in generating soot samples. The impacts of engine operating modes and the start of combustion on soot reactivity were investigated first. Based on preliminary investigations, a test condition of 2400 rpm and 64 Nm, with single and split injection strategies, was chosen for studying the impacts of fuel formulation on the characteristics of diesel soot. Three test fuels were used: an ultra low sulfur diesel fuel (BP15), a pure soybean methyl-ester (B100), and a synthetic Fischer-Tropsch fuel (FT) produced in a gas-to-liquid process. The start of injection (SOI) and fuel rail pressures were adjusted such that the three test fuels have similar combustion phasing, thereby facilitating comparisons between soots from the different fuels. Soot reactivity was investigated by thermogravimetric analysis (TGA). According to TGA, B100 soot exhibits the fastest oxidation on a mass basis followed by BP15 and FT derived soots in order of apparent rate constant. X-ray photoelectron spectroscopy (XPS) indicates no relation between the surface oxygen content and the soot reactivity. Crystalline information for the soot samples was obtained using X-ray diffraction (XRD). The basal plane diameter obtained from XRD was inversely related to the apparent rate constants for soot oxidation. For comparison, high resolution transmission electron microscopy (HRTEM) provided images of the graphene layers. Quantitative image analysis proceeded by a custom algorithm. B100 derived soot possessed the shortest mean fringe length and greatest mean fringe tortuosity. This suggests soot (nano)structural disorder correlates with a faster oxidation rate. Such results are in agreement with the X-ray analysis, as the observed fringe length is a measure of basal plane diameter. Moreover the relation

  9. Formation mechanisms, structure, solution behavior, and reactivity of aminodiborane.

    PubMed

    Li, Huizhen; Ma, Nana; Meng, Wenjuan; Gallucci, Judith; Qiu, Yongqing; Li, Shujun; Zhao, Qianyi; Zhang, Jie; Zhao, Ji-Cheng; Chen, Xuenian

    2015-09-30

    A facile synthesis of cyclic aminodiborane (NH2B2H5, ADB) from ammonia borane (NH3·BH3, AB) and THF·BH3 has made it possible to determine its important characteristics. Ammonia diborane (NH3BH2(μ-H)BH3, AaDB) and aminoborane (NH2BH2, AoB) were identified as key intermediates in the formation of ADB. Elimination of molecular hydrogen occurred from an ion pair, [H2B(NH3) (THF)](+)[BH4](-). Protic-hydridic hydrogen scrambling was proved on the basis of analysis of the molecular hydrogen products, ADB and other reagents through (2)H NMR and MS, and it was proposed that the scrambling occurred as the ion pair reversibly formed a BH5-like intermediate, [(THF)BH2NH2](η(2)-H2)BH3. Loss of molecular hydrogen from the ion pair led to the formation of AoB, most of which was trapped by BH3 to form ADB with a small amount oligomerizing to (NH2BH2)n. Theoretical calculations showed the thermodynamic feasibility of the proposed intermediates and the activation processes. The structure of the ADB·THF complex was found from X-ray single crystal analysis to be a three-dimensional array of zigzag chains of ADB and THF, maintained by hydrogen and dihydrogen bonding. Room temperature exchange of terminal and bridge hydrogens in ADB was observed in THF solution, while such exchange was not observed in diethyl ether or toluene. Both experimental and theoretical results confirm that the B-H-B bridge in ADB is stronger than that in diborane (B2H6, DB). The B-H-B bridge is opened when ADB and NaH react to form sodium aminodiboronate, Na[NH2(BH3)2]. The structure of the sodium salt as its 18-crown-6 ether adduct was determined by X-ray single crystal analysis. PMID:26335760

  10. Chemical Characterization and Reactivity Testing of Fuel-Oxidizer Reaction Product (Test Report)

    NASA Technical Reports Server (NTRS)

    1996-01-01

    The product of incomplete reaction of monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) propellants, or fuel-oxidizer reaction product (FORP), has been hypothesized as a contributory cause of an anomaly which occurred in the chamber pressure (PC) transducer tube on the Reaction Control Subsystem (RCS) aft thruster 467 on flight STS-51. A small hole was found in the titanium-alloy PC tube at the first bend below the pressure transducer. It was surmised that the hole may have been caused by heat and pressure resulting from ignition of FORP. The NASA Johnson Space Center (JSC) White Sands Test Facility (WSTF) was requested to define the chemical characteristics of FORP, characterize its reactivity, and simulate the events in a controlled environment which may have lead to the Pc-tube failure. Samples of FORP were obtained from the gas-phase reaction of MMH with NTO under laboratory conditions, the pulsed firings of RCS thrusters with modified PC tubes using varied oxidizer or fuel lead times, and the nominal RCS thruster firings at WSTF and Kaiser-Marquardt. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), ion chromatography (IC), inductively coupled plasma (ICP) spectrometry, thermogravimetric analysis (TGA) coupled to FTIR (TGA/FTIR), and mechanical impact testing were used to qualitatively and quantitatively characterize the chemical, thermal, and ignition properties of FORP. These studies showed that the composition of FORP is variable but falls within a limited range of compositions that depends on the fuel loxidizer ratio at the time of formation, composition of the post-formation atmosphere (reducing or oxidizing), and reaction or postreaction temperature. A typical composition contains methylhydrazinium nitrate (MMHN), ammonium nitrate (AN), methylammonium nitrate (MAN), and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. The thermal decomposition

  11. Oxidation and formation of deposit precursors in hydrocarbon fuels

    NASA Technical Reports Server (NTRS)

    Mayo, F. R.; Lan, B.; Cotts, D. B.; Buttrill, S. E., Jr.; St.john, G. A.

    1983-01-01

    The oxidation of two jet turbine fuels and some pure hydrocarbons was studied at 130 C with and without the presence of small amounts of N-methyl pyrrole (NMP) or indene. Tendency to form solid-deposit precursors was studied by measuring soluble gum formation as well as dimer and trimer formation using field ionization mass spectrometry. Pure n-dodecane oxidized fastest and gave the smallest amount of procursors. An unstable fuel oil oxidized much slower but formed large amounts of precursors. Stable Jet A fuel oxidized slowest and gave little precursors. Indene either retarded or accelerated the oxidation of n-dodecane, depending on its concentration, but always caused more gum formation. The NMP greatly retarded n-dodecane oxidation but accelerated Jet A oxidation and greatly increased the latter's gum formation. In general, the additive reacted faster and formed most of the gum. Results are interpreted in terms of classical cooxidation theory. The effect of oxygen pressure on gum formation is also reported.

  12. Chemical Reactivity Testing for the National Spent Nuclear Fuel Program. Quality Assurance Project Plan

    SciTech Connect

    Newsom, H.C.

    1999-01-24

    This quality assurance project plan (QAPjP) summarizes requirements used by Lockheed Martin Energy Systems, Incorporated (LMES) Development Division at Y-12 for conducting chemical reactivity testing of Department of Energy (DOE) owned spent nuclear fuel, sponsored by the National Spent Nuclear Fuel Program (NSNFP). The requirements are based on the NSNFP Statement of Work PRO-007 (Statement of Work for Laboratory Determination of Uranium Hydride Oxidation Reaction Kinetics.) This QAPjP will utilize the quality assurance program at Y-12, QA-101PD, revision 1, and existing implementing procedures for the most part in meeting the NSNFP Statement of Work PRO-007 requirements, exceptions will be noted.

  13. A microfluidic direct formate fuel cell on paper.

    PubMed

    Copenhaver, Thomas S; Purohit, Krutarth H; Domalaon, Kryls; Pham, Linda; Burgess, Brianna J; Manorothkul, Natalie; Galvan, Vicente; Sotez, Samantha; Gomez, Frank A; Haan, John L

    2015-08-01

    We describe the first direct formate fuel cell on a paper microfluidic platform. In traditional membrane-less microfluidic fuel cells (MFCs), external pumping consumes power produced by the fuel cell in order to maintain co-laminar flow of the anode stream and oxidant stream to prevent mixing. However, in paper microfluidics, capillary action drives flow while minimizing stream mixing. In this work, we demonstrate a paper MFC that uses formate and hydrogen peroxide as the anode fuel and cathode oxidant, respectively. Using these materials we achieve a maximum power density of nearly 2.5 mW/mg Pd. In a series configuration, our MFC achieves an open circuit voltage just over 1 V, and in a parallel configuration, short circuit of 20 mA absolute current. We also demonstrate that the MFC does not require continuous flow of fuel and oxidant to produce power. We found that we can pre-saturate the materials on the paper, stop the electrolyte flow, and still produce approximately 0.5 V for 15 min. This type of paper MFC has potential applications in point-of-care diagnostic devices and other electrochemical sensors. PMID:25546700

  14. Visible contrail formation from fuels with different sulfur contents

    NASA Astrophysics Data System (ADS)

    Busen, R.; Schumann, U.

    As a test for postulated influences of sulfur emissions on nucleation, the contrail formation from a two-engine jet aircraft was investigated using fuels with different sulfur contents for the two engines during the same flight. The sulfur mass fractions in the fuels were about 2 and 250 ppm, respectively, typical for aviation fuels. Other engine and fuel parameters were about the same for both engines. Contrail formation was observed visually from distances as close as 100 m and documented by video and photos. The flight took place at 302 hPa (9 km altitude), at ambient temperatures of about -50°C, and relative humidity for liquid water of about 34%. Short contrails formed about 30 m after the engines. No visible differences were detected in the contrails forming from the two engines. The observed conditions for contrail formation are close to those predicted by Appleman [1953] if the propulsion efficiency of the aircraft/engine combination during flight is taken into account.

  15. Involvement of Cytochrome P450 in Reactive Oxygen Species Formation and Cancer.

    PubMed

    Hrycay, Eugene G; Bandiera, Stelvio M

    2015-01-01

    This review examines the involvement of cytochrome P450 (CYP) enzymes in the formation of reactive oxygen species in biological systems and discusses the possible involvement of reactive oxygen species and CYP enzymes in cancer. Reactive oxygen species are formed in biological systems as byproducts of the reduction of molecular oxygen and include the superoxide radical anion (∙O2-), hydrogen peroxide (H2O2), hydroxyl radical (∙OH), hydroperoxyl radical (HOO∙), singlet oxygen ((1)O2), and peroxyl radical (ROO∙). Two endogenous sources of reactive oxygen species are the mammalian CYP-dependent microsomal electron transport system and the mitochondrial electron transport chain. CYP enzymes catalyze the oxygenation of an organic substrate and the simultaneous reduction of molecular oxygen. If the transfer of oxygen to a substrate is not tightly controlled, uncoupling occurs and leads to the formation of reactive oxygen species. Reactive oxygen species are capable of causing oxidative damage to cellular membranes and macromolecules that can lead to the development of human diseases such as cancer. In normal cells, intracellular levels of reactive oxygen species are maintained in balance with intracellular biochemical antioxidants to prevent cellular damage. Oxidative stress occurs when this critical balance is disrupted. Topics covered in this review include the role of reactive oxygen species in intracellular cell signaling and the relationship between CYP enzymes and cancer. Outlines of CYP expression in neoplastic tissues, CYP enzyme polymorphism and cancer risk, CYP enzymes in cancer therapy and the metabolic activation of chemical procarcinogens by CYP enzymes are also provided. PMID:26233903

  16. Reactive Tracer Techniques to Quantitatively Monitor Carbon Dioxide Storage in Geologic Formations

    NASA Astrophysics Data System (ADS)

    Matter, J. M.; Carson, C.; Stute, M.; Broecker, W. S.

    2012-12-01

    Injection of CO2 into geologic storage reservoirs induces fluid-rock reactions that may lead to the mineralization of the injected CO2. The long-term safety of geologic CO2 storage is, therefore, determined by in situ CO2-fluid-rock reactions. Currently existing monitoring and verification techniques for CO2 storage are insufficient to characterize the solubility and reactivity of the injected CO2, and to establish a mass balance of the stored CO2. Dissolved and chemically transformed CO2 thus avoid detection. We developed and are testing a new reactive tracer technique for quantitative monitoring and detection of dissolved and chemically transformed CO2 in geologic storage reservoirs. The technique involves tagging the injected carbon with radiocarbon (14C). Carbon-14 is a naturally occurring radioisotope produced by cosmic radiation and made artificially by 14N neutron capture. The ambient concentration is very low with a 14C/12C ratio of 10-12. The concentration of 14C in deep geologic formations and fossil fuels is at least two orders of magnitude lower. This makes 14C an ideal quantitative tracer for tagging underground injections of anthropogenic CO2. We are testing the feasibility of this tracer technique at the CarbFix pilot injection site in Iceland, where approximately 2,000 tons of CO2 dissolved in water are currently injected into a deep basalt aquifer. The injected CO2 is tagged with 14C by dynamically adding calibrated amounts of H14CO3 solution to the injection stream. The target concentration is 12 Bq/kg of injected water, which results in a 14C activity that is 5 times enriched compared to the 1850 background. In addition to 14C as a reactive tracer, trifluormethylsulphur pentafluoride (SF5CF3) and sulfurhexafluoride (SF6) are used as conservative tracers to monitor the transport of the injected CO2 in the subsurface. Fluid samples are collected for tracer analysis from the injection and monitoring wells on a regular basis. Results show a fast

  17. Technical Basis for Peak Reactivity Burnup Credit for BWR Spent Nuclear Fuel in Storage and Transportation Systems

    SciTech Connect

    Marshall, William BJ J; Ade, Brian J; Bowman, Stephen M; Gauld, Ian C; Ilas, Germina; Mertyurek, Ugur; Radulescu, Georgeta

    2015-01-01

    Oak Ridge National Laboratory and the United States Nuclear Regulatory Commission have initiated a multiyear project to investigate application of burnup credit for boiling-water reactor (BWR) fuel in storage and transportation casks. This project includes two phases. The first phase (1) investigates applicability of peak reactivity methods currently used in spent fuel pools (SFPs) to storage and transportation systems and (2) evaluates validation of both reactivity (keff) calculations and burnup credit nuclide concentrations within these methods. The second phase will focus on extending burnup credit beyond peak reactivity. This paper documents the first phase, including an analysis of lattice design parameters and depletion effects, as well as both validation components. Initial efforts related to extended burnup credit are discussed in a companion paper. Peak reactivity analyses have been used in criticality analyses for licensing of BWR fuel in SFPs over the last 20 years. These analyses typically combine credit for the gadolinium burnable absorber present in the fuel with a modest amount of burnup credit. Gadolinium burnable absorbers are used in BWR assemblies to control core reactivity. The burnable absorber significantly reduces assembly reactivity at beginning of life, potentially leading to significant increases in assembly reactivity for burnups less than 15–20 GWd/MTU. The reactivity of each fuel lattice is dependent on gadolinium loading. The number of gadolinium-bearing fuel pins lowers initial lattice reactivity, but it has a small impact on the burnup and reactivity of the peak. The gadolinium concentration in each pin has a small impact on initial lattice reactivity but a significant effect on the reactivity of the peak and the burnup at which the peak occurs. The importance of the lattice parameters and depletion conditions are primarily determined by their impact on the gadolinium depletion. Criticality code validation for BWR burnup

  18. Fuel Cell Manufacturing Diagnostic Techniques: IR Thermography with Reactive Flow through Excitation

    SciTech Connect

    Manak, A. J.; Ulsh, M.; Bender, G.

    2012-01-01

    While design and material considerations for PEMFCs have a large impact on cost, it is also necessary to consider a transition to high volume production of fuel cell systems, including MEA components, to enable economies of scale and reduce per unit cost. One of the critical manufacturing tasks is developing and deploying techniques to provide in‐process measurement of fuel cell components for quality control. This effort requires a subsidiary task: The study of the effect of manufacturing defects on performance and durability with the objective to establish validated manufacturing tolerances for fuel cell components. This work focuses on the development of a potential quality control method for gas diffusion electrodes (GDEs). The method consists of infrared (IR) thermography combined with reactive flow through (RFT) excitation. Detection of catalyst loading reduction defects in GDE catalyst layers will be presented.

  19. Performance of Trasuranic-Loaded Fully Ceramic Micro-Encapsulated Fuel in LWRs Interim Report, Including Void Reactivity Evaluation

    SciTech Connect

    Michael A. Pope; Brian Boer; Gilles Youinou; Abderrafi M. Ougouag

    2011-03-01

    The current focus of the Deep Burn Project is on once-through burning of transuranice (TRU) in light water reactors (LWRs). The fuel form is called Fully-Ceramic Micro-encapsulated (FCM) fuel, a concept that borrows the tri-isotropic (TRISO) fuel particle design from high-temperature reactor technology. In the Deep Burn LWR (DB-LWR) concept, these fuel particles would be pressed into compacts using SiC matrix material and loaded into fuel pins for use in conventional LWRs. The TRU loading comes from the spent fuel of a conventional LWR after 5 years of cooling. Unit cell calculations have been performed using the DRAGON-4 code in order assess the physics attributes of TRU-only FCM fuel in an LWR lattice. Depletion calculations assuming an infinite lattice condition were performed with calculations of various reactivity coefficients performed at each step. Unit cells containing typical UO2 and MOX fuel were analyzed in the same way to provide a baseline against which to compare the TRU-only FCM fuel. Loading of TRU-only FCM fuel into a pin without significant quantities of uranium challenges the design from the standpoint of several key reactivity parameters, particularly void reactivity, and to some degree, the Doppler coefficient. These unit cells, while providing an indication of how a whole core of similar fuel would behave, also provide information of how individual pins of TRU-only FCM fuel would influence the reactivity behavior of a heterogeneous assembly. If these FCM fuel pins are included in a heterogeneous assembly with LEU fuel pins, the overall reactivity behavior would be dominated by the uranium pins while attractive TRU destruction performance of the TRU-only FCM fuel pins may be preserved. A configuration such as this would be similar to CONFU assemblies analyzed in previous studies. Analogous to the plutonium content limits imposed on MOX fuel, some amount of TRU-only FCM pins in an otherwise-uranium fuel assembly may give acceptable reactivity

  20. LOX/hydrocarbon fuel carbon formation and mixing data analysis

    NASA Technical Reports Server (NTRS)

    Fang, J.

    1983-01-01

    By applying the Priem-Heidmann Generalized-Length vaporization correlation, the computer model developed by the present study predicts the spatial variation of propellant vaporization rate using the injector cold flow results to define the streamtubes. The calculations show that the overall and local propellant vaporization rate and mixture ratio change drastically as the injection element type or the injector operating condition is changed. These results are compared with the regions of carbon formation observed in the photographic combustion testing. The correlation shows that the fuel vaporization rate and the local mixture ratio produced by the injector element have first order effects on the degree of carbon formation.

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

    NASA Astrophysics Data System (ADS)

    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.

  2. FUEL EFFICIENT GALAXIES: SUSTAINING STAR FORMATION WITH STELLAR MASS LOSS

    SciTech Connect

    Leitner, Samuel N.; Kravtsov, Andrey V.

    2011-06-10

    We examine the importance of secular stellar mass loss for fueling ongoing star formation in disk galaxies during the late stages of their evolution. For a galaxy of a given stellar mass, we calculate the total mass loss rate of its entire stellar population using star formation histories derived from the observed evolution of the M{sub *}-star formation rate (SFR) relation, along with the predictions of standard stellar evolution models for stellar mass loss for a variety of initial stellar mass functions. Our model shows that recycled gas from stellar mass loss can provide most or all of the fuel required to sustain the current level of star formation in late-type galaxies. Stellar mass loss can therefore remove the tension between the low gas infall rates that are derived from observations and the relatively rapid star formation occurring in disk galaxies. For galaxies where cold gas infall rates have been estimated, we demonstrate explicitly that stellar mass loss can account for most of the deficit between their SFR and infall rate.

  3. Incremental Reactivity Effects on Secondary Organic Aerosol Formation in Urban Atmospheres with and without Biogenic Influence

    NASA Astrophysics Data System (ADS)

    Kacarab, Mary; Li, Lijie; Carter, William P. L.; Cocker, David R., III

    2016-04-01

    Two different surrogate mixtures of anthropogenic and biogenic volatile organic compounds (VOCs) were developed to study secondary organic aerosol (SOA) formation at atmospheric reactivities similar to urban regions with varying biogenic influence levels. Environmental chamber simulations were designed to enable the study of the incremental aerosol formation from select anthropogenic (m‑Xylene, 1,2,4-Trimethylbenzene, and 1-Methylnaphthalene) and biogenic (α-pinene) precursors under the chemical reactivity set by the two different surrogate mixtures. The surrogate reactive organic gas (ROG) mixtures were based on that used to develop the maximum incremental reactivity (MIR) factors for evaluation of O3 forming potential. Multiple incremental aerosol formation experiments were performed in the University of California Riverside (UCR) College of Engineering Center for Environmental Research and Technology (CE-CERT) dual 90m3 environmental chambers. Incremental aerosol yields were determined for each of the VOCs studied and compared to yields found from single precursor studies. Aerosol physical properties of density, volatility, and hygroscopicity were monitored throughout experiments. Bulk elemental chemical composition from high-resolution time of flight aerosol mass spectrometer (HR-ToF-AMS) data will also be presented. Incremental yields and SOA chemical and physical characteristics will be compared with data from previous single VOC studies conducted for these aerosol precursors following traditional VOC/NOx chamber experiments. Evaluation of the incremental effects of VOCs on SOA formation and properties are paramount in evaluating how to best extrapolate environmental chamber observations to the ambient atmosphere and provides useful insights into current SOA formation models. Further, the comparison of incremental SOA from VOCs in varying surrogate urban atmospheres (with and without strong biogenic influence) allows for a unique perspective on the impacts

  4. 78 FR 8050 - Spent Fuel Cask Certificate of Compliance Format and Content

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-02-05

    ... COMMISSION 10 CFR Part 72 Spent Fuel Cask Certificate of Compliance Format and Content AGENCY: Nuclear... that governs the format and content of spent fuel storage cask Certificates of Compliance (CoCs... criteria for the format and content to be included in a spent fuel storage cask Certificate of...

  5. Effects of fracture reactivation and diagenesis on fracture network evolution: Cambrian Eriboll Formation, NW Scotland

    NASA Astrophysics Data System (ADS)

    Hooker, J. N.; Eichhubl, P.; Xu, G.; Ahn, H.; Fall, A.; Hargrove, P.; Laubach, S.; Ukar, E.

    2011-12-01

    The Cambrian Eriboll Formation quartzarenites contain abundant fractures with varying degrees of quartz cement infill. Fractures exist that are entirely sealed; are locally sealed by bridging cements but preserve pore space among bridges; are mostly open but lined with veneers of cement; or are devoid of cement. Fracture propagation in the Eriboll Formation is highly sensitive to the presence of pre-existing fractures. Fracture reactivation occurs in opening mode as individual fractures repeatedly open and are filled or bridged by syn-kinematic cements. As well, reactivation occurs in shear as opening of one fracture orientation coincides with shear displacement along pre-existing fractures of different orientations. The tendency for pre-existing fractures to slip varies in part by the extent of cement infill, yet we observe shear and opening-mode reactivation even among sealed fractures. Paleotemperature analysis of fluid inclusions within fracture cements suggests some fractures now in outcrop formed deep in the subsurface. Fractures within the Eriboll Formation may therefore affect later fracture propagation throughout geologic time. With progressive strain, fault zones develop within fracture networks by a sequence of opening-mode fracture formation, fracture reactivation and linkage, fragmentation, cataclasis, and the formation of slip surfaces. Cataclasite within fault zones is commonly more thoroughly cemented than fractures in the damage zone or outside the fault zone. This variance of cement abundance is likely the result of (1) continued exposure of freshly broken quartz surfaces within cataclasite, promoting quartz precipitation, and (2) possibly more interconnected pathways for mass transfer within the fault zone. Enhanced cementation of cataclasite results in strengthening or diagenetic strain hardening of the evolving fault zone. Further slip is accommodated by shear localization along discrete slip surfaces. With further linkage of fault segments

  6. Stabilization of thylakoid membranes in isoprene-emitting plants reduces formation of reactive oxygen species.

    PubMed

    Velikova, Violeta; Sharkey, Thomas D; Loreto, Francesco

    2012-01-01

    Isoprene is emitted by a significant fraction of the world's vegetation. Isoprene makes leaves more thermotolerant, yet we do not fully understand how. We have recently shown that isoprene stabilizes thylakoid membranes under heat stress. Here we show that heat-stressed, isoprene-emitting transgenic Arabidopsis plants also produce a lower pool of reactive oxygen and reactive nitrogen species, and that this was especially due to a lower accumulation of H2O2 in isoprene emitting plants. It remains difficult to disentangle whether in heat stressed plants isoprene also directly reacts with and quenches reactive oxygen species (ROS), or reduces ROS formation by stabilizing thylakoids. We present considerations that make the latter a more likely mechanism, under our experimental circumstances. PMID:22301981

  7. Reactivity controlled compression ignition drive cycle emissions and fuel economy estimations using vehicle systems simulations - IJER

    DOE PAGESBeta

    Curran, Scott; Gao, Zhiming; Wagner, Robert M

    2015-01-01

    In-cylinder blending of gasoline and diesel to achieve reactivity- controlled compression ignition (RCCI) has been shown to reduce NOX and soot emissions while maintaining or improving brake thermal efficiency as compared with conventional diesel combustion (CDC). The RCCI concept has an advantage over many advanced combustion strategies in that the fuel reactivity can be tailored to the engine speed and load, allowing stable low-temperature combustion to be extended over more of the light-duty drive cycle load range. However, the current range of the experimental RCCI engine map investigated here does not allow for RCCI operation over the entirety of somemore » drive cycles. A multi-mode RCCI strategy is employed where the engine switches from RCCI to CDC when speed and load fall outside of the experimentally determined RCCI range. The potential for RCCI to reduce drive cycle fuel economy and emissions is not clearly understood and is explored here by simulating the fuel economy and emissions for a multi-mode RCCI-enabled vehicle operating over a variety of US drive cycles using experimental engine maps for multi-mode RCCI, CDC, and a 2009 port-fuel injected gasoline engine. Simulations are completed assuming a conventional mid-size passenger vehicle with an automatic transmission. RCCI fuel economy simulation results are compared with the same vehicle powered by a representative 2009 PFI gasoline engine over multiple drive cycles. Engine-out drive cycle emissions are compared to CDC, and observations regarding relative gasoline and diesel tank sizes needed for the various drive cycles are also summarized.« less

  8. Micro-crack formation in direct methanol fuel cell electrodes

    NASA Astrophysics Data System (ADS)

    Li, Qing; Spernjak, Dusan; Zelenay, Piotr; Kim, Yu Seung

    2014-12-01

    This study focuses on the micro-crack formation of Nafion®-based membrane electrode assemblies (MEAs) after extended direct methanol fuel cell (DMFC) operation. All electrodes, both with metal-black and carbon-supported catalysts, contain some micro-cracks initially; the area covered by these cracks increases both in the anode and cathode after 100-hours of DMFC test. X-ray tomography shows an increase in the crack area in both anode and cathode that correlates with methanol feed concentration and methanol crossover. The MEAs with carbon-supported catalysts and thicker membrane are more resistant to the formation of micro-cracks compared to those with metal-black catalysts and thinner membrane, respectively. The impact of the micro-crack formation on cell performance and durability is limited over the 100-hour DMFC operation, with the long-term impact remaining unknown.

  9. The Suitable Geological Formations for Spent Fuel Disposal in Romania

    SciTech Connect

    Marunteanu, C.; Ionita, G.; Durdun, I.

    2007-07-01

    Using the experience in the field of advanced countries and formerly Romanian program data, ANDRAD, the agency responsible for the disposal of radioactive wastes, started the program for spent fuel disposal in deep geological formations with a documentary analysis at the national scale. The potential geological formations properly characterized elsewhere in the world: salt, clay, volcanic tuff, granite and crystalline rocks,. are all present in Romania. Using general or specific selection criteria, we presently consider the following two areas for candidate geological formations: 1. Clay formations in two areas in the western part of Romania: (1) The Pannonian basin Socodor - Zarand, where the clay formation is 3000 m thick, with many bentonitic strata and undisturbed structure, and (2) The Eocene Red Clay on the Somes River, extending 1200 m below the surface. They both need a large investigation program in order to establish and select the required homogeneous, dry and undisturbed zones at a suitable depth. 2. Old platform green schist formations, low metamorphosed, quartz and feldspar rich rocks, in the Central Dobrogea structural unit, not far from Cernavoda NPP (30 km average distance), 3000 m thick and including many homogeneous, fine granular, undisturbed, up to 300 m thick layers. (authors)

  10. An improved alkaline direct formate paper microfluidic fuel cell.

    PubMed

    Galvan, Vicente; Domalaon, Kryls; Tang, Catherine; Sotez, Samantha; Mendez, Alex; Jalali-Heravi, Mehdi; Purohit, Krutarth; Pham, Linda; Haan, John; Gomez, Frank A

    2016-02-01

    Paper-based microfluidic fuel cells (MFCs) are a potential replacement for traditional FCs and batteries due to their low cost, portability, and simplicity to operate. In MFCs, separate solutions of fuel and oxidant migrate through paper due to capillary action and laminar flow and, upon contact with each other and catalyst, produce electricity. In the present work, we describe an improved microfluidic paper-based direct formate FC (DFFC) employing formate and hydrogen peroxide as the anode fuel and cathode oxidant, respectively. The dimensions of the lateral column, current collectors, and cathode were optimized. A maximum power density of 2.53 mW/cm(2) was achieved with a DFFC of surface area 3.0 cm(2) , steel mesh as current collector, 5% carbon to paint mass ratio for cathode electrode and, 30% hydrogen peroxide. The longevity of the MFC's detailed herein is greater than eight hours with continuous flow of streams. In a series configuration, the MFCs generate sufficient energy to power light-emitting diodes and a handheld calculator. PMID:26572774

  11. Endogenous and endobiotic induced reactive oxygen species formation by isolated hepatocytes.

    PubMed

    Siraki, Arno G; Pourahmad, Jalal; Chan, Tom S; Khan, Sumsullah; O'Brien, Peter J

    2002-01-01

    The rat hepatocyte catalyzed oxidation of 2',7'-dichlorofluorescin to form the fluorescent 2,7'-dichlorofluorescein was used to measure endogenous and xenobiotic-induced reactive oxygen species (ROS) formation by intact isolated rat hepatocytes. Various oxidase substrates and inhibitors were then used to identify the intracellular oxidases responsible. Endogenous ROS formation was markedly increased in catalase-inhibited or GSH-depleted hepatocytes, and was inhibited by ROS scavengers or desferoxamine. Endogenous ROS formation was also inhibited by cytochrome P450 inhibitors, but was not affected by oxypurinol, a xanthine oxidase inhibitor, or phenelzine, a monoamine oxidase inhibitor. Mitochondrial respiratory chain inhibitors or hypoxia, on the other hand, markedly increased ROS formation before cytotoxicity ensued. Furthermore, uncouplers of oxidative phosphorylation inhibited endogenous ROS formation. This suggests endogenous ROS formation can largely be attributed to oxygen reduction by reduced mitochondrial electron transport components and reduced cytochrome P450 isozymes. Addition of monoamine oxidase substrates increased antimycin A-resistant respiration and ROS formation before cytotoxicity ensued. Addition of peroxisomal substrates also increased antimycin A-resistant respiration but they were less effective at inducing ROS formation and were not cytotoxic. However, peroxisomal substrates readily induced ROS formation and were cytotoxic towards catalase-inhibited hepatocytes, which suggests that peroxisomal catalase removes endogenous H(2)O(2) formed in the peroxisomes. Hepatocyte catalyzed dichlorofluorescin oxidation induced by oxidase substrates, e.g., benzylamine, was correlated with the cytotoxicity induced in catalase-inhibited hepatocytes. PMID:11755311

  12. Chemical reactivity testing for the National Spent Nuclear Fuel Program. Revision 2

    SciTech Connect

    Koester, L.W.

    2000-02-08

    This quality assurance project plan (QAPjP) summarizes requirements used by Lockheed Martin Energy Systems, Incorporated (LMES) Development Division at Y-12 for conducting chemical reactivity testing of Department of Energy (DOE) owned spent nuclear fuel, sponsored by the National Spent Nuclear Fuel Program (NSNFP). The requirements are based on the NSNFP Statement of work PRO-007 (Statement of Work for Laboratory Determination of Uranium Hydride Oxidation Reaction Kinetics.) This QAPjP will utilize the quality assurance program at Y-12, Y60-101PD, Quality Program Description, and existing implementing procedures for the most part in meeting the NSNFP Statement of Work PRO-007 requirements, exceptions will be noted. The project consists of conducting three separate series of related experiments, ''Passivation of Uranium Hydride Powder With Oxygen and Water'', '''Passivation of Uranium Hydride Powder with Surface Characterization'', and ''Electrochemical Measure of Uranium Hydride Corrosion Rate''.

  13. Formation of reactive oxygen species in rat epithelial cells upon stimulation with fly ash.

    PubMed

    Voelkel, K; Krug, H F; Diabaté, S

    2003-02-01

    Fly ash was used as a model for ambient particulate matter which is under suspicion to cause adverse pulmonary health effects. The fly ash was pre-sized and contained only particles < 20 microm including an ultrafine fraction (< 100 nm) that contributed 31% to the particle number. In our study, we investigated the influence of fly ash on the promotion of early inflammatory reactions like the formation of reactive oxygen species (ROS) in rat lung epithelial cells (RLE-6TN). Furthermore, we determined the formation of nitric oxide (NO). The cells show a clear dose-response relationship concerning the formation of ROS with regard to the mass of particles applied. Lipopolysaccharide (LPS) added as a co-stimulus did not increase the formation of ROS induced by fly ash. Furthermore, in LPS (0.1 microg/ml) and tumour necrosis factor-alpha (TNF-alpha; 1 ng/ml) pre-treated cells no increase in reactive oxygen species comparable to fly ash alone is observable. In presence of the metal chelator, desferrioxamine (DFO), ROS formation can be significantly reduced. Neither fly ash nor LPS induced a significant NO release in RLE-6TN cells. PMID:12682424

  14. Non-destructive assay of spent nuclear fuel using passive neutron Albedo reactivity

    SciTech Connect

    Evans, L G; Schear, M A; Croft, S; Tobin, S J; Swinhoe, M T; Menlove, H O

    2010-01-01

    Passive Neutron Albedo Reactivity (PNAR) is one of fourteen techniques that has been researched and evaluated to form part of a comprehensive and integrated detection system for the non-destructive assay (NDA) of spent nuclear fuel. PNAR implemented with {sup 3}He tubes for neutron detection (PNAR-{sup 3}He) is the measurement of time correlated neutrons from a spent fuel assembly with and without a Cadmium (Cd) layer surrounding the assembly. PNAR utilizes the self-interrogation of the fuel via reflection of neutrons born in the fuel assembly back in to the fuel assembly. The neutrons originate primarily from spontaneous fission events within the fuel itself (Curium-244) but are amplified by multiplication. The presence and removal of the Cd provides two measurement conditions with different neutron energy spectra and therefore different interrogating neutron characteristics. Cd has a high cross-section of absorption for slow neutrons and therefore greatly reduces the low energy (thermal) neutron fluence rate returning. The ratios of the Singles, Doubles and Triples count rates obtained in each case are known as the Cd ratios, which are related to fissile content. A potential safeguards application for which PNAR-{sup 3}He is particularly suited is 'fingerprinting'. Fingerprinting could function as an alternative to plutonium (Pu) mass determination; providing confidence that material was not diverted during transport between sites. PNAR-{sup 3}He has six primary NDA signatures: Singles, Doubles and Triples count rates measured with two energy spectra at both shipping and receiving sites. This is to uniquely identify the fuel assembly, and confirm no changes have taken place during transport. Changes may indicate all attempt to divert material for example. Here, the physics of the PNAR-{sup 3}He concept will be explained, alongside a discussion on the development of a prototypical PNAR-{sup 3}He instrument using simulation. The capabilities and performance of the

  15. Pebble Fuel Handling and Reactivity Control for Salt-Cooled High Temperature Reactors

    SciTech Connect

    Peterson, Per; Greenspan, Ehud

    2015-02-09

    This report documents the work completed on the X-PREX facility under NEUP Project 11- 3172. This project seeks to demonstrate the viability of pebble fuel handling and reactivity control for fluoride salt-cooled high-temperature reactors (FHRs). The research results also improve the understanding of pebble motion in helium-cooled reactors, as well as the general, fundamental understanding of low-velocity granular flows. Successful use of pebble fuels in with salt coolants would bring major benefits for high-temperature reactor technology. Pebble fuels enable on-line refueling and operation with low excess reactivity, and thus simpler reactivity control and improved fuel utilization. If fixed fuel designs are used, the power density of salt- cooled reactors is limited to 10 MW/m3 to obtain adequate duration between refueling, but pebble fuels allow power densities in the range of 20 to 30 MW/m3. This can be compared to the typical modular helium reactor power density of 5 MW/m3. Pebble fuels also permit radial zoning in annular cores and use of thorium or graphite pebble blankets to reduce neutron fluences to outer radial reflectors and increase total power production. Combined with high power conversion efficiency, compact low-pressure primary and containment systems, and unique safety characteristics including very large thermal margins (>500°C) to fuel damage during transients and accidents, salt-cooled pebble fuel cores offer the potential to meet the major goals of the Advanced Reactor Concepts Development program to provide electricity at lower cost than light water reactors with improved safety and system performance.This report presents the facility description, experimental results, and supporting simulation methods of the new X-Ray Pebble Recirculation Experiment (X-PREX), which is now operational and being used to collect data on the behavior of slow dense granular flows relevant to pebble bed reactor core designs. The X

  16. Investigation of the Effect of Fixed Absorbers on the Reactivity of PWR Spent Nuclear Fuel for Burnup Credit

    SciTech Connect

    Wagner, John C.; Sanders, Charlotta E.

    2002-08-15

    The effect of fixed absorbers on the reactivity of pressurized water reactor (PWR) spent nuclear fuel (SNF) in support of burnup-credit criticality safety analyses is examined. A fuel assembly burned in conjunction with fixed absorbers may have a higher reactivity for a given burnup than an assembly that has not used fixed absorbers. As a result, guidance on burnup credit, issued by the U.S. Nuclear Regulatory Commission's Spent Fuel Project Office, recommends restricting the use of burnup credit to assemblies that have not used burnable absorbers. This recommendation eliminates a large portion of the currently discharged SNF from loading in burnup credit casks and thus severely limits the practical usefulness of burnup credit. Therefore, data are needed to support the extension of burnup credit to additional SNF. This research investigates the effect of various fixed absorbers, including integral burnable absorbers, burnable poison rods, control rods, and axial power shaping rods, on the reactivity of PWR SNF. Trends in reactivity with relevant parameters (e.g., initial fuel enrichment, burnup and absorber type, exposure, and design) are established, and anticipated reactivity effects are quantified. Where appropriate, recommendations are offered for addressing the reactivity effects of the fixed absorbers in burnup-credit safety analyses.

  17. The direct formate fuel cell with an alkaline anion exchange membrane

    NASA Astrophysics Data System (ADS)

    Bartrom, Amy M.; Haan, John L.

    2012-09-01

    We demonstrate for the first time an operating Direct Formate Fuel Cell employing formate salts as the anode fuel, air or oxygen as the oxidant, a polymer anion exchange membrane, and metal catalysts at the anode and cathode. Operation of the DFFC at 60 °C using 1 M KOOCH and 2 M KOH as the anode fuel and electrolyte and oxygen gas at the cathode produces 144 mW cm-2 of peak power density, 181 mA cm-2 current density at 0.6 V, and an open circuit voltage of 0.931 V. This performance is competitive with alkaline Direct Liquid Fuel Cells (DLFCs) previously reported in the literature and demonstrates that formate fuel is a legitimate contender with alcohol fuels for alkaline DLFCs. A survey of the literature shows that a formate-oxygen fuel cell has a high theoretical potential, and the safe, renewable formate fuel does not poison the anode catalyst.

  18. In situ formation of magnetite reactive barriers in soil for waste stabilization

    DOEpatents

    Moore, Robert C.

    2003-01-01

    Reactive barriers containing magnetite and methods for making magnetite reactive barriers in situ in soil for sequestering soil contaminants including actinides and heavy metals, organic materials, iodine and technetium are disclosed. According to one embodiment, a two-step reagent introduction into soil takes place. In the first step, free oxygen is removed from the soil by separately injecting into the soil aqueous solutions of iron (II) salt, for example FeCl.sub.2, and base, for example NaOH or NH.sub.3 in about a 1:1 volume ratio. Then, in the second step, similar reagents are injected a second time (however, according to about a 1:2 volume ratio, iron to salt) to form magnetite. The magnetite formation is facilitated, in part, due to slow intrusion of oxygen into the soil from the surface. The invention techniques are suited to injection of reagents into soil in proximity to a contamination plume or source allowing in situ formation of the reactive barrier at the location of waste or hazardous material. Mixing of reagents to form. precipitate is mediated and enhanced through movement of reagents in soil as a result of phenomena including capillary action, movement of groundwater, soil washing and reagent injection pressure.

  19. Formation, Migration, and Reactivity of Au CO Complexes on Gold Surfaces

    DOE PAGESBeta

    Wang, Jun; McEntee, Monica; Tang, Wenjie; Neurock, Matthew; Baddorf, Arthur P.; Maksymovych, Petro; Yates, Jr, John T.

    2016-01-12

    Here, we report experimental as well as theoretical evidence that suggests Au CO complex formation upon the exposure of CO to active sites (step edges and threading dislocations) on a Au(111) surface. Room-temperature scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy, transmission infrared spectroscopy, and density functional theory calculations point to Au CO complex formation and migration. Room-temperature STM of the Au(111) surface at CO pressures in the range from 10^ 8 to 10^ 4 Torr (dosage up to 10^6 langmuir) indicates Au atom extraction from dislocation sites of the herringbone reconstruction, mobile Au CO complex formation and diffusion, and Aumore » adatom cluster formation on both elbows and step edges on the Au surface. The formation and mobility of the Au CO complex result from the reduced Au Au bonding at elbows and step edges leading to stronger Au CO bonding and to the formation of a more positively charged CO (CO +) on Au. These studies indicate that the mobile Au CO complex is involved in the Au nanoparticle formation and reactivity, and that the positive charge on CO increases due to the stronger adsorption of CO at Au sites with lower coordination numbers.« less

  20. Formation, Migration, and Reactivity of Au-CO Complexes on Gold Surfaces.

    PubMed

    Wang, Jun; McEntee, Monica; Tang, Wenjie; Neurock, Matthew; Baddorf, Arthur P; Maksymovych, Petro; Yates, John T

    2016-02-10

    We report experimental as well as theoretical evidence that suggests Au-CO complex formation upon the exposure of CO to active sites (step edges and threading dislocations) on a Au(111) surface. Room-temperature scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy, transmission infrared spectroscopy, and density functional theory calculations point to Au-CO complex formation and migration. Room-temperature STM of the Au(111) surface at CO pressures in the range from 10(-8) to 10(-4) Torr (dosage up to 10(6) langmuir) indicates Au atom extraction from dislocation sites of the herringbone reconstruction, mobile Au-CO complex formation and diffusion, and Au adatom cluster formation on both elbows and step edges on the Au surface. The formation and mobility of the Au-CO complex result from the reduced Au-Au bonding at elbows and step edges leading to stronger Au-CO bonding and to the formation of a more positively charged CO (CO(δ+)) on Au. Our studies indicate that the mobile Au-CO complex is involved in the Au nanoparticle formation and reactivity, and that the positive charge on CO increases due to the stronger adsorption of CO at Au sites with lower coordination numbers. PMID:26754257

  1. 40 CFR Appendix Viii to Part 600 - Fuel Economy Label Formats

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 29 2010-07-01 2010-07-01 false Fuel Economy Label Formats VIII... POLICY FUEL ECONOMY AND CARBON-RELATED EXHAUST EMISSIONS OF MOTOR VEHICLES Pt. 600, App. VIII Appendix VIII to Part 600—Fuel Economy Label Formats EC01MY92.117 EC01MY92.118 EC01MY92.119...

  2. Crystal structure induced residue formation on 4H-SiC by reactive ion etching

    NASA Astrophysics Data System (ADS)

    Liu, Yi-hong; Sun, Yu-jun; Zhao, Gao-jie; Liao, Li-ming; Wang, Tao; Chen, Zhi-zhan

    2016-06-01

    The (000 1 ¯) C face of 4H-SiC wafer was etched by reactive ion etching in SF6/O2 plasma. The effect of etching parameters, such as work pressure, SF6:O2 ratio and etching time, on the residue formation were systematically investigated. The residue morphologies were observed by scanning electron microscopy and atomic force microscopy, respectively. The residues have spike shape and their facets are defined as { 1 1 ¯ 0 2 ¯ } crystal planes. They are formed at beginning of the etching and no new spikes are generated as prolonging etching time. Both work pressure and SF6:O2 ratio play significant role in the spike formation. The residues can be eliminated completely by increasing the SF6:O2 ratio and work pressure. On the basis of experimental results and of 4H-SiC crystal structure, the spike formation model is proposed.

  3. 40 CFR 600.302-08 - Fuel economy label format requirements.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 31 2013-07-01 2013-07-01 false Fuel economy label format requirements. 600.302-08 Section 600.302-08 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) ENERGY POLICY FUEL ECONOMY AND GREENHOUSE GAS EXHAUST EMISSIONS OF MOTOR VEHICLES Fuel Economy Labeling § 600.302-08 Fuel economy label...

  4. 40 CFR 600.302-08 - Fuel economy label format requirements.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 31 2012-07-01 2012-07-01 false Fuel economy label format requirements. 600.302-08 Section 600.302-08 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) ENERGY POLICY FUEL ECONOMY AND GREENHOUSE GAS EXHAUST EMISSIONS OF MOTOR VEHICLES Fuel Economy Labeling § 600.302-08 Fuel economy label...

  5. Extracellular ultrathin fibers sensitive to intracellular reactive oxygen species: Formation of intercellular membrane bridges

    SciTech Connect

    Jung, Se-Hui; Park, Jin-Young; Joo, Jung-Hoon; Kim, Young-Myeong; Ha, Kwon-Soo

    2011-07-15

    Membrane bridges are key cellular structures involved in intercellular communication; however, dynamics for their formation are not well understood. We demonstrated the formation and regulation of novel extracellular ultrathin fibers in NIH3T3 cells using confocal and atomic force microscopy. At adjacent regions of neighboring cells, phorbol 12-myristate 13-acetate (PMA) and glucose oxidase induced ultrathin fiber formation, which was prevented by Trolox, a reactive oxygen species (ROS) scavenger. The height of ROS-sensitive ultrathin fibers ranged from 2 to 4 nm. PMA-induced formation of ultrathin fibers was inhibited by cytochalasin D, but not by Taxol or colchicine, indicating that ultrathin fibers mainly comprise microfilaments. PMA-induced ultrathin fibers underwent dynamic structural changes, resulting in formation of intercellular membrane bridges. Thus, these fibers are formed by a mechanism(s) involving ROS and involved in formation of intercellular membrane bridges. Furthermore, ultrastructural imaging of ultrathin fibers may contribute to understanding the diverse mechanisms of cell-to-cell communication and the intercellular transfer of biomolecules, including proteins and cell organelles.

  6. The Effects of Fuel Stratification and Heat Release Rate Shaping in Reactivity Controlled Compression Ignition (RCCI) Combustion

    NASA Astrophysics Data System (ADS)

    DelVescovo, Dan A.

    Low temperature combustion strategies have demonstrated high thermal efficiency with low emissions of pollutants, including oxides of nitrogen and particulate matter. One such combustion strategy, called Reactivity Controlled Compression Ignition (RCCI), which involves the port injection of a low reactivity fuel such as gasoline, ethanol, or natural gas, and a direct injection of a high reactivity fuel, such as diesel, has demonstrated excellent control over the heat release event due to the introduction of in-cylinder stratification of equivalence ratio and reactivity. The RCCI strategy is inherently fuel flexible, however the direct injection strategy needs to be tailored to the combination of premixed and direct injected fuels. Experimental results demonstrate that, when comparing different premixed fuels, matching combustion phasing with premixed mass percentage or SOI timing is not sufficient to retain baseline efficiency and emissions results. If the bulk characteristics of the heat release event can be matched, however, then the efficiency and emissions can be maintained. A 0-D methodology for predicting the required fuel stratification for a desired heat release for kinetically-controlled stratified-charge combustion strategies is proposed and validated with 3-D reacting and non-reacting CFD simulations performed with KIVA3Vr2 in this work. Various heat release rate shapes, phasing, duration, and premixed and DI fuel chemistries are explored using this analysis. This methodology provides a means by which the combustion process of a stratified-charge, kinetically-controlled combustion strategy could be optimized for any fuel combination, assuming that the fuel chemistry is well characterized.

  7. Winter ozone formation and VOC incremental reactivities in the Upper Green River Basin of Wyoming

    NASA Astrophysics Data System (ADS)

    Carter, William P. L.; Seinfeld, John H.

    2012-04-01

    The Upper Green River Basin (UGRB) in Wyoming experiences ozone episodes in the winter when the air is relatively stagnant and the ground is covered by snow. A modeling study was carried out to assess relative contributions of oxides of nitrogen (NOx) and individual volatile organic compounds (VOCs), and nitrous acid (HONO) in winter ozone formation episodes in this region. The conditions of two ozone episodes, one in February 2008 and one in March 2011, were represented using a simplified box model with all pollutants present initially, but with the detailed SAPRC-07 chemical mechanism adapted for the temperature and radiation conditions arising from the high surface albedo of the snow that was present. Sensitivity calculations were conducted to assess effects of varying HONO inputs, ambient VOC speciation, and changing treatments of temperature and lighting conditions. The locations modeled were found to be quite different in VOC speciation and sensitivities to VOC and NOx emissions, with one site modeled for the 2008 episode being highly NOx-sensitive and insensitive to VOCs and HONO, and the other 2008 site and both 2011 sites being very sensitive to changes in VOC and HONO inputs. Incremental reactivity scales calculated for VOC-sensitive conditions in the UGRB predict far lower relative contributions of alkanes to ozone formation than in the traditional urban-based MIR scale and that the major contributors to ozone formation were the alkenes and the aromatics, despite their relatively small mass contributions. The reactivity scales are affected by the variable ambient VOC speciation and uncertainties in ambient HONO levels. These box model calculations are useful for indicating general sensitivities and reactivity characteristics of these winter UGRB episodes, but fully three-dimensional models will be required to assess ozone abatement strategies in the UGRB.

  8. Analyzing the impact of reactive transport on the repository performance of TRISO fuel

    NASA Astrophysics Data System (ADS)

    Schmidt, Gregory

    graphite surrounding the spent HTGR fuel will impact the release of aqueous uranium from the TRISO fuel. In order to answer this question, the sorption and partitioning behavior of uranium to graphite under a variety of conditions was investigated. Key systematic variables that were analyzed include solution pH, dissolved carbonate concentration, uranium metal concentration and ionic strength. The kinetics and desorption characteristics of uranium/graphite partitioning were studied as well. The graphite used in these experiments was also characterized by a variety of techniques and conclusions are drawn about the relevant surface chemistry of graphite. This data was then used to generate a model for the reactive transport of uranium in a graphite matrix. This model was implemented with the software code CXTFIT and validated through the use of column studies mirroring the predicted system.

  9. Iron hydroxy carbonate formation in zerovalent iron permeable reactive barriers: Characterization and evaluation of phase stability

    SciTech Connect

    Wilkin, Richard T.; Lee, T.R.

    2010-10-22

    Predicting the long-term potential of permeable reactive barriers for treating contaminated groundwater relies on understanding the endpoints of biogeochemical reactions between influent groundwater and the reactive medium. Iron hydroxy carbonate (chukanovite) is frequently observed as a secondary mineral precipitate in granular iron PRBs. Mineralogical characterization was carried out using X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and X-ray absorption spectroscopy on materials collected from three field-based PRBs in the US (East Helena, MT; Elizabeth City, NC; Denver Federal Center, CO). These PRBs were installed to treat a range of contaminants, including chlorinated organics, hexavalent chromium, and arsenic. Results obtained indicate that chukanovite is a prevalent secondary precipitate in the PRBs. Laboratory experiments on high-purity chukanovite separates were carried out to constrain the room-temperature solubility for this mineral. An estimated Gibbs energy of formation ({Delta}{sub f}G{sup o}) for chukanovite is - 1174.4 {+-} 6 kJ/mol. A mineral stability diagram is consistent with observations from the field. Water chemistry from the three reactive barriers falls inside the predicted stability field for chukanovite, at inorganic carbon concentrations intermediate to the stability fields of siderite and ferrous hydroxide. These new data will aid in developing better predictive models of mineral accumulation in zerovalent iron PRBs.

  10. Iron hydroxy carbonate formation in zerovalent iron permeable reactive barriers: characterization and evaluation of phase stability.

    PubMed

    Lee, Tony R; Wilkin, Richard T

    2010-07-30

    Predicting the long-term potential of permeable reactive barriers for treating contaminated groundwater relies on understanding the endpoints of biogeochemical reactions between influent groundwater and the reactive medium. Iron hydroxy carbonate (chukanovite) is frequently observed as a secondary mineral precipitate in granular iron PRBs. Mineralogical characterization was carried out using X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and X-ray absorption spectroscopy on materials collected from three field-based PRBs in the US (East Helena, MT; Elizabeth City, NC; Denver Federal Center, CO). These PRBs were installed to treat a range of contaminants, including chlorinated organics, hexavalent chromium, and arsenic. Results obtained indicate that chukanovite is a prevalent secondary precipitate in the PRBs. Laboratory experiments on high-purity chukanovite separates were carried out to constrain the room-temperature solubility for this mineral. An estimated Gibbs energy of formation (Delta(f)G degrees) for chukanovite is -1174.4 +/- 6 kJ/mol. A mineral stability diagram is consistent with observations from the field. Water chemistry from the three reactive barriers falls inside the predicted stability field for chukanovite, at inorganic carbon concentrations intermediate to the stability fields of siderite and ferrous hydroxide. These new data will aid in developing better predictive models of mineral accumulation in zerovalent iron PRBs. PMID:20554346

  11. Tks5-dependent, Nox-mediated Generation of Reactive Oxygen Species is Necessary for Invadopodia Formation*

    PubMed Central

    Diaz, Begoña; Shani, Gidon; Pass, Ian; Anderson, Diana; Quintavalle, Manuela; Courtneidge, Sara A.

    2009-01-01

    Invadopodia are actin-rich membrane protrusions of cancer cells which facilitate pericellular proteolysis and invasive behavior. We show here that reactive oxygen species (ROS) generated by the NADPH oxidase (Nox) system are necessary for invadopodia formation and function. The invadopodia protein Tks5 is structurally related to p47phox, a Nox component in phagocytic cells. Knockdown of Tks5 reduces total ROS levels in cancer cells. Furthermore, Tks5 and p22phox can associate with each other, suggesting that Tks5 is part of the Nox complex. Tyrosine phosphorylation of Tks5 and Tks4, but not other Src substrates, is reduced by Nox inhibition. We propose that Tks5 facilitates the production of ROS necessary for invadopodia formation, and that in turn ROS modulates Tks5 tyrosine phosphorylation in a positive feedback loop. PMID:19755709

  12. Formation of metal nanoparticles by short-distance sputter deposition in a reactive ion etching chamber

    SciTech Connect

    Nie Min; Meng, Dennis Desheng; Sun Kai

    2009-09-01

    A new method is reported to form metal nanoparticles by sputter deposition inside a reactive ion etching chamber with a very short target-substrate distance. The distribution and morphology of nanoparticles are found to be affected by the distance, the ion concentration, and the sputtering time. Densely distributed nanoparticles of various compositions were fabricated on the substrates that were kept at a distance of 130 mum or smaller from the target. When the distance was increased to 510 mum, island structures were formed, indicating the tendency to form continuous thin film with longer distance. The observed trend for nanoparticle formation is opposite to the previously reported mechanism for the formation of nanoparticles by sputtering. A new mechanism based on the seeding effect of the substrate is proposed to interpret the experimental results.

  13. Controlled formation of anatase and rutile TiO2 thin films by reactive magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Rafieian, Damon; Ogieglo, Wojciech; Savenije, Tom; Lammertink, Rob G. H.

    2015-09-01

    We discuss the formation of TiO2 thin films via DC reactive magnetron sputtering. The oxygen concentration during sputtering proved to be a crucial parameter with respect to the final film structure and properties. The initial deposition provided amorphous films that crystallise upon annealing to anatase or rutile, depending on the initial sputtering conditions. Substoichiometric films (TiOx<2), obtained by sputtering at relatively low oxygen concentration, formed rutile upon annealing in air, whereas stoichiometric films formed anatase. This route therefore presents a formation route for rutile films via lower (<500 °C) temperature pathways. The dynamics of the annealing process were followed by in situ ellipsometry, showing the optical properties transformation. The final crystal structures were identified by XRD. The anatase film obtained by this deposition method displayed high carriers mobility as measured by time-resolved microwave conductance. This also confirms the high photocatalytic activity of the anatase films.

  14. Importance of thermal reactivity for hexamethylenetetramine formation from simulated interstellar ices

    NASA Astrophysics Data System (ADS)

    Vinogradoff, V.; Fray, N.; Duvernay, F.; Briani, G.; Danger, G.; Cottin, H.; Theulé, P.; Chiavassa, T.

    2013-03-01

    Context. Complex organic molecules are observed in a broad variety of astrophysical objects, but little is known about their formation mechanism. Laboratory simulations on interstellar ice analogues are therefore crucial for understanding the origin of these complex organic molecules. In this context, we focus on the thermal reactivity for the formation of the organic residue obtained after photolysis at 25 K of the interstellar ice analogue (H2O:CH3OH:NH3) warmed to 300 K. Aims: We determine the formation mechanism of one major product detected in the organic residue: hexamethylenetetramine (HMT). We compare the warming of the photolysed interstellar ice analogue with the warming of the two non-photolysed specific ice mixtures H2CO:NH3:HCOOH and CH2NH:HCOOH, which are used as references. Using both general and specific approaches, we show the precise role of the UV photons and the thermal processing in the HMT formation. Methods: We used Fourier transform infrared spectroscopy (FTIR) to monitor the chemical changes induced by the heating of the photolysed ice analogue and characterize some important species that will subsequently evolve in the formation of HMT in the residue. Results: We show that the thermal processes play a key role in the HMT formation in photolysed ice analogues heated at 300 K. We identify the stable intermediates in the HMT formation that are formed during the warming: the aminomethanol (NH2CH2OH) and the protonated ion trimethyletriamine (TMTH+, C3H10N3+). We also identify for the first time a new product in the organic residue, the polymethylenimine PMI (-(CH2 -NH)n). Results from this study will be interesting for the analysis of the forthcoming Rosetta mission.

  15. Rapid detection of defects in fuel-cell electrodes using infrared reactive-flow-through technique

    NASA Astrophysics Data System (ADS)

    Das, Prodip K.; Weber, Adam Z.; Bender, Guido; Manak, Austin; Bittinat, Daniel; Herring, Andrew M.; Ulsh, Michael

    2014-09-01

    As fuel cells become more prominent, new manufacturing and production methods will need to be developed to deal efficiently and effectively with increased demand. One necessary component of this industrial growth is the accurate measurement of the variability in the manufacturing process. In this study, we present a diagnostic system that combines infrared thermography with a reactive-flow-through technique to detect catalyst-loading defects in fuel-cell gas-diffusion electrodes accurately with high spatial and temporal resolutions. Experimental results are compared with model predictions of thermal response with good agreement. Data analysis, operating-condition impacts, and detection limits are explored using both experiments and simulation. Overall, the results demonstrate the potential of this technique to measure defects on the millimeter length scale with temporal resolutions appropriate for use on a web-line. Thus we present the first development stage of a next-generation non-destructive diagnostic tool, which may be amenable to eventual use on roll-to-roll manufacturing lines.

  16. Wax D of Mycobacterium tuberculosis induced osteomyelitis accompanied by reactive bone formation in Buffalo rats.

    PubMed

    Kawabata, Y; Semba, I; Hirayama, Y; Koga, T; Nagao, S; Takada, H

    1998-12-01

    A suspension of heat-killed Mycobacterium tuberculosis in liquid paraffin has been reported to induce foot swelling accompanied by new bone formation in Buffalo (BUF) rats, which are low responders to the induction of adjuvant arthritis. In the present study, we found that wax D, a mycobacterial cell wall peptidoglycan fragment-arabinogalactan-mycolic acid complex, was an effective component of this bacterium for the induction of osteomyelitis accompanied by reactive bone formation in BUF rats. Chronic inflammation was produced in BUF rats by a single subcutaneous injection of wax D suspended in liquid paraffin. Other Mycobacterium species and Gordona bronchialis were also capable of inducing this reaction. Other bacterial cells including the acid-fast bacteria Nocardia and Rhodococcus, purified cell walls and peptidoglycans from Lactobacillus plantarum, wax C, cord factor, arabinogalactan and mycolic acid prepared from M. tuberculosis were inactive in this respect. In addition, when wax D was administered as a water-in-oil emulsion (Freund's type adjuvant), bone formation scarcely occurred in BUF rats. In Fisher (F344) and Wistar rats, both of which are responder strains to adjuvant arthritis, wax D in liquid paraffin did not induce bone formation. PMID:9879920

  17. Performance of Transuranic-Loaded Fully Ceramic Micro-Encapsulated Fuel in LWRs Final Report, Including Void Reactivity Evaluation

    SciTech Connect

    Michael A. Pope; R. Sonat Sen; Brian Boer; Abderrafi M. Ougouag; Gilles Youinou

    2011-09-01

    The current focus of the Deep Burn Project is on once-through burning of transuranics (TRU) in light-water reactors (LWRs). The fuel form is called Fully-Ceramic Micro-encapsulated (FCM) fuel, a concept that borrows the tri-isotropic (TRISO) fuel particle design from high-temperature reactor technology. In the Deep Burn LWR (DB-LWR) concept, these fuel particles are pressed into compacts using SiC matrix material and loaded into fuel pins for use in conventional LWRs. The TRU loading comes from the spent fuel of a conventional LWR after 5 years of cooling. Unit cell and assembly calculations have been performed using the DRAGON-4 code to assess the physics attributes of TRU-only FCM fuel in an LWR lattice. Depletion calculations assuming an infinite lattice condition were performed with calculations of various reactivity coefficients performed at each step. Unit cells and assemblies containing typical UO2 and mixed oxide (MOX) fuel were analyzed in the same way to provide a baseline against which to compare the TRU-only FCM fuel. Then, assembly calculations were performed evaluating the performance of heterogeneous arrangements of TRU-only FCM fuel pins along with UO2 pins.

  18. 40 CFR 600.307-95 - Fuel economy label format requirements.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 30 2011-07-01 2011-07-01 false Fuel economy label format requirements. 600.307-95 Section 600.307-95 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) ENERGY POLICY FUEL ECONOMY AND CARBON-RELATED EXHAUST EMISSIONS OF MOTOR VEHICLES Fuel Economy Regulations for 1977 and Later Model Year...

  19. 40 CFR 600.307-86 - Fuel economy label format requirements.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 30 2011-07-01 2011-07-01 false Fuel economy label format requirements. 600.307-86 Section 600.307-86 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) ENERGY POLICY FUEL ECONOMY AND CARBON-RELATED EXHAUST EMISSIONS OF MOTOR VEHICLES Fuel Economy Regulations for 1977 and Later Model Year...

  20. 40 CFR 600.307-08 - Fuel economy label format requirements.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 29 2010-07-01 2010-07-01 false Fuel economy label format requirements. 600.307-08 Section 600.307-08 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) ENERGY POLICY FUEL ECONOMY AND CARBON-RELATED EXHAUST EMISSIONS OF MOTOR VEHICLES Fuel Economy Regulations for 1977 and Later Model Year...

  1. Effect of Fuel Variables on Carbon Formation in Turbojet-Engine Combustors

    NASA Technical Reports Server (NTRS)

    Jonash, Edmund R; Wear, Jerrold D; Cook, William P

    1958-01-01

    Report presents the results of an investigation of the effects of fuel properties and of a number of fuel additives on combustion-chamber carbon deposition and exhaust-gas smoke formation in a single tubular turbojet-engine combustor. Limited tests were conducted with a number of the fuels in several full-scale turbojet engines to verify single-combustor data.

  2. Environmental implications of iron fuel borne catalysts and their effects on diesel particulate formation and composition

    EPA Science Inventory

    Metal fuel borne catalysts can be used with diesel fuels to effectively reduce engine out particle mass emissions. Mixed with the fuel, the metals become incorporated as nanometer-scale occlusions with soot during its formation and are available to promote in-cylinder soot oxida...

  3. Effect of petrochemical industrial emissions of reactive alkenes and NOx on tropospheric ozone formation in Houston, Texas

    NASA Astrophysics Data System (ADS)

    Ryerson, T. B.; Trainer, M.; Angevine, W. M.; Brock, C. A.; Dissly, R. W.; Fehsenfeld, F. C.; Frost, G. J.; Goldan, P. D.; Holloway, J. S.; Hübler, G.; Jakoubek, R. O.; Kuster, W. C.; Neuman, J. A.; Nicks, D. K.; Parrish, D. D.; Roberts, J. M.; Sueper, D. T.; Atlas, E. L.; Donnelly, S. G.; Flocke, F.; Fried, A.; Potter, W. T.; Schauffler, S.; Stroud, V.; Weinheimer, A. J.; Wert, B. P.; Wiedinmyer, C.; Alvarez, R. J.; Banta, R. M.; Darby, L. S.; Senff, C. J.

    2003-04-01

    Petrochemical industrial facilities can emit large amounts of highly reactive hydrocarbons and NOx to the atmosphere; in the summertime, such colocated emissions are shown to consistently result in rapid and efficient ozone (O3) formation downwind. Airborne measurements show initial hydrocarbon reactivity in petrochemical source plumes in the Houston, TX, metropolitan area is primarily due to routine emissions of the alkenes propene and ethene. Reported emissions of these highly reactive compounds are substantially lower than emissions inferred from measurements in the plumes from these sources. Net O3 formation rates and yields per NOx molecule oxidized in these petrochemical industrial source plumes are substantially higher than rates and yields observed in urban or rural power plant plumes. These observations suggest that reductions in reactive alkene emissions from petrochemical industrial sources are required to effectively address the most extreme O3 exceedences in the Houston metropolitan area.

  4. 76 FR 65544 - Standard Format and Content of License Applications for Mixed Oxide Fuel Fabrication Facilities

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-10-21

    ... issuance of the guide (74 FR 36780). The comment period closed on September 21, 2009. The staff's responses... COMMISSION Standard Format and Content of License Applications for Mixed Oxide Fuel Fabrication Facilities... Format and Content of License Applications for Mixed Oxide Fuel Fabrication Facilities.'' This...

  5. 40 CFR 600.307-95 - Fuel economy label format requirements.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 29 2010-07-01 2010-07-01 false Fuel economy label format requirements... Regulations for 1977 and Later Model Year Automobiles-Labeling § 600.307-95 Fuel economy label format...) Printed in a color which contrasts with the paper color. (iii) The label shall have a contrasting...

  6. Formation rates, stability and reactivity of sulfuric acid - amine clusters predicted by computational chemistry

    NASA Astrophysics Data System (ADS)

    Kurtén, Theo; Ortega, Ismael; Kupiainen, Oona; Olenius, Tinja; Loukonen, Ville; Reiman, Heidi; McGrath, Matthew; Vehkamäki, Hanna

    2013-04-01

    Despite the importance of atmospheric particle formation for both climate and air quality, both experiments and non-empirical models using e.g. sulfuric acid, ammonia and water as condensing vapors have so far been unable to reproduce atmospheric observations using realistic trace gas concentrations. Recent experimental and theoretical evidence has shown that this mystery is likely resolved by amines. Combining first-principles evaporation rates for sulfuric acid - dimethylamine clusters with cluster kinetic modeling, we show that even sub-ppt concentrations of amines, together with atmospherically realistic concentrations of sulfuric acid, result in formation rates close to those observed in the atmosphere. Our simulated cluster formation rates are also close to, though somewhat larger than, those measured at the CLOUD experiment in CERN for both sulfuric acid - ammonia and sulfuric acid - dimethylamine systems. A sensitivity analysis indicates that the remaining discrepancy for the sulfuric acid - amine particle formation rates is likely caused by steric hindrances to cluster formation (due to alkyl groups of the amine molecules) rather than by significant errors in the evaporation rates. First-principles molecular dynamic and reaction kinetic modeling shed further light on the microscopic physics and chemistry of sulfuric acid - amine clusters. For example, while the number and type of hydrogen bonds in the clusters typically reach their equilibrium values on a picosecond timescale, and the overall bonding patterns predicted by traditional "static" quantum chemical calculations seem to be stable, the individual atoms participating in the hydrogen bonds continuously change at atmospherically realistic temperatures. From a chemical reactivity perspective, we have also discovered a surprising phenomenon: clustering with sulfuric acid molecules slightly increases the activation energy required for the abstraction of alkyl hydrogens from amine molecules. This implies

  7. Glucocorticoids: Dose-related effects on osteoclast formation and function via reactive oxygen species and autophagy.

    PubMed

    Shi, Jun; Wang, Long; Zhang, Hongyang; Jie, Qiang; Li, Xiaojie; Shi, Qiyue; Huang, Qiang; Gao, Bo; Han, Yuehu; Guo, Kai; Liu, Jian; Yang, Liu; Luo, Zhuojing

    2015-10-01

    Whether glucocorticoids directly enhance or interrupt osteoclastogenesis is still a controversial subject. In this study, we ascertained the dose-dependent positive effects of glucocorticoids on osteoclastogenesis in vivo and in vitro as well as investigated the mechanism in vitro. As the dose of glucocorticoids increased, osteoclastogenesis was stimulated at 0.1 μM, a peak was achieved at 1 μM and a corresponding decrease occurred at 10 μM. Reactive oxygen species (ROS), which play a crucial role in osteoclastogenesis, and autophagy flux activity, a cellular recycling process, were consistently up-regulated along with the dose-dependent effects of the glucocorticoids on osteoclast formation and function. N-acetyl-cysteine (NAC), a ROS scavenger, abrogated the effects of the glucocorticoids on autophagy and osteoclastogenesis. Moreover, 3-methyladenine (3-MA), an autophagy inhibitor, interrupted osteoclastogenesis stimulation by the glucocorticoids. These results implied that with glucocorticoid administration, ROS and autophagy, as a downstream factor of ROS, played vital roles in osteoclast formation and function. 3-MA administration did not enhance ROS accumulation, so that autophagy had no effect on ROS induced by glucocorticoids. Our investigation demonstrated that glucocorticoids had dose-dependent positive effects on osteoclast formation and function via ROS and autophagy. These results provide support for ROS and autophagy as therapeutic targets in glucocorticoid-related bone loss diseases such as glucocorticoid-induced osteoporosis. PMID:26115910

  8. Negative oxygen ion formation in reactive magnetron sputtering processes for transparent conductive oxides

    SciTech Connect

    Welzel, Thomas; Ellmer, Klaus

    2012-11-15

    Reactive d.c. magnetron sputtering in Ar/O{sub 2} gas mixtures has been investigated with energy-resolved mass spectrometry. Different metal targets (Mg, Ti, Zn, In, InSn, and Sn), which are of importance for transparent conductive oxide thin film deposition, have been used to study the formation of negative ions, mainly high-energetic O{sup -}, which are supposed to induce radiation damage in thin films. Besides their energy distribution, the ions have been particularly investigated with respect to their intensity in comparison of the different target materials. To realize the comparability, various calibration factors had to be introduced. After their application, major differences in the negative ion production have been observed for the target materials. The intensity, especially of O{sup -}, differs by about two orders of magnitude. It is shown that this difference results almost exclusively from ions that gain their energy in the target sheath. Those may gain additional energy from the sputtering process or reflection at the target. Low-energetic negative ions are, however, less affected by changes of the target material. The results concerning O{sup -} formation are discussed in term of the sputtering rate from the target and are compared to models for negative ion formation.

  9. Photo-Reactive Nanogel as a Means to Tune Properties during Polymer Network Formation

    PubMed Central

    Liu, JianCheng; Rad, Ima Y.; Sun, Fang; Stansbury, Jeffrey W.

    2013-01-01

    Photo-reactive nanogels with an integrated photoinitiator-based functionality were synthesized via a Reversible Addition-Fragmentation Chain Transfer (RAFT) process. Without additional free initiators, this nanogel is capable of radical generation and initiating polymerization of a secondary monomer (i.e. dimethacrylate) that infiltrates and disperses the nanogel particles. Due to the presence of RAFT functionality and the fact that all initiating sites are initially located within the nanogel structure, gelation can be delayed by sequencing the polymerization from the nanogel to the bulk matrix. During polymerization of a nanogel-filled resin system, a progressive delay of gelation conversion from about 2 % for conventional chain growth polymerization to 18 % for the same monomer containing 20 wt% nanogel additive was achieved. A significant delay of stress development was also observed with much lower final stress achieved with the nanogel-modified systems due to the change of network formation mechanics. Compared with the nanogel-free dimethacrylate control, which contained uniformly distributed free initiator, the flexural modulus and mechanical strength results were maintained for the photopolymers with nanogel contents greater than 10 wt%. There appears to be a critical interparticle spacing of the photo-reactive nanogel that provides effective photopolymerization while providing delayed gelation and substantial stress reduction. PMID:24348753

  10. Conclusive evidence of abrupt coagulation inside the void during cyclic nanoparticle formation in reactive plasma

    NASA Astrophysics Data System (ADS)

    van de Wetering, F. M. J. H.; Nijdam, S.; Beckers, J.

    2016-07-01

    In this letter, we present scanning electron microscopy (SEM) results that confirm in a direct way our earlier explanation of an abrupt coagulation event as the cause for the void hiccup. In a recent paper, we reported on the fast and interrupted expansion of voids in a reactive dusty argon-acetylene plasma. The voids appeared one after the other, each showing a peculiar, though reproducible, behavior of successive periods of fast expansion, abrupt contraction, and continued expansion. The abrupt contraction was termed "hiccup" and was related to collective coagulation of a new generation of nanoparticles growing in the void using relatively indirect methods: electron density measurements and optical emission spectroscopy. In this letter, we present conclusive evidence using SEM of particles collected at different moments in time spanning several growth cycles, which enables us to follow the nanoparticle formation process in great detail.

  11. Divergent reactivity of homologue ortho-allenylbenzaldehydes controlled by the tether length: chromone versus chromene formation.

    PubMed

    Alcaide, Benito; Almendros, Pedro; Fernández, Israel; Martínez del Campo, Teresa; Naranjo, Teresa

    2015-01-19

    The divergent behavior of two homologue allenals, namely, 2-(buta-2,3-dienyloxy)- and 2-(propa-1,2-dienyloxy)benzaldehydes, as cyclization substrates is described. 2-(Buta-2,3-dienyloxy)benzaldehydes suffers a formal allenic carbocyclization reaction to afford chromenes, whereas 2-(propa-1,2-dienyloxy)benzaldehydes react to yield chromones. The formation of chromenes is strictly a formal hydroarylation process divided into two parts, namely, allenic Claisen-type rearrangement and oxycyclization. An unknown N-heterocyclic carbene (NHC)-catalyzed allenic hydroacylation reaction must be invoked to account for the preparation of chromones. ortho-Allenylbenzaldehydes bearing either electron-donating substituents or electron-withdrawing substituents worked well to afford both the hydroarylation and hydroacylation products. This unexpected difference in reactivity can be rationalized by means of density functional theory calculations. PMID:25418081

  12. Formation of thin walled ceramic solid oxide fuel cells

    DOEpatents

    Claar, Terry D.; Busch, Donald E.; Picciolo, John J.

    1989-01-01

    To reduce thermal stress and improve bonding in a high temperature monolithic solid oxide fuel cell (SOFC), intermediate layers are provided between the SOFC's electrodes and electrolyte which are of different compositions. The intermediate layers are comprised of a blend of some of the materials used in the electrode and electrolyte compositions. Particle size is controlled to reduce problems involving differential shrinkage rates of the various layers when the entire structure is fired at a single temperature, while pore formers are provided in the electrolyte layers to be removed during firing for the formation of desired pores in the electrode layers. Each layer includes a binder in the form of a thermosetting acrylic which during initial processing is cured to provide a self-supporting structure with the ceramic components in the green state. A self-supporting corrugated structure is thus formed prior to firing, which the organic components of the binder and plasticizer removed during firing to provide a high strength, high temperature resistant ceramic structure of low weight and density.

  13. Methylmercury-induced reactive oxygen species formation in neonatal cerebral astrocytic cultures is attenuated by antioxidants.

    PubMed

    Shanker, Gouri; Aschner, Michael

    2003-01-31

    Excessive generation of reactive oxygen species (ROS) has been suggested as a causal factor in various neurodegenerative disorders, such as Parkinson's disease and Alzheimer's disease [Brain Res. 830 (1999) 10-15; Biochem. J. 310 (1995) 83-90; Free Radic. Biol. Med. 27 (1999) 612-616]. The present work examined the role of ROS in the neurotoxicity of methylmercury (MeHg). ROS formation in primary astrocytic cultures of neonatal rat cerebral cortex was monitored by 2',7'-dichlorodihydrofluorescein diacetate (H(2)DCF-DA) fluorescence. MeHg, at 10 and 20 microM caused a significant increase in ROS formation (10 microM, P<0.01; 20 microM, P<0.001). Additional studies established the effectiveness of antioxidants/free radical scavengers in attenuating the MeHg-stimulated ROS formation in the following rank-order: (1) Trolox (6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid), a non-thiol containing antioxidant, (2) n-propyl gallate (PG), a free radical scavenger, (3) superoxide dismutase (SOD), an antioxidant enzyme that dismutates superoxide anion radical, (4) alpha-phenyl-tert-butyl nitrone (PBN), a lipophilic hydroxyl radical spin trapping agent. A significant inhibition of MeHg-induced ROS generation was also noted in astrocytes preincubated (3 h) with arachidonyl trifluoromethyl ketone (AACOCF(3,) 20 microM, P<0.05), a specific inhibitor of cytosolic phospholipase A(2) (cPLA(2)). Conversely, pretreatment (24 h) with 100 microM buthionine-L-sulfoxamine [BSO, a glutathione (GSH) synthesis inhibitor], significantly increased (P<0.05) ROS formation in MeHg treated astrocytes compared to controls. Combined, these studies invoke ROS as potent mediators of MeHg cytotoxicity and support the hypothesis that excessive ROS generation, at least in part, plays an important role in MeHg-induced neurotoxicity. PMID:12573536

  14. Oncogene-induced reactive oxygen species fuel hyperproliferation and DNA damage response activation

    PubMed Central

    Ogrunc, M; Di Micco, R; Liontos, M; Bombardelli, L; Mione, M; Fumagalli, M; Gorgoulis, V G; d'Adda di Fagagna, F

    2014-01-01

    Oncogene-induced reactive oxygen species (ROS) have been proposed to be signaling molecules that mediate proliferative cues. However, ROS may also cause DNA damage and proliferative arrest. How these apparently opposite roles can be reconciled, especially in the context of oncogene-induced cellular senescence, which is associated both with aberrant mitogenic signaling and DNA damage response (DDR)-mediated arrest, is unclear. Here, we show that ROS are indeed mitogenic signaling molecules that fuel oncogene-driven aberrant cell proliferation. However, by their very same ability to mediate cell hyperproliferation, ROS eventually cause DDR activation. We also show that oncogenic Ras-induced ROS are produced in a Rac1 and NADPH oxidase (Nox4)-dependent manner. In addition, we show that Ras-induced ROS can be detected and modulated in a living transparent animal: the zebrafish. Finally, in cancer we show that Nox4 is increased in both human tumors and a mouse model of pancreatic cancer and specific Nox4 small-molecule inhibitors act synergistically with existing chemotherapic agents. PMID:24583638

  15. Predicting fissile content of spent nuclear fuel assemblies with the passive neutron Albedo reactivity technique and Monte Carlo code emulation

    SciTech Connect

    Conlin, Jeremy Lloyd; Tobin, Stephen J

    2010-10-13

    There is a great need in the safeguards community to be able to nondestructively quantify the mass of plutonium of a spent nuclear fuel assembly. As part of the Next Generation of Safeguards Initiative, we are investigating several techniques, or detector systems, which, when integrated, will be capable of quantifying the plutonium mass of a spent fuel assembly without dismantling the assembly. This paper reports on the simulation of one of these techniques, the Passive Neutron Albedo Reactivity with Fission Chambers (PNAR-FC) system. The response of this system over a wide range of spent fuel assemblies with different burnup, initial enrichment, and cooling time characteristics is shown. A Monte Carlo method of using these modeled results to estimate the fissile content of a spent fuel assembly has been developed. A few numerical simulations of using this method are shown. Finally, additional developments still needed and being worked on are discussed.

  16. Increased Reactive Oxygen Species Formation and Oxidative Stress in Rheumatoid Arthritis

    PubMed Central

    Mateen, Somaiya; Moin, Shagufta; Khan, Abdul Qayyum; Zafar, Atif; Fatima, Naureen

    2016-01-01

    Background Rheumatoid arthritis (RA) is an autoimmune inflammatory disorder. Highly reactive oxygen free radicals are believed to be involved in the pathogenesis of the disease. In this study, RA patients were sub-grouped depending upon the presence or absence of rheumatoid factor, disease activity score and disease duration. RA Patients (120) and healthy controls (53) were evaluated for the oxidant—antioxidant status by monitoring ROS production, biomarkers of lipid peroxidation, protein oxidation and DNA damage. The level of various enzymatic and non-enzymatic antioxidants was also monitored. Correlation analysis was also performed for analysing the association between ROS and various other parameters. Methods Intracellular ROS formation, lipid peroxidation (MDA level), protein oxidation (carbonyl level and thiol level) and DNA damage were detected in the blood of RA patients. Antioxidant status was evaluated by FRAP assay, DPPH reduction assay and enzymatic (SOD, catalase, GST, GR) and non-enzymatic (vitamin C and GSH) antioxidants. Results RA patients showed a higher ROS production, increased lipid peroxidation, protein oxidation and DNA damage. A significant decline in the ferric reducing ability, DPPH radical quenching ability and the levels of antioxidants has also been observed. Significant correlation has been found between ROS and various other parameters studied. Conclusion RA patients showed a marked increase in ROS formation, lipid peroxidation, protein oxidation, DNA damage and decrease in the activity of antioxidant defence system leading to oxidative stress which may contribute to tissue damage and hence to the chronicity of the disease. PMID:27043143

  17. Effect of process conditions on the microstructural formation of dc reactively sputter deposited AlN

    SciTech Connect

    Ekpe, Samuel D.; Jimenez, Francisco J.; Dew, Steven K.

    2010-09-15

    Thin film aluminum nitride (AlN), because of its attractive properties, is a material with many applications. Its microstructure and hence properties are greatly influenced by the deposition process conditions. In this work, AlN was reactively deposited in a dc magnetron sputtering system at different proportions of nitrogen in the process gas mixture and at different process conditions. The microstructure and composition of the films were analyzed using x-ray diffraction data, energy dispersive spectroscopy, and scanning electron microscopy. Results show that for a process gas pressure of 0.67 Pa, a magnetron power of 100 W, and a substrate-target distance of 10 cm, a near stoichiometeric AlN can be prepared at nitrogen proportions as low as 20%. At these process conditions, (002) was the preferred crystal orientation. Dense fibrous structures were obtained, especially at low deposition rates with high proportions of nitrogen. Increase in magnetron power and decrease in distance result in a more porous structure. High kinetic energies (average) of the sputtered Al particles and high deposition rates tend to favor AlN(101) formation, while low kinetic energies of the Al particles and low deposition rates generally favor more of the AlN(100) formation.

  18. Absence of reactive intermediates in the formation of catechol estrogens by rat liver microsomes.

    PubMed

    Jellinck, P H; Hahn, E F; Fishman, J

    1986-06-15

    Release of 3H2O from regiospecifically labeled estradiol was measured during 2-hydroxylation of this estrogen by rat liver microsomes. The amount of tritium remaining in the isolated catechol estrogen was also determined. Virtually all the tritium was removed from C-2 during the reaction confirming the absence of an NIH shift. About 20% of the tritium at C-1 was also lost without any such change occurring at C-4 or C-6,7 of the steroid molecule. These findings provide evidence for the formation of an arene oxide or o-semiquinone intermediate during the conversion of estradiol to 2-hydroxyestradiol. No indication of adduct formation at either C-1 or C-4 during this biotransformation was obtained although the 2-hydroxylated product was able to react with a nucleophile such as glutathione. The different regiospecificity of tritium loss in the generation of catechol estrogens and in their subsequent reaction leads to the important conclusion that the reactive intermediates in the two processes must be different. The possible role of catechol estrogens in neoplastic transformation is discussed. PMID:3011797

  19. Ambient Fine Particulate Matter Induces Apoptosis of Endothelial Progenitor Cells Through Reactive Oxygen Species Formation

    PubMed Central

    Cui, Yuqi; Xie, Xiaoyun; Jia, Fengpeng; He, Jianfeng; Li, Zhihong; Fu, Minghuan; Hao, Hong; Liu, Ying; Liu, Jason Z.; Cowan, Peter J.; Zhu, Hua; Sun, Qinghua; Liu, Zhenguo

    2015-01-01

    Background/Aims Bone marrow (BM)-derived endothelial progenitor cells (EPCs) play a critical role in angiogenesis and vascular repair. Some environmental insults, like fine particulate matter (PM) exposure, significantly impair cardiovascular functions. However, the mechanisms for PM-induced adverse effects on cardiovascular system remain largely unknown. The present research was to study the detrimental effects of PM on EPCs and explore the potential mechanisms. Methods PM was intranasal-distilled into male C57BL/6 mice for one month. Flow cytometry was used to measure the number of EPCs, apoptosis level of circulating EPCs and intracellular reactive oxygen species (ROS) formation. Serum TNF-α and IL-1β were measured using ELISA. To determine the role of PM-induced ROS in EPC apoptosis, PM was co-administrated with the antioxidant N-acetylcysteine (NAC) in wild type mice or used in a triple transgenic mouse line (TG) with overexpression of antioxidant enzyme network (AON) composed of superoxide dismutase (SOD)1, SOD3, and glutathione peroxidase (Gpx-1) with decreased in vivo ROS production. Results PM treatment significantly decreased circulating EPC population, promoted apoptosis of EPCs in association with increased ROS production and serum TNF-α and IL-1β levels, which could be effectively reversed by either NAC treatment or overexpression of AON. Conclusion PM exposure significantly decreased circulating EPCs population due to increased apoptosis via ROS formation in mice. PMID:25591776

  20. Coupled Reactive Transport Modeling of CO2 Injection in Mt. Simon Sandstone Formation, Midwest USA

    NASA Astrophysics Data System (ADS)

    Liu, F.; Lu, P.; Zhu, C.; Xiao, Y.

    2009-12-01

    CO2 sequestration in deep geological formations is one of the promising options for CO2 emission reduction. While several large scale CO2 injections in saline aquifers have shown to be successful for the short-term, there is still a lack of fundamental understanding on key issues such as CO2 storage capacity, injectivity, and security over multiple spatial and temporal scales that need to be addressed. To advance these understandings, we applied multi-phase coupled reactive mass transport modeling to investigate the fate of injected CO2 and reservoir responses to the injection into Mt. Simon Formation. We developed both 1-D and 2-D reactive transport models in a radial region of 10,000 m surrounding a CO2 injection well to represent the Mt. Simon sandstone formation, which is a major regional deep saline reservoir in the Midwest, USA. Supercritical CO2 is injected into the formation for 100 years, and the modeling continues till 10,000 years to monitor both short-term and long-term behavior of injected CO2 and the associated rock-fluid interactions. CO2 co-injection with H2S and SO2 is also simulated to represent the flue gases from coal gasification and combustion in the Illinois Basin. The injection of CO2 results in acidified zones (pH ~3 and 5) adjacent to the wellbore, causing progressive water-rock interactions in the surrounding region. In accordance with the extensive dissolution of authigenic K-feldspar, sequential precipitations of secondary carbonates and clay minerals are predicted in this zone. The vertical profiles of CO2 show fingering pattern from the top of the reservoir to the bottom due to the density variation of CO2-impregnated brine, which facilitate convection induced mixing and solubility trapping. Most of the injected CO2 remains within a radial distance of 2500 m at the end of 10,000 years and is sequestered and immobilized by solubility and residual trapping. Mineral trapping via secondary carbonates, including calcite, magnesite

  1. Modeling the Influence of Interaction Layer Formation on Thermal Conductivity of U–Mo Dispersion Fuel

    SciTech Connect

    Burkes, Douglas; Casella, Andrew M.; Huber, Tanja K.

    2015-01-01

    The Global Threat Reduction Initiative Program continues to develop existing and new plate- and rod-type research and test reactor fuels with maximum attainable uranium loadings capable of potentially converting a number of the world’s remaining high-enriched uranium fueled reactors to low-enriched uranium fuel. Currently, the program is focused on assisting with the development and qualification of an even higher density fuel type consisting of a uranium-molybdenum (U-Mo) alloy dispersed in an aluminum matrix. Thermal conductivity is an important consideration in determining the operational temperature of the fuel plate and can be influenced by interaction layer formation between the fuel and matrix, porosity that forms during fabrication of the fuel plates, and upon the concentration of the dispersed phase within the matrix. This paper develops and validates a simple model to study the influence of interaction layer formation and conductivity, fuel particle size, and volume fraction of fuel dispersed in the matrix on the effective conductivity of the composite. The model shows excellent agreement with results previously presented in the literature. In particular, the thermal conductivity of the interaction layer does not appear to be important in determining the overall conductivity of the composite, while formation of the interaction layer and subsequent consumption of the matrix reveals a rather significant effect. The effective thermal conductivity of the composite can be influenced by the fuel particle distribution by minimizing interaction layer formation and preserving the higher thermal conductivity matrix.

  2. Oxidation and formation of deposit precursors in hydrocarbon fuels

    NASA Technical Reports Server (NTRS)

    Buttrill, S. E., Jr.; Mayo, F. R.; Lan, B.; St.john, G. A.; Dulin, D.

    1982-01-01

    A practical fuel, home heating oil no. 2 (Fuel C), and the pure hydrocarbon, n-dodecane, were subjected to mild oxidation at 130 C and the resulting oxygenated reaction products, deposit precursors, were analyzed using field ionization mass spectrometry. Results for fuel C indicated that, as oxidation was initially extended, certain oxygenated reaction products of increasing molecular weights in the form of monomers, dimers and some trimers were produced. Further oxidation time increase resulted in further increase in monomers but a marked decrease in dimers and trimers. This suggests that these larger molecular weight products have proceeded to form deposit and separated from the fuel mixture. Results for a dodecane indicated that yields for dimers and trimers were very low. Dimers were produced as a result of interaction between oxygenated products with each other rather than with another fuel molecule. This occurred even though fuel molecule concentration was 50 times, or more greater than that for these oxygenated reaction products.

  3. Iron Hydroxy Carbonate Formation in Zerovalent Iron Permeable Reactive Barriers: Characterization and Evaluation of Phase Stability

    EPA Science Inventory

    Predicting the long-term potential of permeable reactive barriers for treating contaminated groundwater relies on understanding the endpoints of biogeochemical reactions between influent groundwater and the reactive medium. Iron hydroxy carbonate (chukanovite) is frequently obs...

  4. Formation, characterization and reactivity of adsorbed oxygen on BaO/Pt(111)

    SciTech Connect

    Mudiyanselage, Kumudu; Mei, Donghai; Yi, Cheol-Woo; Weaver, Jason F.; Szanyi, Janos

    2010-12-02

    The formation of adsorbed O (Oad) species and their reactivities in CO oxidation on BaO/Pt(111) (at two BaO coverages) were studied with temperature programmed desorption (TPD), infrared reflection absorption (IRA) and X-ray photoelectron (XP) spectroscopies. In neither of these two systems was the Pt(111) surface completely covered with BaO. On the system with lower BaO coverage (~45 % of the Pt(111) surface is covered by BaO), two different Oad species form following the adsorption of O2 at 300 K: O adsorbed on BaO-free Pt(111) sites (OPt) and at the Pt-BaO interface (Oint). On the system with higher BaO coverage (~60 % of the Pt(111) surface is covered by BaO), two types of Oint are seen at the Pt-BaO interface. The desorption of OPt from the BaO-free portion of the Pt(111) surface gives an O2 desorption peak with a maximum desorption rate at ~690 K. Migration of Oint to the Pt(111) sites and their recombinative desorption give two explosive desorption features at ~760 and ~790 K in the TPD spectrum. The reactivities of these Oad species with CO to form CO2 follow their sequence of desorption; i.e., the OPt associated with the BaO-free Pt(111) surface, which desorbs at 690 K, reacts first with CO, followed by the Oint species at the Pt-BaO interface (first the one that desorbs at ~760 K and finally the one that is bound the most strongly to the interface, and desorbs at ~790 K). This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  5. Role of Reactive Intermediates in Manganese Oxide Formation By Filamentous Ascomycete Fungi

    NASA Astrophysics Data System (ADS)

    Zeiner, C. A.; Anderton, C.; Wu, S.; Purvine, S.; Zink, E.; Paša-Tolić, L.; Santelli, C. M.; Hansel, C. M.

    2014-12-01

    Biogenic manganese (Mn) oxide minerals are ubiquitous in the environment, and their high reactivity can profoundly impact the fate of contaminants and cycling of carbon and nutrients. In contrast to bacteria, the pathways utilized by fungi to oxidize Mn(II) to Mn(III,IV) oxides remain largely unknown. Here, we explore the mechanisms of Mn(II) oxidation by a phylogenetically diverse group of filamentous Ascomycete fungi using a combination of chemical assays and bulk and spatially-resolved mass spectrometry. We show that the mechanisms of Mn(II) oxidation vary with fungal species, over time during secretome compositional changes, and in the presence of other fungi. Specifically, our work implicates a dynamic transition in Mn(II) oxidation pathways that varies between species. In particular, while reactive oxygen species (ROS) produced via transmembrane NADPH oxidases are involved in initial oxidation, over time, secreted enzymes become important Mn(II) oxidation mediators for some species. In addition, the overall secretome oxidation capacity varies with time and fungal species. Secretome analysis reveals a surprising absence of enzymes currently considered to be Mn(II)-oxidizing enzymes in these organisms, and instead highlights a wide variety of redox-active enzymes. Furthermore, we implicate fungal cell defense mechanisms in the formation of distinct Mn oxide patterns when fungi are grown in head-to-head competition. The identification and regulation of these secreted enzymes are under current investigation within the bulk secretome and within the interaction zone of structured fungal communities. Overall, our findings illustrate that Ascomycete Mn(II) oxidation mechanisms are highly variable and are dictated by complex environmental and ecological interactions. Future work will explore the connection between Ascomycete Mn(II) oxidation and the ability to degrade cellulose, a key carbon reservoir for biofuel production.

  6. Computation Sheds Insight into Iron Porphyrin Carbenes' Electronic Structure, Formation, and N-H Insertion Reactivity.

    PubMed

    Sharon, Dina A; Mallick, Dibyendu; Wang, Binju; Shaik, Sason

    2016-08-01

    Iron porphyrin carbenes constitute a new frontier of species with considerable synthetic potential. Exquisitely engineered myoglobin and cytochrome P450 enzymes can generate these complexes and facilitate the transformations they mediate. The current work harnesses density functional theoretical methods to provide insight into the electronic structure, formation, and N-H insertion reactivity of an iron porphyrin carbene, [Fe(Por)(SCH3)(CHCO2Et)](-), a model of a complex believed to exist in an experimentally studied artificial metalloenzyme. The ground state electronic structure of the terminal form of this complex is an open-shell singlet, with two antiferromagnetically coupled electrons residing on the iron center and carbene ligand. As we shall reveal, the bonding properties of [Fe(Por)(SCH3)(CHCO2Et)](-) are remarkably analogous to those of ferric heme superoxide complexes. The carbene forms by dinitrogen loss from ethyl diazoacetate. This reaction occurs preferentially through an open-shell singlet transition state: iron donates electron density to weaken the C-N bond undergoing cleavage. Once formed, the iron porphyrin carbene accomplishes N-H insertion via nucleophilic attack. The resulting ylide then rearranges, using an internal carbonyl base, to form an enol that leads to the product. The findings rationalize experimentally observed reactivity trends reported in artificial metalloenzymes employing iron porphyrin carbenes. Furthermore, these results suggest a possible expansion of enzymatic substrate scope, to include aliphatic amines. Thus, this work, among the first several computational explorations of these species, contributes insights and predictions to the surging interest in iron porphyrin carbenes and their synthetic potential. PMID:27347808

  7. Impacts of powdered activated carbon addition on trihalomethane formation reactivity of dissolved organic matter in membrane bioreactor effluent.

    PubMed

    Ma, Defang; Gao, Yue; Gao, Baoyu; Wang, Yan; Yue, Qinyan; Li, Qian

    2014-12-01

    Characteristics and trihalomethane (THM) formation reactivity of dissolved organic matter (DOM) in effluents from two membrane bioreactors (MBRs) with and without powdered activated carbon (PAC) addition (referred to as PAC/MBR and MBR, respectively) were examined to investigate the effects of PAC addition on THM formation of MBR effluent during chlorination. PAC addition increased the specific UV absorbance. Hydrophobic DOM especially hydrophobic acids in PAC/MBR effluent (50%) were more than MBR effluent (42%). DOM with molecular weight <1 kDa constituted 12% of PAC/MBR effluent DOM, which was less than that of MBR effluent (16%). Data obtained from excitation and emission matrix fluorescence spectroscopy revealed that PAC/MBR effluent DOM contained more simple aromatic protein, but had less fulvic acid-like and soluble microbial by-product-like. PAC addition reduced the formation of bromine-containing THMs during chlorination of effluents, but increased THM formation reactivity of effluent DOM. PMID:25150685

  8. Chemical functionalities at the silica surface determining its reactivity when inhaled. Formation and reactivity of surface radicals.

    PubMed

    Fubini, B; Giamello, E; Volante, M; Bolis, V

    1990-12-01

    Reactive radicals at the surface of quartz or other SiO2 polymorphs have been studied by EPR in relation to their possible role in pathogenicity. All the examined dusts bear the characteristic radicals of silica ground in air: Si, SiO., SiO.2 (peroxyradical) and O2.- (superoxide ion), but some also show additional spectral lines belonging to other radical forms. Comparison of standard quartz dusts (DQ-12, Min-u-sil 5) with a natural quartz and with what obtained by grinding a very pure quartz crystal indicates that to a higher purity corresponds a higher radical population. Cristobalite and vitreous silica exhibit similar spectra, with larger proportion by respect to quartz, of partially reduced oxygen forms. The reactivity of the silica surface towards O2 and NaClO aqueous solutions are investigated by examining the modification in the EPR spectra induced by these treatments. A possible mechanism for fibrogenicity is proposed whereby, within the activated macrophage, a catalytic reaction occurs between surface functionalities and macrophage oxygen metabolites. This reaction would trigger the abnormal production of fibroblast stimulating factors, ending up with silicosis. PMID:1965871

  9. A Study of Pollutant Formation from the Lean Premixed Combustion of Gaseous Fuel Alternatives to Natural Gas

    NASA Astrophysics Data System (ADS)

    Fackler, Keith Boyd, Jr.

    emissions decrease with increasing H2 fuel fraction for combustion of CH4/H2 blends. This appears to be caused by a reduction in the amount of NO made by the prompt pathway involving the reaction of N2 with hydrocarbon radicals as the CH4 is replaced by H2. 2.) For category 2 (the process and refinery blend) and category 5 (the LNG, shale, and associated gases), NOx emissions increase with the addition of C2 and C3 hydrocarbons. This could be due to an increased production of free radicals resulting from increasing CO production when higher molecular weight hydrocarbons are broken down. 3.) For category 3 (the O2 blown gasified coal/petcoke), NOx emissions increase with increasing CO fuel fraction. The reason for this is attributed to CO producing more radicals per unit heat release than H2. When CO replaces H2, an increase in NOx emissions is seen due to an increase in the productivity of the N2O, NNH, and Zeldovich pathways. 4.) For category 4 (the landfill gas) the addition of diluents such as CO2 and N2 at constant air flow produces more NOx per kg of CH4 consumed, and N2 is more effective than CO 2 in increasing the NOx emission index. The increase in emission index appears to be due to an enhancement of the prompt NOx pathway as the diluents are added and the mixture moves towards stoichiometric. In addition, the presence of CO2 as a diluent catalyzes the loss of flame radicals, leading to less NOx formation than when an equivalent amount of N2 is used as a diluent. For a selected set of fuels, detailed spacial reactor probing is carried out. At the nominal temperature and residence time, the experimental results show the following trends for flame structure as a function of fuel type: 1.) Pure H2 is far more reactive in comparison to CH4 and all other pure alkane fuels. This results in relatively flat NO x and temperature profiles; whereas, the alkane fuels drop in both temperature and NOx production in the jet, where more fresh reactor feed gases are present. 2

  10. A Statistical Approach to Predict the Failure Enthalpy and Reliability of Irradiated PWR Fuel Rods During Reactivity-Initiated Accidents

    SciTech Connect

    Nam, Cheol; Jeong, Yong-Hwan; Jung, Youn-Ho

    2001-11-15

    During the last decade, the failure behavior of high-burnup fuel rods under a reactivity-initiated accident (RIA) condition has been a serious concern since fuel rod failures at low enthalpy have been observed. This has resulted in the reassessment of existing licensing criteria and failure-mode study. To address the issue, a statistics-based methodology is suggested to predict failure probability of irradiated fuel rods under an RIA. Based on RIA simulation results in the literature, a failure enthalpy correlation for an irradiated fuel rod is constructed as a function of oxide thickness, fuel burnup, and pulse width. Using the failure enthalpy correlation, a new concept of ''equivalent enthalpy'' is introduced to reflect the effects of the three primary factors as well as peak fuel enthalpy into a single damage parameter. Moreover, the failure distribution function with equivalent enthalpy is derived, applying a two-parameter Weibull statistical model. Finally, the sensitivity analysis is carried out to estimate the effects of burnup, corrosion, peak fuel enthalpy, pulse width, and cladding materials used.

  11. COMBINED EFFECTS OF ORGANIC REACTIVITY AND NMHC/NOX RATIO ON PHOTOCHEMICAL OXIDANT FORMATION - A MODELING STUDY

    EPA Science Inventory

    A modeling study was undertaken to assess the effect of organic reactivity on photochemical oxidant formation. A six-component hydrocarbon model was developed and tested against data collected in a smog chamber study of irradiated auto exhaust and oxides of nitrogen (NO sub x) mi...

  12. Using fluorescence-activated flow cytometry to determine reactive oxygen species formation and membrane lipid peroxidation in viable boar spermatozoa

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fluorescence-activated flow cytometry analyses were developed for determination of reactive oxygen species (ROS) formation and membrane lipid peroxidation in live spermatozoa loaded with, respectively, hydroethidine (HE) or the lipophilic probe 4,4-difluoro-5-(4-phenyl-1,3-butadienyl)-4-bora-3a,4a-d...

  13. Uncertainty in the reactive transport model response to analkaline perturbation in a clay formation

    SciTech Connect

    Burnol, A.; Blanc, P.; Xu, T.; Spycher, N.; Gaucher, E.C.

    2006-03-15

    The mineral alteration in the concrete barrier and in the clay formation around long-lived intermediate-level radioactive waste in the French deep geological disposal concept is evaluated using numerical modeling. There are concerns that the mineralogical composition of the surrounded clay will not be stable under the high alkaline pore fluid conditions caused by concrete (pH {approx} 12). Conversely, the infiltration of CO{sub 2}-rich groundwater from the clay formation into initially unsaturated concrete, at the high temperature (T {approx} 70 C) produced from the decay of radionuclides, could cause carbonation, thereby potentially affecting critical performance functions of this barrier. This could also lead to significant changes in porosity, which would affect aqueous diffusive transport of long-lived radionuclides. All these processes are therefore intimately coupled and advanced reactive transport models are required for long-term performance assessment. The uncertainty in predictions of these models is one major question that must be answered. A mass-transfer model response to an alkaline perturbation in clay with standard model values is first simulated using the two-phase non-isothermal reactive transport code TOUGHREACT. The selection of input parameters is thereafter designed to sample uncertainties in a wide range of physico-chemical processes without making a priori assumptions about the relative importance of different feedbacks. This 'base-case' simulation is perturbed by setting a parameter to a minimum, intermediate or maximum value or by switching on/off a process. This sensitivity analysis is conducted using grid computing facilities of BRGM (http://iggi.imag.fr). Our evaluation of the preliminary results suggests that the resaturation and the heating of the near-field will be of long enough duration to cause a limited carbonation through all the width of the concrete barrier. Another prediction is the possibility of self-sealing at the concrete

  14. Fuel Efficient Strategies for Reducing Contrail Formations in United States Air Space

    NASA Technical Reports Server (NTRS)

    Sridhar, Banavar; Chen, Neil Y.; Ng, Hok K.

    2010-01-01

    This paper describes a class of strategies for reducing persistent contrail formation in the United States airspace. The primary objective is to minimize potential contrail formation regions by altering the aircraft's cruising altitude in a fuel-efficient way. The results show that the contrail formations can be reduced significantly without extra fuel consumption and without adversely affecting congestion in the airspace. The contrail formations can be further reduced by using extra fuel. For the day tested, the maximal reduction strategy has a 53% contrail reduction rate. The most fuel-efficient strategy has an 8% reduction rate with 2.86% less fuel-burnt compared to the maximal reduction strategy. Using a cost function which penalizes extra fuel consumed while maximizing the amount of contrail reduction provides a flexible way to trade off between contrail reduction and fuel consumption. It can achieve a 35% contrail reduction rate with only 0.23% extra fuel consumption. The proposed fuel-efficient contrail reduction strategy provides a solution to reduce aviation-induced environmental impact on a daily basis.

  15. Secondary Organic Aerosol Formation by Reactive Condensation of Glyoxal and Water Vapor

    NASA Astrophysics Data System (ADS)

    Hastings, W. P.; Koehler, C. A.; de Haan, D. O.

    2004-05-01

    The formation of secondary organic aerosol particles by particle-phase reactions is currently of great interest. Glyoxal has been identified as a significant component in the particle phase in recent smog chamber aromatic oxidation studies. This is surprising because glyoxal has a high vapor pressure and phase partitioning theory would predict that it remain almost entirely in the gas phase. Growth of inorganic seed aerosol in a particle chamber was monitored by scanning mobility particle sizing during addition of gas-phase glyoxal and small amounts of water vapor. Glyoxal was observed to condense on inorganic seed aerosol at concentrations that are at least 100 times below its vapor pressure. This behavior can be explained by a chemical reaction: glyoxal is known to polymerize when exposed to water vapor. This polymerization may be a general mechanism for secondary aerosol formation by alpha-dicarbonyl compounds. The reactivity of hydrated and polymerized forms of glyoxal during analysis by gas chromatography was assessed. Hydrated glyoxal was found to convert to glyoxal at even slightly elevated temperatures in GC injection ports. We then showed that breakdown of solid-phase glyoxal trimer dihydrate, forming gas phase glyoxal and water vapor, occurs at temperatures just above 50 *C, the boiling point of glyoxal. These observations suggest that reports of particle-phase glyoxal are likely caused by GC sampling artifacts, and that the actual particulate species are instead polymerized forms of glyoxal. It does not appear that chemical derivatization protects glyoxal polymers from thermal breakdown during GC analysis. The existence in the particle phase of glyoxal polymers with negligable vapor pressures, rather than volatile glyoxal, is consistent with phase partitioning theory.

  16. Kinetics of ceramic-metal composite formation by reactive metal penetration

    SciTech Connect

    Fahrenholtz, W.G.; Ewsuk, K.G.; Loehman, R.E.; Lu, P.

    1998-10-01

    The rate of composite formation via reactive metal penetration has been determined. The metal penetration depth (i.e., the reaction-layer thickness) was measured from cross sections of partially reacted samples. Samples were fabricated by immersing dense mullite preforms in a bath of molten aluminum at temperatures of 900--1300 C and reacting the combination for up to 250 min. In general, the reaction-layer thickness increased linearly as the time increased. Penetration rates as high as 6.0 mm/h were measured; however, the aluminum penetration rate varied dramatically with time and temperature. The penetration rate increased when the reaction temperature was increased from 900 C to 1100 C, and the reaction-layer thickness increased linearly as the time increased in this temperature range. At temperatures of 1150 C and above, reaction-layer formation slowed or stopped after a relatively short period of rapid linear growth, because of an increase in silicon concentration near the reaction interface. The duration of the rapid linear growth, because of an increase in silicon concentration near the reaction interface. The duration of the rapid linear growth period decreased from 25 min at 1150 C to <1 min at 1250 C. At temperatures of 1300 C and above, no reaction layer was detected by using optical microscopy. Kinetics data and transmission electron microscopy analysis suggest that the reaction was inhibited at higher reaction temperatures and longer times, because of silicon buildup and saturation at the reaction front. Calculations show that, as the reaction temperature increased, the silicon production increased aster than the silicon transport. The two gates were approximately equal at a temperature of 1100 C.

  17. Iberis amara Extract Induces Intracellular Formation of Reactive Oxygen Species and Inhibits Colon Cancer

    PubMed Central

    Plauth, Annabell; Wowro, Sylvia J.; Fischer, Cornelius; Abdel-Aziz, Heba; Sauer, Sascha

    2016-01-01

    Massively increasing global incidences of colorectal cancer require efficient treatment and prevention strategies. Here, we report unexpected anticancerogenic effects of hydroethanolic Iberis amara extract (IAE), which is known as a widely used phytomedical product for treating gastrointestinal complaints. IAE significantly inhibited the proliferation of HT-29 and T84 colon carcinoma cells with an inhibitory concentration (IC50) of 6 and 9 μg/ml, respectively, and further generated inhibitory effects in PC-3 prostate and MCF7 breast cancer cells. Inhibition of proliferation in HT-29 cells was associated with a G2/M phase cell cycle arrest including reduced expression of various regulatory marker proteins. Notably, in HT-29 cells IAE further induced apoptosis by intracellular formation of reactive oxygen species (ROS). Consistent with predictions derived from our in vitro experiments, bidaily oral gavage of 50 mg/kg of IAE over 4 weeks resulted in significant inhibition of tumor growth in a mouse HT-29 tumor xenograft model. Taken together, Iberis amara extracts could become useful alternatives for preventing and treating the progression of colon cancer. PMID:27050665

  18. Modulation of reactivity in the cavity of liposomes promotes the formation of peptide bonds.

    PubMed

    Grochmal, Anna; Prout, Luba; Makin-Taylor, Robert; Prohens, Rafel; Tomas, Salvador

    2015-09-30

    In living cells, reactions take place in membrane-bound compartments, often in response to changes in the environment. Learning how the reactions are influenced by this compartmentalization will help us gain an optimal understanding of living organisms at the molecular level and, at the same time, will offer vital clues on the behavior of simple compartmentalized systems, such as prebiotic precursors of cells and cell-inspired artificial systems. In this work we show that a reactive building block (an activated amino acid derivative) trapped in the cavity of a liposome is protected against hydrolysis and reacts nearly quantitatively with another building block, which is membrane-permeable and free in solution, to form the dipeptide. By contrast, when the activated amino acid is found outside the liposome, hydrolysis is the prevalent reaction, showing that the cavity of the liposomes promotes the formation of peptide bonds. We attribute this result to the large lipid concentration in small compartments from the point of view of a membrane-impermeable molecule. Based on this result, we show how the outcome of the reaction can be predicted as a function of the size of the compartment. The implications of these results on the behavior of biomolecules in cell compartments, abiogenesis, and the design of artificial cell-inspired systems are considered. PMID:26356087

  19. JAEA Studies on High Burnup Fuel Behaviors during Reactivity-Initiated Accident and Loss-of-Coolant Accident

    SciTech Connect

    Fuketa, Toyoshi; Sugiyama, Tomoyuki; Nagase, Fumihisa; Suzuki, Motoe

    2007-07-01

    The objectives of fuel safety research program at Japan Atomic Energy Agency (JAEA) are; to evaluate adequacy of present safety criteria and safety margins; to provide a database for future regulation on higher burnup UO{sub 2} and MOX fuels, new cladding and pellets; and to provide reasonably mechanistic computer codes for regulatory application. The JAEA program is comprised of reactivity-initiated accident (RIA) studies including pulse-irradiation experiments in the NSRR and cladding mechanical tests, loss-of-coolant accident (LOCA) tests including integral thermal shock test and oxidation rate measurement, development and verification of computer codes FEMAXI-6 and RANNS, and so on. In addition to an overview of the fuel safety research at JAEA, most recent progresses in the RIA and LOCA tests programs and the codes development are described and discussed in the paper. (authors)

  20. 40 CFR Appendix Viii to Part 600 - Fuel Economy Label Formats

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 30 2011-07-01 2011-07-01 false Fuel Economy Label Formats VIII Appendix VIII to Part 600 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) ENERGY POLICY FUEL ECONOMY AND CARBON-RELATED EXHAUST EMISSIONS OF MOTOR VEHICLES Pt. 600, App. VIII...

  1. Sucrose-fueled, energy dissipative, transient formation of molecular hydrogels mediated by yeast activity.

    PubMed

    Angulo-Pachón, César A; Miravet, Juan F

    2016-04-01

    A biologically mediated, energy dissipative, reversible formation of fibrillar networks is reported. The process of gelation is linked to sucrose-fueled production of CO2 by baker's yeast (Saccharomyces cerevisiae). Continuous fueling of the system is required to maintain the self-assembled fibrillar network. PMID:27009800

  2. 40 CFR 600.310-12 - Fuel economy label format requirements-electric vehicles.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-electric vehicles. 600.310-12 Section 600.310-12 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Labeling § 600.310-12 Fuel economy label format requirements—electric vehicles. Fuel economy labels for electric vehicles must meet the specifications described in § 600.302, with the following modifications:...

  3. IGNITION AND COMBUSTION OF LIQUID FUEL DROPLETS. PART 1: IMPACT ON POLLUTANT FORMATION

    EPA Science Inventory

    The paper gives results of a study of the ignition process of liquid fuel droplets and its impact on the formation of soot and nitrogen oxides (NOx). The system studied consists of a laboratory flame maintained by a vertical, monosized liquid fuel droplet array surrounded by a la...

  4. The contribution of lubricant to the formation of particulate matter with reactivity controlled compression ignition in light-duty diesel engines

    DOE PAGESBeta

    Storey, John Morse; Curran, Scott; Dempsey, Adam B.; Lewis, Sr., Samuel Arthur; Reitz, Rolf; Walker, N. Ryan; Wright, Chris

    2014-12-25

    Reactivity controlled compression ignition (RCCI) has been shown in single- and multi-cylinder engine research to achieve high thermal efficiencies with ultra-low NOX and soot emissions. The nature of the particulate matter (PM) produced by RCCI operation has been shown in recent research to be different than that of conventional diesel combustion and even diesel low-temperature combustion. Previous research has shown that the PM from RCCI operation contains a large amount of organic material that is volatile and semi-volatile. However, it is unclear if the organic compounds are stemming from fuel or lubricant oil. The PM emissions from dual-fuel RCCI weremore » investigated in this study using two engine platforms, with an emphasis on the potential contribution of lubricant. Both engine platforms used the same base General Motors (GM) 1.9-L diesel engine geometry. The first study was conducted on a single-cylinder research engine with primary reference fuels (PRFs), n-heptane, and iso-octane. The second study was conducted on a four-cylinder GM 1.9-L ZDTH engine which was modified with a port fuel injection (PFI) system while maintaining the stock direct injection fuel system. Multi-cylinder RCCI experiments were run with PFI gasoline and direct injection of 2-ethylhexyl nitrate (EHN) mixed with gasoline at 5 % EHN by volume. In addition, comparison cases of conventional diesel combustion (CDC) were performed. Particulate size distributions were measured, and PM filter samples were collected for analysis of lube oil components. Triplicate PM filter samples (i.e., three individual filter samples) for both gas chromatography-mass spectroscopy (GC-MS; organic) analysis and X-ray fluorescence (XRF; metals) were obtained at each operating point and queued for analysis of both organic species and lubricant metals. Here, the results give a clear indication that lubricants do not contribute significantly to the formation of RCCI PM.« less

  5. The contribution of lubricant to the formation of particulate matter with reactivity controlled compression ignition in light-duty diesel engines

    SciTech Connect

    Storey, John Morse; Curran, Scott; Dempsey, Adam B.; Lewis, Sr., Samuel Arthur; Reitz, Rolf; Walker, N. Ryan; Wright, Chris

    2014-12-25

    Reactivity controlled compression ignition (RCCI) has been shown in single- and multi-cylinder engine research to achieve high thermal efficiencies with ultra-low NOX and soot emissions. The nature of the particulate matter (PM) produced by RCCI operation has been shown in recent research to be different than that of conventional diesel combustion and even diesel low-temperature combustion. Previous research has shown that the PM from RCCI operation contains a large amount of organic material that is volatile and semi-volatile. However, it is unclear if the organic compounds are stemming from fuel or lubricant oil. The PM emissions from dual-fuel RCCI were investigated in this study using two engine platforms, with an emphasis on the potential contribution of lubricant. Both engine platforms used the same base General Motors (GM) 1.9-L diesel engine geometry. The first study was conducted on a single-cylinder research engine with primary reference fuels (PRFs), n-heptane, and iso-octane. The second study was conducted on a four-cylinder GM 1.9-L ZDTH engine which was modified with a port fuel injection (PFI) system while maintaining the stock direct injection fuel system. Multi-cylinder RCCI experiments were run with PFI gasoline and direct injection of 2-ethylhexyl nitrate (EHN) mixed with gasoline at 5 % EHN by volume. In addition, comparison cases of conventional diesel combustion (CDC) were performed. Particulate size distributions were measured, and PM filter samples were collected for analysis of lube oil components. Triplicate PM filter samples (i.e., three individual filter samples) for both gas chromatography-mass spectroscopy (GC-MS; organic) analysis and X-ray fluorescence (XRF; metals) were obtained at each operating point and queued for analysis of both organic species and lubricant metals. Here, the results give a clear indication that lubricants do not contribute significantly to the formation of RCCI PM.

  6. Study of net soot formation in hydrocarbon reforming for hydrogen fuel cells. Final report

    SciTech Connect

    Edelman, R. B.; Farmer, R. C.; Wang, T. S.

    1982-08-01

    The hydrogen fuel cell is expected to be a valuable addition to the electric utility industry; however, the current fuel supply availability requires that conventional heavier hydrocarbon fuels also be considered as primary fuels. Typical heavier fuels would be No. 2 fuel oil with its accompanying sulfur impurities, compared with the currently used light hydrocarbon gases. The potential future use of alternate fuels which are rich in aromatics would exacerbate the problems associated with hydrogen production. Among the more severe of these problems, is the greater tendency of heavier hydrocarbons to form soot. The development of a quasi-global kinetics model to represent the homogeneous and heterogeneous reactions which control the autothermal hydrogen reforming process and the accompanying soot formation and gasification was the objective of this study.

  7. Reassessment of the basis for NRC fuel damage criteria for reactivity transients

    SciTech Connect

    McCardell, R.K.

    1994-10-01

    The present basis for NRC Fuel Damage Criteria was obtained from experiments performed in the Special Power Excursion Reactor Test (SPERT) IV Reactor Capsule Driver Core (CDC) at the Idaho National Engineering Laboratory (INEL) between 1967 and 1970. Most of the CDC test fuel rods were previously unirradiated and the failure threshold for these unirradiated fuel rods was measured to be about 200 calories per gram of UO{sub 2} radially averaged fuel enthalpy at the axial peak.

  8. Fuel-optimal low-thrust formation reconfiguration via Radau pseudospectral method

    NASA Astrophysics Data System (ADS)

    Li, Jing

    2016-07-01

    This paper investigates fuel-optimal low-thrust formation reconfiguration near circular orbit. Based on the Clohessy-Wiltshire equations, first-order necessary optimality conditions are derived from the Pontryagin's maximum principle. The fuel-optimal impulsive solution is utilized to divide the low-thrust trajectory into thrust and coast arcs. By introducing the switching times as optimization variables, the fuel-optimal low-thrust formation reconfiguration is posed as a nonlinear programming problem (NLP) via direct transcription using multiple-phase Radau pseudospectral method (RPM), which is then solved by a sparse nonlinear optimization software SNOPT. To facilitate optimality verification and, if necessary, further refinement of the optimized solution of the NLP, formulas for mass costate estimation and initial costates scaling are presented. Numerical examples are given to show the application of the proposed optimization method. To fix the problem, generic fuel-optimal low-thrust formation reconfiguration can be simplified as reconfiguration without any initial and terminal coast arcs, whose optimal solutions can be efficiently obtained from the multiple-phase RPM at the cost of a slight fuel increment. Finally, influence of the specific impulse and maximum thrust magnitude on the fuel-optimal low-thrust formation reconfiguration is analyzed. Numerical results shown the links and differences between the fuel-optimal impulsive and low-thrust solutions.

  9. Photoirradiation of dehydropyrrolizidine alkaloids--formation of reactive oxygen species and induction of lipid peroxidation.

    PubMed

    Zhao, Yuewei; Xia, Qingsu; Yin, Jun Jie; Lin, Ge; Fu, Peter P

    2011-09-10

    Pyrrolizidine alkaloid (PA)-containing plants are widespread in the world and are probably the most common poisonous plants affecting livestock, wildlife, and human. PAs require metabolic activation to generate pyrrolic metabolites (dehydro-PAs) that bind cellular protein and DNA, leading to hepatotoxicity and genotoxicity, including tumorigenicity. In this study we report that UVA photoirradiation of a series of dehydro-PAs, e.g., dehydromonocrotaline, dehydroriddelliine, dehydroretrorsine, dehydrosenecionine, dehydroseneciphylline, dehydrolasiocarpine, dehydroheliotrine, and dehydroretronecine (DHR) at 0-70 J/cm2 in the presence of a lipid, methyl linoleate, resulted in lipid peroxidation in a light dose-responsive manner. When irradiated in the presence of sodium azide, the level of lipid peroxidation decreased; lipid peroxidation was enhanced when methanol was replaced by deuterated methanol. These results suggest that singlet oxygen is a photo-induced product. When irradiated in the presence of superoxide dismutase, the level of lipid peroxidation decreased, indicating that lipid peroxidation is also mediated by superoxide. Electron spin resonance (ESR) spin trapping studies confirmed that both singlet oxygen and superoxide anion radical were formed during photoirradiation. These results indicate that UVA photoirradiation of dehydro-PAs generates reactive oxygen species (ROS) that mediated the initiation of lipid peroxidation. UVA irradiation of the parent PAs and other PA metabolites, including PA N-oxides, under similar experimental conditions did not produce lipid peroxidation. It is known that PAs induce skin cancer and are secondary (hepatogenous) photosensitization agents. Our results suggest that dehydro-PAs are the active metabolites responsible for skin cancer formation and PA-induced secondary photosensitization. PMID:21723383

  10. Pyrite-driven reactive oxygen species formation in simulated lung fluid: implications for coal workers' pneumoconiosis.

    PubMed

    Harrington, Andrea D; Hylton, Shavonne; Schoonen, Martin A A

    2012-08-01

    The origin of coal worker's pneumoconiosis (CWP) has been long debated. A recent epidemiological study shows a correlation between what is essentially the concentration of pyrite within coal and the prevalence of CWP in miners. Hydrogen peroxide and hydroxyl radical, both reactive oxygen species (ROS), form as byproducts of pyrite oxidative dissolution in air-saturated water. Motivated by the possible importance of ROS in the pathogenesis of CWP, we conducted an experimental study to evaluate if ROS form as byproducts in the oxidative dissolution of pyrite in simulated lung fluid (SLF) under biologically applicable conditions and to determine the persistence of pyrite in SLF. While the rate of pyrite oxidative dissolution in SLF is suppressed by 51% when compared to that in air-saturated water, the initial amount of hydrogen peroxide formed as a byproduct in SLF is nearly doubled. Hydroxyl radical is also formed in the experiments with SLF, but at lower concentrations than in the experiments with water. The formation of these ROS indicates that the reaction mechanism for pyrite oxidative dissolution in SLF is no different from that in water. The elevated hydrogen peroxide concentration in SLF suggests that the decomposition, via the Fenton mechanism to hydroxyl radical or with Fe(III) to form water and molecular oxygen, is initially inhibited by the presence of SLF components. On the basis of the oxidative dissolution rate of pyrite measured in this paper, it is calculated that a respirable two micron pyrite particle will take over 3 years to dissolve completely. PMID:21989857

  11. Soot formation in synthetic-fuel droplets. First quarterly technical progress report

    SciTech Connect

    England, G.; Kramlich, J.; Payne, R.

    1981-01-01

    The objective of this project is to provide detailed information on methods of minimizing soot formation during synthetic liquid fuel combustion under conditions which minimize fuel nitrogen conversion to nitric oxide. The program consists of two tasks. The purpose of the first task, Fuel Screening Studies, is to investigate the impact of fuel properties on particulate production, to establish the importance of droplet size and examine atomizer effects, and to develop techniques for surrogate fuels productions. In the second task, Flame Studies, the fundamental details of soot formation from synfuel droplet combustion will be investigated in variable slip velocity configurations. This present report describes technical progress during the first three months of the program effort (October-December 1980). During this initial period, attention has focused on the definition of the different experimental efforts and on the design and construction of the required hardware. Aspects of this work are discussed.

  12. Partial reactivation of a huge deep-seated ancient rock slide: recognition, formation mechanism, and stability

    NASA Astrophysics Data System (ADS)

    Tang, Minggao; Xu, Qiang; Li, Yusheng; Huang, Runqiu; Rengers, Niek; Zhu, Xing

    2016-08-01

    About 18 years ago, a large-scale discontinuous layer in properties and colour was found in the new Fengjie town at the shore of the Three Gorges Reservoir area in China. There are many resettled residents and buildings on the sloping area, the safety of which is potentially affected by this layer, so it has become the focus of attention. Before this study started there were two viewpoints regarding the origin of this layer. One was that is was from a huge ancient slide and the other was that is was from a fault graben. In order to find out how it was formed and to be able to carry out a stability analysis of the slope the authors have carried out a research program, including geological field investigations and mapping, a deep drilling hole, a geotechnical centrifuge model test, and a simulation analysis. The results of the research led to the conclusion that the layer is the sliding plane of a huge deep-seated ancient rock slide, which we called the Sanmashan landslide. An important argument for the conclusion is the recognition of a regional compressive tectonic stress field in this area, which cannot lead to the formation of a fault graben because it needs a tensional tectonic stress field. Moreover, numerous unique geological features, sliding marks, and other relics of the ancient slide have been discovered in the field. The formation process of the ancient slide could be repeated in a large geotechnical centrifuge model test. The test shows that a deformation and failure process of "creep-crack-cut" has occurred. The type of the ancient slide can be classified as a "successive rotational rock slide". Finally, the role of seepage in the stability of the Sanmashan landslide has been analysed. Our final conclusions are that, during rainfall and filling-drawdown cycles in the Three Gorges Reservoir, the Sanmashan landslide as a whole is dormant and stable and the secondary landslides in the toe area of the slope are presently stable but can be reactivated. This

  13. Inhibitors of biofilm formation by fuel ethanol contaminants

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Industrial fuel ethanol production suffers from chronic and acute infections that reduce yields and cause “stuck fermentations” that result in costly shutdowns. Lactic acid bacteria, particularly Lactobacillus sp., are recognized as major contaminants. In previous studies, we observed that certain...

  14. Formation and reactivation ages of a lunar mare ridge in northern Imbrium

    NASA Astrophysics Data System (ADS)

    Daket, Yuko; Yamaji, Atsushi; Sato, Katsushi; Morota, Tomokatsu; Haruyama, Junichi; Ohtake, Makiko; Matsunaga, Tsuneo

    2013-04-01

    Mare ridges and lobate scarps are the manifestations of ancient or recent horizontal compression in the shallow part of the Moon. Regional and global stress fields have been controlled possibly by mascon loading (e.g., Solomon and Head, 1980) and/or global cooling, the latter of which is affected by the origin of the Moon (e.g., Prichard and Stevenson, 2000). On the other hand, mascon loading results in tectonic deformations immediately after the deposition of mare fills (Mohit and Phillips, 2006). Therefore, the timing of deformations is a clue to distinguish the mechanisms. We constrained the formation age of a mare ridge in northern Mare Imbrium as follows. Mare basalts were so inviscid that their lava fields have level surfaces. And, lava flows would have been dammed by pre-existing mare ridges. Therefore, the depositional ages of the mare units-the one involved in the ridge and the other dammed by the ridge, indicate the range of the formation age of the ridge. Using images taken by SELENE (Kaguya), we found such an ENE-WSW trending ridge in northern Imbrium with the height, width and length of 300-400 m, 30 km and ~150 km, respectively. We defined spectrally distinctive two basaltic units in this area: Ti-poor basalt makes up the ridge, and relatively Ti-rich one lies on the plain at the foot of the ridge. Their boundary runs along the southern foot of the ridge. There are no fissures along the boundary that could have fed the Ti-rich basalt. Their model ages were estimated by crater-size frequency distribution measurements using craters of 250 m to 1 km in diameter. As a result, the Ti-poor and Ti-rich units gave the ages at 2.97 +0.16/-0.23 and 2.07 +0.17/-0.17 Ga, respectively, indicating the ridge was formed between ~3.0 and ~2.0 Ga. The majority of mare basalts in mare Imbrium were deposited before ~3.0 Ga (Solomon and Head, 1980), indicating that the ridge formation is explained as a latest event of the mascon loading. However, the unit boundary does

  15. Characteristics and trihalomethane formation reactivity of dissolved organic matter in effluents from membrane bioreactors with and without filamentous bulking.

    PubMed

    Xia, Chufan; Ma, Defang; Gao, Baoyu; Hu, Xinxiao; Yue, Qinyan; Meng, Yingjie; Kang, Shuyu; Zhang, Bei; Qi, Yuanfeng

    2016-07-01

    In this study, synthetic wastewater was treated by two identical membrane bioreactors (MBRs): the normal sludge MBR (NS-MBR) and the bulking sludge MBR (BS-MBR). Effects of filamentous bulking on the characteristics and trihalomethane (THM) formation reactivity of MBR effluent dissolved organic matter (EfOM) were investigated. Filamentous sludge bulking had no significant influence on the regulated MBR effluent water quality except NO2-N and NO3-N. NS-MBR effluent had more low molecular weight (LMW) (<5kDa) EfOM (92.43%) than BS-MBR (75.18%). About two-thirds of EfOM from BS-MBR were hydrophilic substances. On the contrary, EfOM from NS-MBR exhibited higher hydrophobicity. The ratio of polysaccharides and proteins in MBR effluents increased after filamentous bulking. There were more protein-like materials, fulvic acid-like and humic acid-like in BS-MBR EfOM. The THM formation reactivity of BS-MBR EfOM was 30.15% of NS-MBR EfOM, whereas BS-MBR EfOM exhibited higher formation reactivity of bromine containing species. PMID:27017128

  16. The development of reactive fuel grains for pyrophoric relight of in-space hybrid rocket thrusters

    NASA Astrophysics Data System (ADS)

    Steiner, Matthew Wellington

    This study presents and investigates a novel hybrid fuel grain that reacts pyrophorically with gaseous oxidizer to achieve restart of a hybrid rocket motor propulsion system while reducing cost and handling concerns. This reactive fuel grain (RFG) relies on the pyrophoric nature of finely divided metal particles dispersed in a solid dicyclopentadiene (DCPD) binder, which has been shown to encapsulate air-sensitive additives until they are exposed to combustion gases. An RFG is thus effectively inert in open air in the absence of an ignition source, though the particles encapsulated within remain pyrophoric. In practice, this means that an RFG that is ignited in the vacuum of space and then extinguished will expose unoxidized pyrophoric particles, which can be used to generate sufficient heat to relight the propellant when oxidizer is flowed. The experiments outlined in this work aim to develop a suitable pyrophoric material for use in an RFG, demonstrate pyrophoric relight, and characterize performance under conditions relevant to a hybrid rocket thruster. Magnesium, lithium, calcium, and an alloy of titanium, chromium, and manganese (TiCrMn) were investigated to determine suitability of pure metals as RFG additives. Additionally, aluminum hydride (AlH3), lithium aluminum hydride (LiAlH4), lithium borohydride (LiBH4), and magnesium hydride (MgH2) were investigated to determine suitability of metals hydrides as RFG additives or as precursors for pure-metal RFG additives. Pyrophoric metals have been previously investigated as additives for increasing the regression rate of hybrid fuels, but to the author's knowledge, these materials have not been specifically investigated for their ability to ignite a propellant pyrophorically. Commercial research-grade metals were obtained as coarse powders, then ball-milled to attempt to reduce particle size below a critical diameter needed for pyrophoricity. Magnesium hydride was ball-milled and then cycled in a hydride cycling

  17. Liquid phase products and solid deposit formation from thermally stressed model jet fuels

    NASA Technical Reports Server (NTRS)

    Kim, W. S.; Bittker, D. A.

    1984-01-01

    The relationship between solid deposit formation and liquid degradation product concentration was studied for the high temperature (400 C) stressing of three hydrocarbon model fuels. A Jet Fuel Thermal Oxidation Tester was used to simulate actual engine fuel system conditions. The effects of fuel type, dissolved oxygen concentration, and hot surface contact time (reaction time) were studied. Effects of reaction time and removal of dissolved oxygen on deposit formation were found to be different for n-dodecane and for 2-ethylnaphthalene. When ten percent tetralin is added to n-dodecane to give a simpler model of an actual jet fuel, the tetralin inhibits both the deposit formation and the degradation of n-dodecane. For 2-ethylnaphthalene primary product analyses indicate a possible self-inhibition at long reaction times of the secondary reactions which form the deposit precursors. The mechanism of the primary breakdown of these fuels is suggested and the primary products which participate in these precursor-forming reactions are identified. Some implications of the results to the thermal degradation of real jet fuels are given.

  18. Spacecraft fuel-optimal and balancing maneuvers for a class of formation reconfiguration problems

    NASA Astrophysics Data System (ADS)

    Yoo, Sung-Moon; Lee, Sangjin; Park, Chandeok; Park, Sang-Young

    2013-10-01

    This paper presents fuel optimal and balancing methodologies for reconfiguring multiple spacecraft in formation subject to a Newtonian gravity field. For a kind of continuous-thrust propulsion system, a fuel-optimal control problem is formulated to minimize the integral squared control subject to the linearized Hill or Clohessy-Wiltshire dynamics of relative motion with respect to a circular reference orbit. Palmer's analytical solution for general reconfiguration is adapted to maneuvers between projected circular orbits, resulting in the optimal fuel consumption index as a function of configuration parameters such as orbit radius, phase angle, and transfer time. Parametric analyses reveal unique characteristics of individual fuel optimality and gross fuel consumption: for an arbitrary selection of initial/terminal orbit radii, (i) there exist special transfer times such that individual fuel consumption is optimally uniform for all phase angles, and (ii) the total fuel expenditure for a group of three or more spacecraft is invariant for the relatively same configuration with respect to the departure phase. These results serve to effectively design fuel balancing strategies for formation reconfiguration of multiple spacecraft.

  19. Effects of uncertainty in SAPRC90 rate constants and selected product yields on reactivity adjustment factors for alternative fuel vehicle emissions. Final report

    SciTech Connect

    Bergin, M.S.; Russell, A.G.; Yang, Y.J.; Milford, J.B.; Kirchner, F.; Stockwell, W.R.

    1996-07-01

    Tropospheric ozone is formed in the atmosphere by a series of reactions involving volatile organic compounds (VOCs) and nitrogen oxides (NO{sub x}). While NOx emissions are primarily composed of only two compounds, nitrogen oxide (NO) and nitrogen dioxide (NO{sub 2}), there are hundreds of different VOCs being emitted. In general, VOCs promote ozone formation, however, the rate and extent of ozone produced by the individual VOCs varies considerably. For example, it is widely acknowledged that formaldehyde (HCHO) is a very reactive VOC, and produces ozone rapidly and efficiently under most conditions. On the other hand, VOCs such as methane, ethane, propane, and methanol do not react as quickly, and are likely to form less urban ozone than a comparable mass of HCHO. The difference in ozone forming potential is one of the bases for the use of alternative fuels. The fuels considered in this study included compressed natural gas, LPG, mixtures of methanol and gasoline, ethanol and gasoline, and a reformulated gasoline.

  20. (Formation of fuel via photochemical electron transfer). Annual report

    SciTech Connect

    Jones, G.

    1985-03-04

    Accomplishments for the past year are reported under the following three main headings, in addition to several other related studies: (1) heterocyclic sulfur compounds which display unusual properties as electron relays which may be important in chemical or fuel forming reactions; (2) cationic dyes which tend to aggregate in interesting ways when bound to polyanion in water; and (3) photochemistry of viologen or pyridinium ions which are complexed or ion-paired with electron donors. A publications update is appended with references cited in this report.

  1. Electrochemical synthesis and reactivity screening of a ternary composition gradient for combinatorial discovery of fuel cell catalysts

    NASA Astrophysics Data System (ADS)

    Jayaraman, S.; Hillier, A. C.

    2005-01-01

    This paper describes a method for synthesis of multi-component gradient libraries for combinatorial catalyst discovery. A 'gel-transfer' synthesis method is demonstrated that involves localized diffusion of aqueous precursor metal salts into a hydrated gel to establish spatially varying concentration fields. Electrodeposition is then used to transfer the gradient in metal precursors to a surface. To illustrate the utility of this method, a platinum-ruthenium-rhodium (PtxRuyRhz) catalyst gradient was constructed, and its reactivity towards several fuel cell reactions evaluated. An optical screening technique based upon the pH-sensitive fluorescence of quinine was used to visualize the spatial onset of reactivity on the ternary catalyst gradient. The evolution of protons from several reactions of interest for low temperature fuel cells was visualized by quinine fluorescence. The oxidation of hydrogen, carbon monoxide, methanol and ethanol were tested on the catalyst library. Catalyst regions that exhibited fluorescence (and hence the onset of activity) at lowest potentials were identified for each of the above reactions.

  2. Methods and apparatuses for reagent delivery, reactive barrier formation, and pest control

    DOEpatents

    Gilmore, Tyler [Pasco, WA; Kaplan, Daniel I [Aiken, SC; Last, George [Richland, WA

    2002-07-09

    A reagent delivery method includes positioning reagent delivery tubes in contact with soil. The tubes can include a wall that is permeable to a soil-modifying reagent. The method further includes supplying the reagent in the tubes, diffusing the reagent through the permeable wall and into the soil, and chemically modifying a selected component of the soil using the reagent. The tubes can be in subsurface contact with soil, including groundwater, and can be placed with directional drilling equipment independent of groundwater well casings. The soil-modifying reagent includes a variety of gases, liquids, colloids, and adsorbents that may be reactive or non-reactive with soil components. The method may be used inter alia to form reactive barriers, control pests, and enhance soil nutrients for microbes and plants.

  3. Isotope effects in methanol synthesis and the reactivity of copper formates on a Cu/SiO2 catalyst

    SciTech Connect

    Yang, Yong; Mims, Charles A.; Disselkamp, Robert S.; Mei, Donghai; Kwak, Ja Hun; Szanyi, Janos; Peden, Charles HF; Campbell, C. T.

    2008-10-01

    Here we investigate isotope effects on the catalytic methanol synthesis reaction and the reactivity of copper-bound formate species in CO2-H2 atmospheres on Cu/SiO2 catalysts by simultaneous IR and MS measurements, both steady-state and transient. Studies of isotopic variants (H/D, 12C/13C) reveal that bidentate formate dominates the copper surface at steady state. The steady-state formate coverages of HCOO (in 6 bar 3:1 H2:CO2) and DCOO (in D2:CO2) are similar and the steady-state formate coverages in both systems decrease by ~80% from 350 K to 550 K. Over the temperature range 413K – 553K, the steady-state methanol synthesis rate shows a weak H/D isotope effect (1.05 ± 0.05) with somewhat higher activation energies in H2:CO2 (79 kJ/mole) than D2:CO2 (71 kJ/mole) over the range 473K-553K. The reverse water gas shift (RWGS) rates are higher than methanol synthesis and also shows a weak positive H/D isotope effect with higher activation energy for H2/CO2 than D2/CO2 (108 vs. and 102 kJ/mole). The reactivity of the resulting formate species in 6 bar H2, 6 bar D2 and 6 bar Ar is strongly dominated by decomposition back to CO2 and H2. H2 and D2 exposure compared to Ar do not enhance the formate decomposition rate. The decomposition profiles on the supported catalyst deviate from first order decay, indicating distributed surface reactivity. The average decomposition rates are similar to values previously reported on single crystals. The average activation energies for formate decomposition are 90 ± 17 kJ/mole for HCOO and 119 ± 11 kJ/mole for DCOO. By contrast to the catalytic reaction rates, the formate decomposition rate shows a strong H/D kinetic isotope effect (H/D ~ 8 at 413K), similar to previously observed values on Cu(110).

  4. Mechanical performance of reactive-air-brazed (RAB) ceramic/metal joints for solid oxide fuel cells at ambient temperature

    NASA Astrophysics Data System (ADS)

    Kuhn, B.; Wetzel, F. J.; Malzbender, J.; Steinbrech, R. W.; Singheiser, L.

    Mechanical integrity of the sealants in planar SOFC stacks is a key prerequisite for reliable operation. In this respect joining with metals rather than brittle glass-ceramics is considered to have advantages. Hence, as one of the joining solutions for SOFCs of planar design, reactive air brazing of ceramic cells into metallic frames gains increasing interest. Fracture experiments are carried out to characterize fracture energy and failure mechanisms of silver-based reactive-air-brazes, used for joining the zirconia electrolytes of anode supported planar cells with metallic Crofer22APU frames. The specimens are mechanically tested in notched beam bending geometry. In-situ observation in optical and SEM resolution reveals specific failure mechanisms. The influence of braze formulation and associated interfacial reactions on the crack path location is addressed. Discussion of the results focuses in particular on the role of oxide scale formation.

  5. Manipulation of combustion waves in carbon-nanotube/fuel composites by highly reactive Mg nanoparticles.

    PubMed

    Lee, Kang Yeol; Hwang, Hayoung; Shin, Dongjoon; Choi, Wonjoon

    2015-10-28

    Manipulating the interface of micro/nanostructured materials and chemical fuels can change the fundamental characteristics of combustion waves that are generated during a reaction. In this study, we report that Mg/MgO nanoparticles actively amplify the propagation of combustion waves at the interface of multi-walled carbon nanotubes (MWCNTs) and chemical fuels. Fuel/MWCNT and fuel/MWCNT-Mg/MgO composite films were prepared by a facile synthetic method. We present complete physiochemical characterization of these composite films and evaluate the propagating velocities and real-time surface temperatures of combustion waves. Mg/MgO nanoparticles at the interface enhanced the reaction front velocity by 41%. The resulting explosive reactions supplied additional thermal energy to the chemical fuel, accelerating flame propagation. Furthermore, the surface temperatures of the composites with Mg/MgO nanoparticles were much lower, indicating how the transient heat from the reaction would ignite the unreacted fuels at lower surface temperatures despite not reaching the necessary activation energy for a chain reaction. This mechanism contributed to thermopower waves that amplified the output voltage. Furthermore, large temperature gradients due to the presence of nanoparticles increased charge transport inside the nanostructured material, due to the increased thermoelectric effects. This manipulation could contribute to the active control of interfacially driven combustion waves along nanostructured materials, yielding many potential applications. PMID:26419765

  6. Electrospray formation of gelled nano-aluminum microspheres with superior reactivity.

    PubMed

    Wang, Haiyang; Jian, Guoqiang; Yan, Shi; DeLisio, Jeffery B; Huang, Chuan; Zachariah, Michael R

    2013-08-14

    Nanometallic fuels with high combustion enthalpy, such as aluminum, have been proposed as a potential fuel replacement for conventional metallic fuel to improve propellant performance in a variety of propulsive systems. Nevertheless, nanometallic fuels suffer from the processing challenges in polymer formulations such as increased viscosity and large agglomeration, which hinder their implementation. In this letter, we employ electrospray as a means to create a gel within a droplet, via a rapid, solvent evaporation-induced aggregation of aluminum nanoparticles, containing a small mass fraction of an energetic binder. The gelled aluminum microspheres were characterized and tested for their burning behavior by rapid wire heating ignition experiments. The gelled aluminum microspheres show enhanced combustion behavior compared to nanoaluminum, which possibly benefits from the nitrocellulose coating and the gelled microstructure, and is far superior to the corresponding dense micrometer-sized aluminum. PMID:23875780

  7. Photocatalytic Reactive Oxygen Species Formation by Semiconductor-Metal Hybrid Nanoparticles. Toward Light-Induced Modulation of Biological Processes.

    PubMed

    Waiskopf, Nir; Ben-Shahar, Yuval; Galchenko, Michael; Carmel, Inbal; Moshitzky, Gilli; Soreq, Hermona; Banin, Uri

    2016-07-13

    Semiconductor-metal hybrid nanoparticles manifest efficient light-induced spatial charge separation at the semiconductor-metal interface, as demonstrated by their use for hydrogen generation via water splitting. Here, we pioneer a study of their functionality as efficient photocatalysts for the formation of reactive oxygen species. We observed enhanced photocatalytic activity forming hydrogen peroxide, superoxide, and hydroxyl radicals upon light excitation, which was significantly larger than that of the semiconductor nanocrystals, attributed to the charge separation and the catalytic function of the metal tip. We used this photocatalytic functionality for modulating the enzymatic activity of horseradish peroxidase as a model system, demonstrating the potential use of hybrid nanoparticles as active agents for controlling biological processes through illumination. The capability to produce reactive oxygen species by illumination on-demand enhances the available peroxidase-based tools for research and opens the path for studying biological processes at high spatiotemporal resolution, laying the foundation for developing novel therapeutic approaches. PMID:27224678

  8. Reactive retinal microglia, neuronal survival and the formation of retinal folds and detachments

    PubMed Central

    Fischer, Andy J.; Zelinka, Christopher; Milani-Nejad, Nima

    2014-01-01

    Reactive microglia and macrophages are prevalent in damaged retinas. Accordingly, we investigate how the activation or ablation of microglia/macrophages influences the survival of neurons in the chick retina in vivo. We applied intraocular injections of interleukin 6 (IL6) to stimulate the reactivity of microglia/macrophages and clodronate-liposomes to ablate microglia/macrophages. Activation of the microglia/macrophages with IL6 delays the death of retinal neurons from N-methyl-D-aspartate (NMDA) -induced excitotoxicity. In addition, activation of microglia/macrophages combined with colchicine-mediated retinal damage diminished the survival of ganglion cells. Application of IL6 after an excitotoxic insult greatly exacerbates the damage, and causes widespread retinal detachments and folds, accompanied by accumulation of microglia/macrophages in the subretinal space. Damage-induced retinal folds and detachments were significantly reduced by the ablation of microglia/macrophages. We conclude that microglial reactivity is detrimental to the survival of ganglion cells in colchicine-damaged retinas and detrimental to the survival of photoreceptors in retinal folds. In addition, we conclude that IL6-treatment transiently protects amacrine and bipolar cells against an excitotoxic insult. We propose that suppressing reactivity of microglia/macrophages may be an effective means to lessen the damage and vision loss resulting from damage, in particular during retinal detachment injuries. PMID:25231952

  9. MODELING THE ATMOSPHERE FORMATION OF REACTIVE MERCURY IN FLORIDA AND THE GREAT LAKES

    EPA Science Inventory

    Reactive mercury in the troposphere is affected by a complex mix of local emissions, global-scale transport, and gas and aqueous-phase chemistry. Here, we describe a modified version of the EPA model for urban/regional air quality (CMAQ) to include the chemistry of mercury, and m...

  10. The Role of Proactive and Reactive Aggression in the Formation and Development of Boys' Friendships.

    ERIC Educational Resources Information Center

    Poulin, Francois; Boivin, Michel

    2000-01-01

    Tested the hypothesis that friends are more similar in proactive aggression than in reactive aggression with 185 fourth- to sixth-grade boys and examined interpersonal processes that may account for this similarity. Suggested that proactively aggressive boys tended to select proactively aggressive peers as friends; however, mutual influence…

  11. Electrochemistry-Mass Spectrometry Unveils the Formation of Reactive Triclocarban MetabolitesS⃞

    PubMed Central

    Baumann, A.; Lohmann, W.; Rose, T.; Ahn, K. C.; Hammock, B. D.; Karst, U.

    2010-01-01

    Triclocarban (3,4,4′-trichlorocarbanilide, TCC) is a widely used antibacterial agent in personal care products and is frequently detected as an environmental pollutant in waste waters and surface waters. In this study, we report novel reactive metabolites potentially formed during biotransformation of TCC. The oxidative metabolism of TCC has been predicted using an electrochemical cell coupled online to liquid chromatography and electrospray ionization mass spectrometry. The electrochemical oxidation unveils the fact that hydroxylated metabolites of TCC may form reactive quinone imines. Moreover, a so-far unknown dechlorinated and hydroxylated TCC metabolite has been identified. The results were confirmed by in vitro studies with human and rat liver microsomes. The reactivity of the newly discovered quinone imines was demonstrated by their covalent binding to glutathione and macromolecules, using β-lactoglobulin A as a model protein. The results regarding the capability of the electrochemical cell to mimic the oxidative metabolism of TCC are discussed. Moreover, the occurrence of reactive metabolites is compared with findings from earlier in vivo studies and their relevance in vivo is argued. PMID:20861155

  12. Electrochemistry-mass spectrometry unveils the formation of reactive triclocarban metabolites.

    PubMed

    Baumann, A; Lohmann, W; Rose, T; Ahn, K C; Hammock, B D; Karst, U; Schebb, N H

    2010-12-01

    Triclocarban (3,4,4'-trichlorocarbanilide, TCC) is a widely used antibacterial agent in personal care products and is frequently detected as an environmental pollutant in waste waters and surface waters. In this study, we report novel reactive metabolites potentially formed during biotransformation of TCC. The oxidative metabolism of TCC has been predicted using an electrochemical cell coupled online to liquid chromatography and electrospray ionization mass spectrometry. The electrochemical oxidation unveils the fact that hydroxylated metabolites of TCC may form reactive quinone imines. Moreover, a so-far unknown dechlorinated and hydroxylated TCC metabolite has been identified. The results were confirmed by in vitro studies with human and rat liver microsomes. The reactivity of the newly discovered quinone imines was demonstrated by their covalent binding to glutathione and macromolecules, using β-lactoglobulin A as a model protein. The results regarding the capability of the electrochemical cell to mimic the oxidative metabolism of TCC are discussed. Moreover, the occurrence of reactive metabolites is compared with findings from earlier in vivo studies and their relevance in vivo is argued. PMID:20861155

  13. The effect of the composition of plutonium loaded on the reactivity change and the isotopic composition of fuel produced in a fast reactor

    SciTech Connect

    Blandinskiy, V. Yu.

    2014-12-15

    This paper presents the results of a numerical investigation into burnup and breeding of nuclides in metallic fuel consisting of a mixture of plutonium and depleted uranium in a fast reactor with sodium coolant. The feasibility of using plutonium contained in spent nuclear fuel from domestic thermal reactors and weapons-grade plutonium is discussed. It is shown that the largest production of secondary fuel and the least change in the reactivity over the reactor lifetime can be achieved when employing plutonium contained in spent nuclear fuel from a reactor of the RBMK-1000 type.

  14. The effect of the composition of plutonium loaded on the reactivity change and the isotopic composition of fuel produced in a fast reactor

    NASA Astrophysics Data System (ADS)

    Blandinskiy, V. Yu.

    2014-12-01

    This paper presents the results of a numerical investigation into burnup and breeding of nuclides in metallic fuel consisting of a mixture of plutonium and depleted uranium in a fast reactor with sodium coolant. The feasibility of using plutonium contained in spent nuclear fuel from domestic thermal reactors and weapons-grade plutonium is discussed. It is shown that the largest production of secondary fuel and the least change in the reactivity over the reactor lifetime can be achieved when employing plutonium contained in spent nuclear fuel from a reactor of the RBMK-1000 type.

  15. Long-term kinetic effects and colloid formations in dissolution of LWR spent fuels

    SciTech Connect

    Ahn, T.M.

    1996-11-01

    This report evaluates continuous dissolution and colloid formation during spent-fuel performance under repository conditions in high-level waste disposal. Various observations suggest that reprecipitated layers formed on spent-fuel surfaces may not be protective. This situation may lead to continuous dissolution of highly soluble radionuclides such as C-14, Cl-36, Tc-99, I-129, and Cs-135. However, the diffusion limits of various species involved may retard dissolution significantly. For low-solubility actinides such as Pu-(239+240) or Am-(241+243), various processes regarding colloid formation have been analyzed. The processes analyzed are condensation, dispersion, and sorption. Colloid formation may lead to significant releases of low-solubility actinides. However, because there are only limited data available on matrix dissolution, colloid formation, and solubility limits, many uncertainties still exist. These uncertainties must be addressed before the significance of radionuclide releases can be determined. 118 refs.

  16. Using fluorescence-activated flow cytometry to determine reactive oxygen species formation and membrane lipid peroxidation in viable boar spermatozoa.

    PubMed

    Guthrie, H David; Welch, Glenn R

    2010-01-01

    Fluorescence-activated flow cytometry analyses were developed for determination of reactive oxygen species (ROS) formation and membrane lipid peroxidation in live spermatozoa loaded with, respectively, hydroethidine (HE) or the lipophilic probe 4,4-difluoro-5-(4-phenyl-1,3-butadienyl)-4-bora-3a,4a-diaza-s-indacene-3-undecanoic acid, C(11)BODIPY(581/591) (BODIPY). ROS was detected by red fluorescence emission from oxidization of HE and membrane lipid peroxidation was detected by green fluorescence emission from oxidation of BODIPY in individual live sperm. Of the reactive oxygen species generators tested, BODIPY oxidation was specific for FeSo4/ascorbate (FeAc), because menadione and H(2)O(2) had little or no effect. The oxidization of hydroethidine to ethidium was specific for menadione and H(2)O(2); FeAc had no effect. The incidence of basal or spontaneous ROS formation and membrane lipid peroxidation were low in boar sperm (<1% of live sperm) in fresh semen or after low temperature storage; however the sperm were quite susceptible to treatment-induced ROS formation and membrane lipid peroxidation. PMID:20072917

  17. Manipulation of combustion waves in carbon-nanotube/fuel composites by highly reactive Mg nanoparticles

    NASA Astrophysics Data System (ADS)

    Lee, Kang Yeol; Hwang, Hayoung; Shin, Dongjoon; Choi, Wonjoon

    2015-10-01

    Manipulating the interface of micro/nanostructured materials and chemical fuels can change the fundamental characteristics of combustion waves that are generated during a reaction. In this study, we report that Mg/MgO nanoparticles actively amplify the propagation of combustion waves at the interface of multi-walled carbon nanotubes (MWCNTs) and chemical fuels. Fuel/MWCNT and fuel/MWCNT-Mg/MgO composite films were prepared by a facile synthetic method. We present complete physiochemical characterization of these composite films and evaluate the propagating velocities and real-time surface temperatures of combustion waves. Mg/MgO nanoparticles at the interface enhanced the reaction front velocity by 41%. The resulting explosive reactions supplied additional thermal energy to the chemical fuel, accelerating flame propagation. Furthermore, the surface temperatures of the composites with Mg/MgO nanoparticles were much lower, indicating how the transient heat from the reaction would ignite the unreacted fuels at lower surface temperatures despite not reaching the necessary activation energy for a chain reaction. This mechanism contributed to thermopower waves that amplified the output voltage. Furthermore, large temperature gradients due to the presence of nanoparticles increased charge transport inside the nanostructured material, due to the increased thermoelectric effects. This manipulation could contribute to the active control of interfacially driven combustion waves along nanostructured materials, yielding many potential applications.Manipulating the interface of micro/nanostructured materials and chemical fuels can change the fundamental characteristics of combustion waves that are generated during a reaction. In this study, we report that Mg/MgO nanoparticles actively amplify the propagation of combustion waves at the interface of multi-walled carbon nanotubes (MWCNTs) and chemical fuels. Fuel/MWCNT and fuel/MWCNT-Mg/MgO composite films were prepared by a facile

  18. Nondestructive determination of plutonium mass in spent fuel: prelliminary modeling results using the passive neutron Albedo reactivity technique

    SciTech Connect

    Evans, Louise G; Tobin, Stephen J; Schear, Melissa A; Menlove, Howard O; Lee, Sang Y; Swinhoe, Martyn T

    2009-01-01

    There are a variety of motivations for quantifying plutonium (Pu) in spent fuel assemblies by means of nondestructive assay (NDA) including the following: strengthening the capability of the International Atomic Energy Agency (LAEA) to safeguard nuclear facilities, quantifying shipper/receiver difference, determining the input accountability value at pyrochemical processing facilities, providing quantitative input to burnup credit and final safeguards measurements at a long-term repository. In order to determine Pu mass in spent fuel assemblies, thirteen NDA techniques were identified that provide information about the composition of an assembly. A key motivation of the present research is the realization that none of these techniques, in isolation, is capable of both (1) quantifying the Pu mass of an assembly and (2) detecting the diversion of a significant number of rods. It is therefore anticipated that a combination of techniques will be required. A 5 year effort funded by the Next Generation Safeguards Initiative (NGSI) of the U.S. DOE was recently started in pursuit of these goals. The first two years involves researching all thirteen techniques using Monte Carlo modeling while the final three years involves fabricating hardware and measuring spent fuel. Here, we present the work in two main parts: (1) an overview of this NGSI effort describing the motivations and approach being taken; (2) The preliminary results for one of the NDA techniques - Passive Neutron Albedo Reactivity (PNAR). The PNAR technique functions by using the intrinsic neutron emission of the fuel (primarily from the spontaneous fission of curium) to self-interrogate any fissile material present. Two separate measurements of the spent fuel are made, both with and without cadmium (Cd) present. The ratios of the Singles, Doubles and Triples count rates obtained in each case are analyzed; known as the Cd ratio. The primary differences between the two measurements are the neutron energy spectrum

  19. The role of proactive and reactive aggression in the formation and development of boys' friendships.

    PubMed

    Poulin, F; Boivin, M

    2000-03-01

    This study tested the hypothesis that friends are more similar in proactive aggression than in reactive aggression. Interpersonal processes that may account for this similarity (i.e., selection and mutual influence) were also examined. In the fall and spring of the school year, the friendships of 185 4th-, 5th-, and 6th-grade boys were identified. Proactive and reactive aggressive behavior were assessed with a teacher-rating instrument for each boy. The results support the general hypothesis and suggest that proactively aggressive boys tend to select proactively aggressive peers as friends; however, mutual influence between stable friends does not appear to account for similarity. These findings are discussed within the framework of G. R. Patterson, J. B. Reid, and T. J. Dishion's (1992) theory of antisocial behavior. PMID:10749080

  20. Formate: an Energy Storage and Transport Bridge between Carbon Dioxide and a Formate Fuel Cell in a Single Device.

    PubMed

    Vo, Tracy; Purohit, Krutarth; Nguyen, Christopher; Biggs, Brenna; Mayoral, Salvador; Haan, John L

    2015-11-01

    We demonstrate the first device to our knowledge that uses a solar panel to power the electrochemical reduction of dissolved carbon dioxide (carbonate) into formate that is then used in the same device to operate a direct formate fuel cell (DFFC). The electrochemical reduction of carbonate is carried out on a Sn electrode in a reservoir that maintains a constant carbon balance between carbonate and formate. The electron-rich formate species is converted by the DFFC into electrical energy through electron release. The product of DFFC operation is the electron-deficient carbonate species that diffuses back to the reservoir bulk. It is possible to continuously charge the device using alternative energy (e.g., solar) to convert carbonate to formate for on-demand use in the DFFC; the intermittent nature of alternative energy makes this an attractive design. In this work, we demonstrate a proof-of-concept device that performs reduction of carbonate, storage of formate, and operation of a DFFC. PMID:26510492

  1. ICP-Enhanced Sputter Deposition for Reactivity Control and Low-Temperature Formation of a-IGZO Films

    NASA Astrophysics Data System (ADS)

    Setsuhara, Yuichi; Nakata, Keitaro; Satake, Yoshikatsu; Takenaka, Kosuke; Uchida, Giichiro; Ebe, Akinori

    2015-09-01

    Inductively coupled plasma (ICP) - enhanced sputter deposition for a-IGZO channel TFTs fabrication have been performed. This advantage of fine control of reactivity during the deposition process is of great significance for film deposition of the transparent amorphous oxide semiconductor, a-InGaZnOx (a-IGZO), whose electrical properties are significantly sensitive to the reactivity during the film deposition. The a-IGZO film deposition with addition of H2 gas were performed in order to control oxidation process during a-IGZO film formation via balance between oxidation-reduction. The results of optical emission spectrum indicate the possibility for the suppression of oxidation by oxygen atoms of a-IGZO films during deposition due to addition of H2 gas. The characteristics of TFT fabricated with IGZO film via plasma-enhanced magnetron sputter deposition system have been investigated. The result exhibits that the possibility of expanding process window for control of balance between oxidization and reduction by addition of H2 gas. The a-IGZO channel TFTs fabricated plasma-enhanced reactive sputtering system with addition of H2 gas exhibited good performance of field-effect mobility 15.3 cm2(Vs)-1 and subthreshold gate voltage swing (S) of 0.48 V decade-1. This work was partly supported by ASTEP (JST) and Grant-in-Aid for Challenging Exploratory Research (JSPS).

  2. REACTIVE DESORPTION AND RADIATIVE ASSOCIATION AS POSSIBLE DRIVERS OF COMPLEX MOLECULE FORMATION IN THE COLD INTERSTELLAR MEDIUM

    SciTech Connect

    Vasyunin, A. I.; Herbst, Eric E-mail: eh2ef@virginia.edu

    2013-05-20

    The recent discovery of terrestrial-type organic species such as methyl formate and dimethyl ether in the cold interstellar gas has proved that the formation of organic matter in the Galaxy begins at a much earlier stage of star formation than was previously thought. This discovery represents a challenge for astrochemical modelers. The abundances of these molecules cannot be explained by the previously developed ''warm-up'' scenario, in which organic molecules are formed via diffusive chemistry on surfaces of interstellar grains starting at 30 K, and then released to the gas at higher temperatures during later stages of star formation. In this article, we investigate an alternative scenario in which complex organic species are formed via a sequence of gas-phase reactions between precursor species formed on grain surfaces and then ejected into the gas via efficient reactive desorption, a process in which non-thermal desorption occurs as a result of conversion of the exothermicity of chemical reactions into the ejection of products from the surface. The proposed scenario leads to reasonable if somewhat mixed results at temperatures as low as 10 K and may be considered as a step toward the explanation of abundances of terrestrial-like organic species observed during the earliest stages of star formation.

  3. From the Nano- to the Formation Scale: Accessible Reactive Surface Area in a CO2 Saline Reservoir

    NASA Astrophysics Data System (ADS)

    Swift, A.; Cole, D. R.; Sheets, J. M.; Anovitz, L. M.

    2015-12-01

    Among the outstanding subsurface science challenges today is the translation of our improved understanding of pore-scale reactive transport and bench-scale geochemical rates of reaction to the prediction of long-term formation response to the sequestration of carbon dioxide. The emergent complexity of CO2-brine-rock interactions, on a large scale, over long periods of time (up to 1000 years) arises from a number of imperfectly understood factors. Of these, the accessibility of reactive surfaces distinguishes natural materials from powders commonly used in reaction rate studies, and geologic heterogeneity requires a workflow that connects samples, not to depths, but to material types that, combined, constitute a subsurface formation. To this end, core samples targeting every lithology type (quartz arenite, quartz-feldspar arenite, hematitic matrix-rich sandstone, clay-silt lens) observed in two bore holes through the Mt. Simon Sandstone of Ohio have been interrogated. Small- and ultra small-angle neutron scattering (SANS, USANS) and mercury and gas porosimetry (MICP, BET) have been used to quantify pore and pore throat distributions, and therefore pore volume accessibility at any given intrusion pressure. Mineral surface area is calculated using high-resolution SEM-BSE imagery combined with energy dispersive X-ray mineral mapping, and then extended beyond the limit of image-based techniques by using BET estimates for specific minerals. Combined, these datasets enable the quantification of mineral-specific, connected surface area as a function of pore/fracture scale. This is a defining feature of a pore-mineral assemblage, the microanalysis analogue of a macroscale lithology. The whole formation is then reconstructed by connecting pore-mineral assemblages to lithologies, defined by permeability/porosity and by mineralogy, and these in turn to the whole vertical extent of the formation using coarser-scale images of whole core. This effort therefore contributes both to

  4. Measurement of the atmospheric reactivity of emissions from gasoline and alternative-fueled vehicles: Assessment of available methodologies. Part 1. Indoor smog chamber study of reactivity. Final report for the first year, January 1-December 31, 1993

    SciTech Connect

    Kelly, N.A.; Wang, P.; Japar, S.M.; Hurley, M.D.; Wallington, T.J.

    1994-06-30

    A set of multiple indoor smog chambers were used to measure the increase in smog formation (smog = NO oxidation + O3 formation) from a series of individual test volatile organic compounds (VOC`s), as well as carbon monoxide (CO), when they were added to a standard urban mixture and irradiated for 10-12 hours with a solar simulator. The chambers and the mixtures were designed to simulate the Carter incremental reactivity concept that is being used in California. The test compounds covered a wide range of mechanistic uncertainties and predicted reactivities (reactivity is the increase in smog divided by the amount of test compound added). Also, the chambers were used to test the recently developed Integrated Empirical Rate (IER) Model which predicts that the smog formation of a mixture is constant and independent of NOx in the so-called light-limited regime.

  5. Organic aerosol formation from the reactive uptake of isoprene epoxydiols (IEPOX) onto non-acidified inorganic seeds

    NASA Astrophysics Data System (ADS)

    Nguyen, T. B.; Coggon, M. M.; Bates, K. H.; Zhang, X.; Schwantes, R. H.; Schilling, K. A.; Loza, C. L.; Flagan, R. C.; Wennberg, P. O.; Seinfeld, J. H.

    2014-04-01

    The reactive partitioning of cis and trans β-IEPOX was investigated on hydrated inorganic seed particles, without the addition of acids. No organic aerosol (OA) formation was observed on dry ammonium sulfate (AS); however, prompt and efficient OA growth was observed for the cis and trans β-IEPOX on AS seeds at liquid water contents of 40-75% of the total particle mass. OA formation from IEPOX is a kinetically limited process, thus the OA growth continues if there is a reservoir of gas-phase IEPOX. There appears to be no differences, within error, in the OA growth or composition attributable to the cis / trans isomeric structures. Reactive uptake of IEPOX onto hydrated AS seeds with added base (NaOH) also produced high OA loadings, suggesting the pH dependence for OA formation from IEPOX is weak for AS particles. No OA formation, after particle drying, was observed on seed particles where Na+ was substituted for NH4+. The Henry's Law partitioning of IEPOX was measured on NaCl particles (ionic strength ~9 M) to be 3 × 107 M atm-1 (-50 / +100%). A small quantity of OA was produced when NH4+ was present in the particles, but the chloride (Cl-) anion was substituted for sulfate (SO42-), possibly suggesting differences in nucleophilic strength of the anions. Online time-of-flight aerosol mass spectrometry and offline filter analysis provide evidence of oxygenated hydrocarbons, organosulfates, and amines in the particle organic composition. The results are consistent with weak correlations between IEPOX-derived OA and particle acidity or liquid water observed in field studies, as the chemical system is nucleophile-limited and not limited in water or catalyst activity.

  6. A Study of Pollutant Formation from the Lean Premixed Combustion of Gaseous Fuel Alternatives to Natural Gas

    NASA Astrophysics Data System (ADS)

    Fackler, Keith Boyd, Jr.

    emissions decrease with increasing H2 fuel fraction for combustion of CH4/H2 blends. This appears to be caused by a reduction in the amount of NO made by the prompt pathway involving the reaction of N2 with hydrocarbon radicals as the CH4 is replaced by H2. 2.) For category 2 (the process and refinery blend) and category 5 (the LNG, shale, and associated gases), NOx emissions increase with the addition of C2 and C3 hydrocarbons. This could be due to an increased production of free radicals resulting from increasing CO production when higher molecular weight hydrocarbons are broken down. 3.) For category 3 (the O2 blown gasified coal/petcoke), NOx emissions increase with increasing CO fuel fraction. The reason for this is attributed to CO producing more radicals per unit heat release than H2. When CO replaces H2, an increase in NOx emissions is seen due to an increase in the productivity of the N2O, NNH, and Zeldovich pathways. 4.) For category 4 (the landfill gas) the addition of diluents such as CO2 and N2 at constant air flow produces more NOx per kg of CH4 consumed, and N2 is more effective than CO 2 in increasing the NOx emission index. The increase in emission index appears to be due to an enhancement of the prompt NOx pathway as the diluents are added and the mixture moves towards stoichiometric. In addition, the presence of CO2 as a diluent catalyzes the loss of flame radicals, leading to less NOx formation than when an equivalent amount of N2 is used as a diluent. For a selected set of fuels, detailed spacial reactor probing is carried out. At the nominal temperature and residence time, the experimental results show the following trends for flame structure as a function of fuel type: 1.) Pure H2 is far more reactive in comparison to CH4 and all other pure alkane fuels. This results in relatively flat NO x and temperature profiles; whereas, the alkane fuels drop in both temperature and NOx production in the jet, where more fresh reactor feed gases are present. 2

  7. Formation of Reactive Sulfite-Derived Free Radicals by the Activation of Human Neutrophils: An ESR Study

    PubMed Central

    Ranguelova, Kalina; Rice, Annette B.; Khajo, Abdelahad; Triquigneaux, Mathilde; Garantziotis, Stavros; Magliozzo, Richard S.; Mason, Ronald P.

    2012-01-01

    The objective of the present study is to determine the effect of (bi)sulfite (hydrated sulfur dioxide) on human neutrophils and the ability of these immune cells to produce reactive free radicals due to (bi)sulfite oxidation. Myeloperoxidase (MPO) is an abundant heme protein in neutrophils that catalyzes the formation of cytotoxic oxidants implicated in asthma and inflammatory disorders. In the present study sulfite (•SO3−) and sulfate (SO4•−) anion radicals are characterized with the ESR spin-trapping technique using 5,5-dimethyl-1-pyrroline N-oxide (DMPO) in the reaction of (bi)sulfite oxidation by human MPO and human neutrophils via sulfite radical chain reaction chemistry. After treatment with (bi)sulfite, PMA-stimulated neutrophils produced DMPO-sulfite anion radical, -superoxide, and -hydroxyl radical adducts. The latter adduct probably resulted, in part, from the conversion of DMPO-sulfate to DMPO-hydroxyl radical adduct via a nucleophilic substitution reaction of the radical adduct. This anion radical (SO4•−) is highly reactive and, presumably, can oxidize target proteins to protein radicals, thereby initiating protein oxidation. Therefore, we propose that the potential toxicity of (bi)sulfite during pulmonary inflammation or lung-associated diseases such as asthma may be related to free radical formation. PMID:22326772

  8. Evaluation of a High-Throughput Peptide Reactivity Format Assay for Assessment of the Skin Sensitization Potential of Chemicals

    PubMed Central

    Wong, Chin Lin; Lam, Ai-Leen; Smith, Maree T.; Ghassabian, Sussan

    2016-01-01

    The direct peptide reactivity assay (DPRA) is a validated method for in vitro assessment of the skin sensitization potential of chemicals. In the present work, we describe a peptide reactivity assay using 96-well plate format and systematically identified the optimal assay conditions for accurate and reproducible classification of chemicals with known sensitizing capacity. The aim of the research is to ensure that the analytical component of the peptide reactivity assay is robust, accurate, and reproducible in accordance with criteria that are used for the validation of bioanalytical methods. Analytical performance was evaluated using quality control samples (QCs; heptapeptides at low, medium, and high concentrations) and incubation of control chemicals (chemicals with known sensitization capacity, weak, moderate, strong, extreme, and non-sensitizers) with each of three synthetic heptapeptides, viz Cor1-C420 (Ac-NKKCDLF), cysteine- (Ac-RFAACAA), and lysine- (Ac-RFAAKAA) containing heptapeptides. The optimal incubation temperature for all three heptapeptides was 25°C. Apparent heptapeptide depletion was affected by vial material composition. Incubation of test chemicals with Cor1-C420, showed that peptide depletion was unchanged in polypropylene vials over 3-days storage in an autosampler but this was not the case for borosilicate glass vials. For cysteine-containing heptapeptide, the concentration was not stable by day 3 post-incubation in borosilicate glass vials. Although the lysine-containing heptapeptide concentration was unchanged in both polypropylene and borosilicate glass vials, the apparent extent of lysine-containing heptapeptide depletion by ethyl acrylate, differed between polypropylene (24.7%) and glass (47.3%) vials. Additionally, the peptide-chemical complexes for Cor1-C420-cinnamaldehyde and cysteine-containing heptapeptide-2, 4-dinitrochlorobenzene were partially reversible during 3-days of autosampler storage. These observations further highlight

  9. Nanograss and nanostructure formation on silicon using a modified deep reactive ion etching

    SciTech Connect

    Mehran, M.; Mohajerzadeh, S.; Sanaee, Z.; Abdi, Y.

    2010-05-17

    Silicon nanograss and nanostructures are realized using a modified deep reactive ion etching technique on both plane and vertical surfaces of a silicon substrate. The etching process is based on a sequential passivation and etching cycle, and it can be adjusted to achieve grassless high aspect ratio features as well as grass-full surfaces. The incorporation of nanostructures onto vertically placed parallel fingers of an interdigital capacitive accelerometer increases the total capacitance from 0.45 to 30 pF. Vertical structures with features below 100 nm have been realized.

  10. Chemical reactivity parameters (HSAB) applied to magma evolution and ore formation

    NASA Astrophysics Data System (ADS)

    Vigneresse, Jean-Louis

    2012-11-01

    Magmas are commonly described through the usual content of 10 major oxides. This requires a complex dimensional plot. Concepts of hard-soft acid-base (HSAB) interactions allow estimating chemical reactivity of elements, such as electronegativity, i.e. the chemical potential changed of sign, hardness and electrophilicity. For complex system, those values result from equalization methods, i.e. the equalization of the respective chemical potentials, or from ab-initio computations through density functional theory (DFT). They help to characterize silicate magmas by a single value describing their reactivity. Principles of minimum electrophilicity (mEP), maximum hardness (MHP) and minimum polarizability (mPP) indicate trends towards regions of higher stability. Those parameters are plotted within a fitness landscape diagram, highlighting toward which principle reactions trend. Major oxides, main minerals and magmas determine the respective fields in which evolve natural rocks. Three poles are identified, represented by silica and alkalis, whereas oxidation forms the third trend. Mantle-derived rocks show a large variation in electrophilicity compared to hardness. They present all characters of a closed chemical system, being simply described by the free Gibbs energy. Conversely, rocks contaminated within the continental crust show a large variation in hardness between a silica pole and an alkaline, defining two separate trends. The trends show the character of an open chemical system, requiring a Grand Potential description (i.e. taking into account the difference in chemical potential). The terms open and closed systems refer to thermodynamical description, implying contamination for the crust and recycling for the mantle. The specific role of alkalis contrasts with other cations, pointing to their behavior in modifying silicate polymer structures. A second application deals with the reactivity of the melt and its fluid phase. It leads to a better understanding on the

  11. Formation of cubic boron-nitride by the reactive sputter deposition of boron

    SciTech Connect

    Jankowski, A.F.; Hayes, J.P.; Makowiecki, D.W.; McKeman, M.A.

    1997-03-01

    Boron-nitride films are synthesized by RF magnetron sputtering boron targets where the deposition parameters of gas pressure, flow and composition are varied along with substrate temperature and applied bias. The films are analyzed using Auger electron spectroscopy, transmission electron microscopy, nanoindentation, Raman spectroscopy and x-ray absorption spectroscopy. These techniques provide characterization of film composition, crystalline structure, hardness and chemical bonding, respectively. Reactive, rf-sputtering process parameters are established which lead to the growth of crystalline BN phases. The deposition of stable and adherent boron nitride coatings consisting of the cubic phase requires 400 `C substrate heating and the application of a 300 V negative bias.

  12. Superparamagnetic iron oxide nanoparticles as radiosensitizer via enhanced reactive oxygen species formation.

    PubMed

    Klein, Stefanie; Sommer, Anja; Distel, Luitpold V R; Neuhuber, Winfried; Kryschi, Carola

    2012-08-24

    Internalization of citrate-coated and uncoated superparamagnetic iron oxide nanoparticles by human breast cancer (MCF-7) cells was verified by transmission electron microscopy imaging. Cytotoxicity studies employing metabolic and trypan blue assays manifested their excellent biocompatibility. The production of reactive oxygen species in iron oxide nanoparticle loaded MCF-7 cells was explained to originate from both, the release of iron ions and their catalytically active surfaces. Both initiate the Fenton and Haber-Weiss reaction. Additional oxidative stress caused by X-ray irradiation of MCF-7 cells was attributed to the increase of catalytically active iron oxide nanoparticle surfaces. PMID:22842461

  13. Lens proteins block the copper-mediated formation of reactive oxygen species during glycation reactions in vitro.

    PubMed

    Ortwerth, B J; James, H L

    1999-06-16

    The formation of advanced glycation endproducts (AGEs) from glucose in vitro requires both oxygen and a transition metal ion, usually copper. These elements combine to produce reactive oxygen species (ROS) which degrade glucose to AGE-forming compounds. We measured the ability of Cu(2+) to accelerate ROS formation, and the effect of added lens proteins on these reactions. Increasing levels of Cu(2+) accelerated the formation of superoxide anion with glucose and fructosyl-lysine, but the addition of 2.0 mg/ml calf lens proteins completely blocked superoxide formation up to 100 microM of added Cu(2+). Lens proteins, however, had no effect on superoxide generated by the hypoxanthine/xanthine oxidase system. The oxidation of ascorbic acid was increased 170-fold by the addition of 10 microM Cu(2+), but was also completely prevented by added lens proteins. Hydroxyl radical formation, as measured by the conversion of benzoate to salicylate, was increased to 30 nmoles/ml after 18 h by the addition of 100 microM Cu(2+) and 2.5 mM H2O2. This increase was also blocked by the addition of lens proteins. However, hydroxyl radical formation, as estimated by the crosslinking and fragmentation of lens proteins, was observed in the presence of 100 microM Cu(2+), likely at the sites of Cu(2+) binding. Since the ratio of lens proteins to Cu(2+) in human lens is at least 1000-fold higher than those used here, the data argue that Cu(2+) in the lens would be tightly bound to protein, preventing ROS-mediated AGE formation from glucose in vivo. PMID:10364483

  14. Formation, Reactivity, and Properties of Nondative Late Transition Metal–Oxygen and–Nitrogen Bonds

    PubMed Central

    FULTON, J. ROBIN; HOLLAND, ANDREW W.; FOX, DANIEL J.; BERGMAN*, ROBERT G.

    2005-01-01

    Complexes containing bonds between heteroatoms such as nitrogen and oxygen and “late” transition metals (i.e., those located on the right side of the transition series) have been implicated as reactive intermediates in numerous important catalytic systems. Despite this, our understanding of such M–X linkages still lags behind that of their M–H and M–C analogues. New synthetic strategies have now made possible the isolation and study of a variety of monomeric late-metal alkoxide, aryloxide, and amide complexes, including parent hydroxide and amide species. The heteroatoms in these materials form surprisingly strong bonds to their metal centers, and their bond energies do not necessarily correlate with the energies of the corresponding H–X bonds. The M–X complexes typically exhibit nucleophilic reactivity, in some cases form strong hydrogen bonds to proton donors, and even deprotonate relatively weak acids. These observations, as well as thermodynamic investigations, suggest that late metal–heteroatom bonds are strongly polarized and possess significant ionic character, properties that play an important role in their interactions with organic compounds. PMID:11790088

  15. Reactive oxygen product formation by human neutrophils as an early marker for biocompatibility of dialysis membranes.

    PubMed Central

    Rosenkranz, A R; Templ, E; Traindl, O; Heinzl, H; Zlabinger, G J

    1994-01-01

    Production of reactive oxygen intermediates (ROI) by neutrophils (PMN) in vivo was examined by a whole blood assay using dichlorofluorescein-diacetate (DCFH-DA) in 10 patients each dialysed consecutively with two different dialyser membranes. Haemodialysis (HD) with cuprophan membrane (CM) led to a significantly (P < 0.001) more pronounced ROI production by PMN (2.4 +/- 0.5-fold increase in intracellular oxidation of DCFH-DA) compared with HD with polysulfone membranes (PM; 1.5 +/- 0.2-fold). HD with CM induced a decrease in PMN count by about 90%, whereas PM induced a decrease by only 25% (P < 0.001). In CM patients maximal ROI production coincided with the nadir in PMN count. All patients dialysed with CM showed a clear increase in serum levels of Bb fragments, whereas PM-dialysed patients did not. In this respect, however, no clear time relationship was seen to the kinetics of ROI production, nor to the disappearance of neutrophils from the circulation. Evaluating a direct effect of the dialysis membranes on PMN demonstrated that incubation of neutrophils with hollow fibres of the CM but not of the PM in the absence of plasma induces significant ROI production by PMN. Our study thus indicates that ROI production by PMN during HD correlates to membrane biocompatibility. Furthermore, one might speculate that also independently from but perhaps in addition to complement activation, reactive oxygen products are critically involved in the generation of haemodialysis-associated neutrophil emigration. PMID:7955536

  16. Pore Scale Modeling of the Reactive Transport of Chromium in the Cathode of a Solid Oxide Fuel Cell

    SciTech Connect

    Ryan, Emily M.; Tartakovsky, Alexandre M.; Recknagle, Kurtis P.; Khaleel, Mohammad A.; Amon, Cristina

    2011-01-01

    We present a pore scale model of a solid oxide fuel cell (SOFC) cathode. Volatile chromium species are known to migrate from the current collector of the SOFC into the cathode where over time they decrease the voltage output of the fuel cell. A pore scale model is used to investigate the reactive transport of chromium species in the cathode and to study the driving forces of chromium poisoning. A multi-scale modeling approach is proposed which uses a cell level model of the cathode, air channel and current collector to determine the boundary conditions for a pore scale model of a section of the cathode. The pore scale model uses a discrete representation of the cathode to explicitly model the surface reactions of oxygen and chromium with a cathode material. The pore scale model is used to study the reaction mechanisms of chromium by considering the effects of reaction rates, diffusion coefficients, chromium vaporization, and oxygen consumption on chromium’s deposition in the cathode. The study shows that chromium poisoning is most significantly affected by the chromium reaction rates in the cathode and that the reaction rates are a function of the local current density in the cathode.

  17. Determining fissile content in PWR spent fuel assemblies using a passive neutron Albedo reactivity with fission chambers technique

    SciTech Connect

    Conlin, Jeremy Lloyd; Tobin, Stephen J

    2010-01-01

    State regulatory bodies and organizations such as the IAEA that are concerned with preventing the proliferation of nuclear weapons are interested in a means of quantifying the amount of plutonium in a given spent fuel assembly. The complexity of spent nuclear fuel makes the measurement of plutonium content challenging. There are a variety of techniques that can measure various properties of spent nuclear fuel including burnup, and mass of fissile content. No single technique can provide all desired information, necessitating an approach using multiple detector systems and types. This paper presents our analysis of the Passive Neutron Albedo Reactivity Fission Chamber (PNAR-FC) detector system. PNAR-FC is a simplified version of the PNAR technique originally developed in 1997. This earlier research was performed with a high efficiency, {sup 3}He-based system (PNAR-3He) with which multiplicty analysis was performed. With the PNAR technique a portion of the spent fuel assembly is wrapped in a 1 mm thick cadmium liner. Neutron count rates are measured both with and without the cadmium liner present. The ratio of the count rate with the cadmium liner to the count rate without the cadmium liner is calculated and called the cadmium ratio. In the PNAR-3He technique, multiplicity measurements were made and the cadmium ratio was shown to scale with the fissile content of the material being measured. PNAR-FC simplifies the PNAR technique by using only a few fission chambers instead of many {sup 3}He tubes. Using a simplified PNAR-FC technique provides for a cheaper, lighter, and thus more portable detector system than was possible with the PNAR-3He system. The challenge with the PNAR-FC system are two-fold: (1) the change in the cadmium ratio is weaker as a afunction of the changing fissile content relative to multiplicity count rates, and (2) the efficiency for the fission chamber based system are poorer than for the {sup 3}He based detectors. In this paper, we present our

  18. Characteristics of Reactive Ni3Sn4 Formation and Growth in Ni-Sn Interlayer Systems

    NASA Astrophysics Data System (ADS)

    Lis, Adrian; Kenel, Christoph; Leinenbach, Christian

    2016-06-01

    The near-isothermal growth and formation of Ni3Sn4 intermetallic compounds (IMC) in Ni-Sn interlayer systems was studied in the solid state at 473 K (200 °C) and under solid-liquid conditions at 523 and 573 K (250 °C and 300 °C) from an initial state of a few seconds. Scalloped solid-state IMC formation was mainly driven by grain boundary diffusion of Ni through the IMC layer combined with the grain coarsening of the IMC layer. Under solid-liquid conditions, the formation of faceted and needle-shaped Ni3Sn4 grains as well as an atypical IMC growth behavior with similar parabolic growth constants for 523 K and 573 K (250 °C and 300 °C) was observed within the first 180 seconds of the holding time, and IMC growth occurred as an isothermal solidification from the Ni-saturated Sn melt. Due to the progressive densification of the IMC layer and the diffusion-controlled growth, the kinetics slowed down by approximately one order of magnitude after 180 seconds of annealing. The final stage was characterized by the formation of IMC islands ahead of the interfacial Ni3Sn4 layer. Needle-like IMC growth was effectively suppressed under combined solid-state and solid-liquid conditions. Textured Ni3Sn4 IMC formation at the Ni-Sn interface was approved with pole figure measurements. The activation energy Q for solid-liquid IMC formation was calculated as 43.3 kJ/mol, and processing maps for IMC growth and Sn consumption were derived as functions of temperature and time, respectively.

  19. Characteristics of Reactive Ni3Sn4 Formation and Growth in Ni-Sn Interlayer Systems

    NASA Astrophysics Data System (ADS)

    Lis, Adrian; Kenel, Christoph; Leinenbach, Christian

    2016-03-01

    The near-isothermal growth and formation of Ni3Sn4 intermetallic compounds (IMC) in Ni-Sn interlayer systems was studied in the solid state at 473 K (200 °C) and under solid-liquid conditions at 523 and 573 K (250 °C and 300 °C) from an initial state of a few seconds. Scalloped solid-state IMC formation was mainly driven by grain boundary diffusion of Ni through the IMC layer combined with the grain coarsening of the IMC layer. Under solid-liquid conditions, the formation of faceted and needle-shaped Ni3Sn4 grains as well as an atypical IMC growth behavior with similar parabolic growth constants for 523 K and 573 K (250 °C and 300 °C) was observed within the first 180 seconds of the holding time, and IMC growth occurred as an isothermal solidification from the Ni-saturated Sn melt. Due to the progressive densification of the IMC layer and the diffusion-controlled growth, the kinetics slowed down by approximately one order of magnitude after 180 seconds of annealing. The final stage was characterized by the formation of IMC islands ahead of the interfacial Ni3Sn4 layer. Needle-like IMC growth was effectively suppressed under combined solid-state and solid-liquid conditions. Textured Ni3Sn4 IMC formation at the Ni-Sn interface was approved with pole figure measurements. The activation energy Q for solid-liquid IMC formation was calculated as 43.3 kJ/mol, and processing maps for IMC growth and Sn consumption were derived as functions of temperature and time, respectively.

  20. A Terminal Osmium(IV) Nitride: Ammonia Formation and Ambiphilic Reactivity.

    PubMed

    Schendzielorz, Florian S; Finger, Markus; Volkmann, Christian; Würtele, Christian; Schneider, Sven

    2016-09-12

    Low-valent osmium nitrides are discussed as intermediates in nitrogen fixation schemes. However, rational synthetic routes that lead to isolable examples are currently unknown. Here, the synthesis of the square-planar osmium(IV) nitride [OsN(PNP)] (PNP=N(CH2 CH2 P(tBu)2 )2 ) is reported upon reversible deprotonation of osmium(VI) hydride [Os(N)H(PNP)](+) . The Os(IV) complex shows ambiphilic nitride reactivity with SiMe3 Br and PMe3 , respectively. Importantly, the hydrogenolysis with H2 gives ammonia and the polyhydride complex [OsH4 (HPNP)] in 80 % yield. Hence, our results directly demonstrate the role of low-valent osmium nitrides and of heterolytic H2 activation for ammonia synthesis with H2 under basic conditions. PMID:27529412

  1. Multilayered Al/CuO thermite formation by reactive magnetron sputtering: Nano versus micro

    NASA Astrophysics Data System (ADS)

    Petrantoni, M.; Rossi, C.; Salvagnac, L.; Conédéra, V.; Estève, A.; Tenailleau, C.; Alphonse, P.; Chabal, Y. J.

    2010-10-01

    Multilayered Al/CuO thermite was deposited by a dc reactive magnetron sputtering method. Pure Al and Cu targets were used in argon-oxygen gas mixture plasma and with an oxygen partial pressure of 0.13 Pa. The process was designed to produce low stress (<50 MPa) multilayered nanoenergetic material, each layer being in the range of tens nanometer to one micron. The reaction temperature and heat of reaction were measured using differential scanning calorimetry and thermal analysis to compare nanostructured layered materials to microstructured materials. For the nanostructured multilayers, all the energy is released before the Al melting point. In the case of the microstructured samples at least 2/3 of the energy is released at higher temperatures, between 1036 and 1356 K.

  2. Formation and chemical reactivity of carbon fibers prepared by defluorination of graphite fluoride

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Cheh

    1994-01-01

    Defluorination of graphite fluoride (CFX) by heating to temperatures of 250 to 450 C in chemically reactive environments was studied. This is a new and possibly inexpensive process to produce new carbon-based materials. For example, CF 0.68 fibers, made from P-100 carbon fibers, can be defluorinated in BrH2C-CH = CH-CH2Br (1,4-dibromo-2butene) heated to 370 C, and graphitized to produce fibers with an unusually high modulus and a graphite layer structure that is healed and cross-linked. Conversely, a sulfur-doped, visibly soft carbon fiber was produced by defluorinating CF 0.9 fibers, made from P-25, in sulfur (S) vapor at 370 C and then heating to 660 C in nitrogen (N2). Furthermore, defluorination of the CF 0.68 fibers in bromine (Br2) produced fragile, structurally damaged carbon fibers. Heating these fragile fibers to 1100 C in N2 caused further structural damage, whereas heating to 150 C in bromoform (CHBr3) and then to 1100 C in N2 healed the structural defects. The defluorination product of CFX, tentatively called activated graphite, has the composition and molecular structure of graphite, but is chemically more reactive. Activated graphite is a scavenger of manganese (Mn), and can be intercalated with magnesium (Mg). Also, it can easily collect large amounts of an alloy made from copper (Cu) and type 304 stainless steel to form a composite. Finally, there are indications that activated graphite can wet metals or ceramics, thereby forming stronger composites with them than the pristine carbon fibers can form.

  3. Effects of the Oxygenation level on Formation of Different Reactive Oxygen Species During Photodynamic Therapy

    PubMed Central

    Price, Michael; Heilbrun, Lance; Kessel, David

    2012-01-01

    We examined the effect of the oxygenation level on efficacy of two photosensitizing agents, both of which target lysosomes for photodamage but via different photochemical pathways. Upon irradiation, the chlorin termed NPe6 forms singlet oxygen in high yield while the bacteriopheophorbide WST11 forms only oxygen radicals (in an aqueous environment). Photokilling efficacy by WST11 in cell culture was impaired when the atmospheric oxygen concentration was reduced from 20% to 1%, while photokilling by NPe6 was unaffected. Studies in a cell-free system revealed that rates of photobleaching of these agents, as a function of the oxygenation level, were correlated with results described above. Moreover, the rate of formation of oxygen radicals by either agent was more sensitive to the level of oxygenation than was singlet oxygen formation by NPe6. These data indicate that the photochemical process that leads to oxygen radical formation is more dependent on the oxygenation level than is the pathway leading to formation of singlet oxygen. PMID:23216021

  4. Modeling the influence of precursor volatility and molecular structure on secondary organic aerosol formation using evaporated fuel experiments

    NASA Astrophysics Data System (ADS)

    Jathar, S. H.; Donahue, N. M.; Adams, P. J.; Robinson, A. L.

    2013-09-01

    We use SOA production data from an ensemble of evaporated fuels to test various SOA formation models. Except for gasoline, traditional SOA models focusing exclusively on volatile species in the fuels under-predict the observed SOA formation. These models can be improved dramatically by accounting for lower volatility species, but at the cost of a large set of free parameters. In contrast, a SOA model based only on the volatility of the precursor, starting with the volatility distribution of the evaporated fuels and optimized for the volatility reduction of first-generation products, reasonably reproduces the observed SOA formation with relatively few free parameters. The exceptions are exotic fuels such as Fischer-Tropsch fuels that expose the central assumption of the volatility based model that most emissions consist of complex mixtures displaying reasonably average behavior. However, for the vast majority of fuels, the volatility based model performs well.

  5. Effects of Air-Fuel Spray and Flame Formation in a Compression-Ignition Engine

    NASA Technical Reports Server (NTRS)

    Rothrock, A M; Waldron, C D

    1937-01-01

    High-speed motion pictures were taken at the rate of 2,500 frames per second of the fuel spray and flame formation in the combustion chamber of the NACA combustion apparatus. The compression ratio was 13.2 and the speed 1,500 revolutions per minute. An optical indicator was used to record the time-pressure relationship in the combustion chamber. The air-fuel ratio was varied from 10.4 to 365. The results showed that as the air-fuel ratio was increased definite stratification of the charge occurred in the combustion chamber even though moderate air flow existed. The results also showed the rate of vapor diffusion to be relatively slow.

  6. Importance of solid fuel properties to nitrogen oxide formation through HCN and NH[sub 3] in small particle combustion

    SciTech Connect

    Aho, M.J.; Haemaelaeinen, J.P.; Tummavuori, J.L. Univ. of Jyvaeskylae . Dept. of Chemistry)

    1993-10-01

    The formation of nitrogen oxides from fuel-nitrogen through intermediates was studied by measuring first fuel-O/fuel-N ratios and nitrogen functionality in selected solid fuels. Then the ratios of the yields (fuel-N [r arrow] HCN)/(fuel-N [r arrow] NH[sub 3]) in a nearly inert atmosphere at 800 C in an entrained flow reactor was measured and finally the ratio (fuel-N [r arrow] N[sub 2]O)/(fuel-N [r arrow] NO) in an oxidizing atmosphere at 800 C The fuels studied were coal, brown coal, S- and C-type peat, fir bark, birch bark and pine bark, all milled to a particle size < 63[mu]m. The ratios of O/N in the fuel, measured by elemental analysis, ranged from 7 to 150. Nitrogen functionality (mass percent of the total nitrogen content) was determined by XPS. the (fuel-N [r arrow] HCN)/(fuel-N [r arrow] NH[sub 3]) conversion ratio in the absence of O[sub 2], and also the (fuel-N [r arrow] N[sub 2]O)/(fuel-N [r arrow] NO) conversion ratio with O[sub 2] present, decreased with increasing ratio of fuel-O/fuel-N, but neither ratio decreased regularly with the increasing ratio of pyrrolic to pyridinic nitrogen in the fuel. Thus, fuel-oxygen plays a more important role than nitrogen functionality in the chemistry of nitrogen oxide formation. The strong effect of (fuel-O/fuel-N) ratio on the (fuel-N [r arrow] HCN)/(fuel-N [r arrow] NH[sub 3]) ratio may be due to the reaction between OH radicals and HCN to form NH[sub 3] near the fuel particle. The importance of this reaction is considered. Charring the fuel sample before combustion led to a sharp drop in the conversion of fuel-N to N[sub 2]O compared with the virgin fuels. Thus, heterogeneous combustion reactions produced much less N[sub 2]O than homogeneous combustion reactions.

  7. Reactivity of Iron-bearing Minerals in Deep Saline Formations subjected to Carbon Injection

    NASA Astrophysics Data System (ADS)

    Schoonen, M. A.; Sklute, E. C.; Strongin, D. R.; Dyar, M. D.

    2013-12-01

    Deep saline aquifers are being considered as repositories for captured CO2. Here the influence of co-injected hydrogen sulfide and sulfur dioxide on the reactivity of hematite-bearing sandstones was evaluated as a function of salt content and water/rock ratio. The reactivity of the Triassic Moenkopi red sandstone under scCO2-dominated conditions (supercritical fluid around the point of injection) and water-dominated conditions (aqueous phase influenced by the injection of scCO2) was studied. Flow-through experiments were used to simulate scCO2-dominated conditions. Crushed sandstone packed in a column was exposed to a co-mingled stream of supercritical CO2 and an aqueous H2S or SO2 solution (75°C). Batch experiments to simulate water-dominated conditions were conducted in small autoclaves that were loaded with crushed sandstone, a small amount of water, and dry ice before to 75°C. The role of water/rock ratio was explored by conducting experiments at a water/rock ratio of 4.3/1 and 1.4/1. The reacted sandstones were recovered at the conclusion of each type of experiment and analyzed for changes in mineralogical composition using X-ray Diffraction. Selected reaction products were also studied using Mössbauer spectroscopy, FTIR, and Visible Near Infrared (VNIR) spectroscopy. The results of the flow through experiments, simulating scCO2-dominated conditions, showed no changes in the iron mineralogy of the sand, regardless of whether pure scCO2 or scCO2 co-mingled with SO2 or H2S was used. By contrast, batch experiments, simulating water-dominated conditions, showed significant changes in iron mineralogy. The presence of sulfide led to the conversion of the hematite component in the sandstone to pyrite at all salt concentrations (0-6M NaCl). In experiments with sulfide and sulfite, siderite and pyrite formed, but siderite was favored at higher salinity and lower water/rock ratio. Availability of water at the mineral surface might be a critical factor in the

  8. Highly reactive {001} facets of TiO2-based composites: synthesis, formation mechanism and characterization.

    PubMed

    Ong, Wee-Jun; Tan, Lling-Lling; Chai, Siang-Piao; Yong, Siek-Ting; Mohamed, Abdul Rahman

    2014-02-21

    Titanium dioxide (TiO2) is one of the most widely investigated metal oxides due to its extraordinary surface, electronic and catalytic properties. However, the large band gap of TiO2 and massive recombination of photogenerated electron-hole pairs limit its photocatalytic and photovoltaic efficiency. Therefore, increasing research attention is now being directed towards engineering the surface structure of TiO2 at the most fundamental and atomic level namely morphological control of {001} facets in the range of microscale and nanoscale to fine-tune its physicochemical properties, which could ultimately lead to the optimization of its selectivity and reactivity. The synthesis of {001}-faceted TiO2 is currently one of the most active interdisciplinary research areas and demonstrations of catalytic enhancement are abundant. Modifications such as metal and non-metal doping have also been extensively studied to extend its band gap to the visible light region. This steady progress has demonstrated that TiO2-based composites with {001} facets are playing and will continue to play an indispensable role in the environmental remediation and in the search for clean and renewable energy technologies. This review encompasses the state-of-the-art research activities and latest advancements in the design of highly reactive {001} facet-dominated TiO2via various strategies, including hydrothermal/solvothermal, high temperature gas phase reactions and non-hydrolytic alcoholysis methods. The stabilization of {001} facets using fluorine-containing species and fluorine-free capping agents is also critically discussed in this review. To overcome the large band gap of TiO2 and rapid recombination of photogenerated charge carriers, modifications are carried out to manipulate its electronic band structure, including transition metal doping, noble metal doping, non-metal doping and incorporating graphene as a two-dimensional (2D) catalyst support. The advancements made in these aspects are

  9. Highly reactive {001} facets of TiO2-based composites: synthesis, formation mechanism and characterization

    NASA Astrophysics Data System (ADS)

    Ong, Wee-Jun; Tan, Lling-Lling; Chai, Siang-Piao; Yong, Siek-Ting; Mohamed, Abdul Rahman

    2014-01-01

    Titanium dioxide (TiO2) is one of the most widely investigated metal oxides due to its extraordinary surface, electronic and catalytic properties. However, the large band gap of TiO2 and massive recombination of photogenerated electron-hole pairs limit its photocatalytic and photovoltaic efficiency. Therefore, increasing research attention is now being directed towards engineering the surface structure of TiO2 at the most fundamental and atomic level namely morphological control of {001} facets in the range of microscale and nanoscale to fine-tune its physicochemical properties, which could ultimately lead to the optimization of its selectivity and reactivity. The synthesis of {001}-faceted TiO2 is currently one of the most active interdisciplinary research areas and demonstrations of catalytic enhancement are abundant. Modifications such as metal and non-metal doping have also been extensively studied to extend its band gap to the visible light region. This steady progress has demonstrated that TiO2-based composites with {001} facets are playing and will continue to play an indispensable role in the environmental remediation and in the search for clean and renewable energy technologies. This review encompasses the state-of-the-art research activities and latest advancements in the design of highly reactive {001} facet-dominated TiO2via various strategies, including hydrothermal/solvothermal, high temperature gas phase reactions and non-hydrolytic alcoholysis methods. The stabilization of {001} facets using fluorine-containing species and fluorine-free capping agents is also critically discussed in this review. To overcome the large band gap of TiO2 and rapid recombination of photogenerated charge carriers, modifications are carried out to manipulate its electronic band structure, including transition metal doping, noble metal doping, non-metal doping and incorporating graphene as a two-dimensional (2D) catalyst support. The advancements made in these aspects are

  10. Hematin−Hematin Self-Association States Involved in the Formation and Reactivity of the Malaria Parasite Pigment, Hemozoin

    SciTech Connect

    Klonis, Nectarios; Dilanian, Ruben; Hanssen, Eric; Darmanin, Connie; Streltsov, Victor; Deed, Samantha; Quiney, Harry; Tilley, Leann

    2010-10-22

    The malaria parasite pigment, hemozoin, is a crystal of ferriprotoporphyrin IX (FP-Fe(III)), a product of hemoglobin digestion. Hemozoin formation is essential for FP-Fe(III) detoxification in the parasite; it is the main target of quinoline antimalarials and can modulate immune and inflammation responses. To gain further insight into the likely mechanisms of crystal formation and hemozoin reactivity, we have reanalyzed the crystal structure data for {beta}-hematin and solved the crystal structure of Plasmodium falciparum hemozoin. The analysis reveals that the structures are very similar and highlights two previously unexplored modes of FP-Fe(III) self-association involving {pi}-{pi} interactions that may initiate crystal formation and help to stabilize the extended structure. Hemozoin can be considered to be a crystal composed of {pi}-{pi} dimers stabilized by iron-carboxylate linkages. As a result, it is predicted that two surfaces of the crystal would consist of {pi}-{pi} dimers with Fe(III) partly exposed to solvent and capable of undergoing redox reactions. Accordingly, we demonstrate that the crystal possesses both general peroxidase activity and the ability to cause lipid oxidation.

  11. Reactivity of atomically dispersed Pt(2+) species towards H2: model Pt-CeO2 fuel cell catalyst.

    PubMed

    Lykhach, Yaroslava; Figueroba, Alberto; Camellone, Matteo Farnesi; Neitzel, Armin; Skála, Tomáš; Negreiros, Fabio R; Vorokhta, Mykhailo; Tsud, Nataliya; Prince, Kevin C; Fabris, Stefano; Neyman, Konstantin M; Matolín, Vladimír; Libuda, Jörg

    2016-03-01

    The reactivity of atomically dispersed Pt(2+) species on the surface of nanostructured CeO2 films and the mechanism of H2 activation on these sites have been investigated by means of synchrotron radiation photoelectron spectroscopy and resonant photoemission spectroscopy in combination with density functional calculations. Isolated Pt(2+) sites are found to be inactive towards H2 dissociation due to high activation energy required for H-H bond scission. Trace amounts of metallic Pt are necessary to initiate H2 dissociation on Pt-CeO2 films. H2 dissociation triggers the reduction of Ce(4+) cations which, in turn, is coupled with the reduction of Pt(2+) species. The mechanism of Pt(2+) reduction involves reverse oxygen spillover and formation of oxygen vacancies on Pt-CeO2 films. Our calculations suggest the existence of a threshold concentration of oxygen vacancies associated with the onset of Pt(2+) reduction. PMID:26908194

  12. Nanopore formation process in artificial cell membrane induced by plasma-generated reactive oxygen species.

    PubMed

    Tero, Ryugo; Yamashita, Ryuma; Hashizume, Hiroshi; Suda, Yoshiyuki; Takikawa, Hirofumi; Hori, Masaru; Ito, Masafumi

    2016-09-01

    We investigated morphological change of an artificial lipid bilayer membrane induced by oxygen radicals which were generated by non-equilibrium atmospheric pressure plasma. Neutral oxygen species, O((3)Pj) and O2((1)Δg), were irradiated of a supported lipid bilayer existing under a buffer solution at various conditions of dose time and distances, at which the dose amounts of the oxygen species were calculated quantitatively. Observation using an atomic force microscope and a fluorescence microscope revealed that dose of the neutral oxygen species generated nanopores with the diameter of 10-50 nm in a phospholipid bilayer, and finally destructed the bilayer structure. We found that protrusions appeared on the lipid bilayer surface prior to the formation of nanopores, and we attributed the protrusions to the precursor of the nanopores. We propose a mechanism of the pore formation induced by lipid oxidation on the basis of previous experimental and theoretical studies. PMID:27216034

  13. Reactive uptake of Isoprene-derived epoxydiols to submicron aerosol particles: implications for IEPOX lifetime and SOA formation

    NASA Astrophysics Data System (ADS)

    Thornton, J. A.; Gaston, C.; Riedel, T.; Zhang, Z.; Gold, A.; Surratt, J. D.

    2014-12-01

    The reactive uptake of isoprene-derived epoxydiols (IEPOX) is thought to be a significant source of atmospheric secondary organic aerosol (SOA). However, the IEPOX reaction probability (γIEPOX) and its dependence upon particle composition remain poorly constrained. We report measurements of γIEPOX for trans-b-IEPOX, the predominant IEPOX isomer, on submicron particles as a function of composition, acidity, and relative humidity (RH). Particle acidity had the strongest effect. γIEPOX is more than 500 times larger on ammonium bisulfate (γ ~ 0.05) than on ammonium sulfate (γ ≤ 1 x 10-4). We could accurately predict γIEPOX using an acid-catalyzed, epoxide ring-opening mechanism and a high Henry's law coefficient (1.6 x 108 M/atm). Suppression of γIEPOX was observed in particles containing both ammonium bisulfate and polyethylene glycol (PEG-300), likely due to diffusion and solubility limitations within a PEG-300 coating, suggesting that IEPOX uptake could be self-limiting. Using the measured uptake kinetics, the predicted atmospheric lifetime of IEPOX is a few hours in the presence of highly acidic particles (pH < 0), but is greater than a day on less acidic particles (pH > 3). We connect these net reactive uptake measurements to chamber studies of the SOA yield from IEPOX multiphase chemistry and discuss the implications of these findings for modeling the anthropogenic influence upon SOA formation from isoprene.

  14. Isoprene Epoxydiols as Precursors to Secondary Organic Aerosol Formation: Acid-Catalyzed Reactive Uptake Studies with Authentic Compounds

    PubMed Central

    Lin, Ying-Hsuan; Zhang, Zhenfa; Docherty, Kenneth S.; Zhang, Haofei; Budisulistiorini, Sri Hapsari; Rubitschun, Caitlin L.; Shaw, Stephanie L.; Knipping, Eladio M.; Edgerton, Eric S.; Kleindienst, Tadeusz E.; Gold, Avram; Surratt, Jason D.

    2011-01-01

    Isoprene epoxydiols (IEPOX), formed from the photooxidation of isoprene under low-NOx conditions, have recently been proposed as precursors of secondary organic aerosol (SOA) on the basis of mass spectrometric evidence. In the present study, IEPOX isomers were synthesized in high purity (> 99%) to investigate their potential to form SOA via reactive uptake in a series of controlled dark chamber studies followed by reaction product analyses. IEPOX-derived SOA was substantially observed only in the presence of acidic aerosols, with conservative lower-bound yields of 4.7–6.4% for β-IEPOX and 3.4–5.5% for δ-IEPOX, providing direct evidence for IEPOX isomers as precursors to isoprene SOA. These chamber studies demonstrate that IEPOX uptake explains the formation of known isoprene SOA tracers found in ambient aerosols, including 2-methyltetrols, C5-alkene triols, dimers, and IEPOX-derived organosulfates. Additionally, we show reactive uptake on the acidified sulfate aerosols supports a previously unreported acid-catalyzed intramolecular rearrangement of IEPOX to cis- and trans-3-methyltetrahydrofuran-3,4-diols (3-MeTHF-3,4-diols) in the particle phase. Analysis of these novel tracer compounds by aerosol mass spectrometry (AMS) suggests that they contribute to a unique factor resolved from positive matrix factorization (PMF) of AMS organic aerosol spectra collected from low-NOx, isoprene-dominated regions influenced by the presence of acidic aerosols. PMID:22103348

  15. Overexpression of FGF9 in prostate epithelial cells augments reactive stroma formation and promotes prostate cancer progression.

    PubMed

    Huang, Yanqing; Jin, Chengliu; Hamana, Tomoaki; Liu, Junchen; Wang, Cong; An, Lei; McKeehan, Wallace L; Wang, Fen

    2015-01-01

    Bone metastasis is the major cause of morbidity and mortality of prostate cancer (PCa). Fibroblast growth factor 9 (FGF9) has been reported to promote PCa bone metastasis. However, the mechanism by which overexpression of FGF9 promotes PCa progression and metastasis is still unknown. Herein, we report that transgenic mice forced to express FGF9 in prostate epithelial cells (F9TG) developed high grade prostatic intraepithelial neoplasia (PIN) in an expression level- and time-dependent manner. Moreover, FGF9/TRAMP bigenic mice (F9TRAMP) grew advanced PCa earlier and had higher frequencies of metastasis than TRAMP littermates. We observed tumor microenvironmental changes including hypercellularity and hyperproliferation in the stromal compartment of F9TG and F9TRAMP mice. Expression of TGFβ1, a key signaling molecule overexpressed in reactive stroma, was increased in F9TG and F9TRAMP prostates. Both in vivo and in vitro data indicated that FGF9 promoted TGFβ1 expression via increasing cJun-mediated signaling. Moreover, in silico analyses showed that the expression level of FGF9 was positively associated with expression of TGFβ1 and its downstream signaling molecules in human prostate cancers. Collectively, our data demonstrated that overexpressing FGF9 in PCa cells augmented the formation of reactive stroma and promoted PCa initiation and progression. PMID:26157349

  16. Neutrophil myeloperoxidase and its substrates: formation of specific markers and reactive compounds during inflammation.

    PubMed

    Kato, Yoji

    2016-03-01

    Myeloperoxidase is an inflammatory enzyme that generates reactive hypochlorous acid in the presence of hydrogen peroxide and chloride ion. However, this enzyme also uses bromide ion or thiocyanate as a substrate to form hypobromous or hypothiocyanous acid, respectively. These species play important roles in host defense against the invasion of microorganisms. In contrast, these enzyme products modify biomolecules in hosts during excess inflammation, indicating that the action of myeloperoxidase is both beneficial and harmful. Myeloperoxidase uses other endogenous compounds, such as serotonin, urate, and l-tyrosine, as substrates. This broad-range specificity may have some biological implications. Target molecules of this enzyme and its products vary, including low-molecular weight thiols, proteins, nucleic acids, and lipids. The modified products represent biomarkers of myeloperoxidase action. Moderate inhibition of this enzyme might be critical for the prevention/modulation of excess, uncontrolled inflammatory events. Some phytochemicals inhibit myeloperoxidase, which might explain the reductive effect caused by the intake of vegetables and fruits on cardiovascular diseases. PMID:27013775

  17. Respiratory long-term facilitation following intermittent hypoxia requires reactive oxygen species formation

    PubMed Central

    MacFarlane, PM; Mitchell, GS

    2008-01-01

    Acute intermittent hypoxia (AIH) elicits a form of respiratory plasticity known as long-term facilitation (LTF). LTF is a progressive and sustained increase in respiratory motor output as expressed in phrenic and hypoglossal (XII) nerve activity. Since reactive oxygen species (ROS) play important roles in several forms of neuroplasticity, and ROS production is increased by intermittent hypoxia, we tested the hypothesis that ROS are necessary for phrenic and hypoglossal LTF following AIH. Urethane anesthetized, paralyzed, vagotomized and pump ventilated Sprague Dawley rats were exposed to AIH (11% O2, 3, 5 min episodes, 5 min intervals), and both phrenic and XII nerve activity were monitored for 60 min post-AIH. Although phrenic and XII LTF were observed in control rats, intravenous Manganese (III) tetrakis (1-methyl-4-pyridyl) porphyrin pentachloride (MnTMPyP), a superoxide anion scavenger, attenuated both phrenic and XII LTF in a dose dependent manner. Localized application of MnTMPyP (5.5mM; 10µl) to the intrathecal space of the cervical spinal cord (C4) abolished phrenic, but not XII LTF. Thus, ROS are necessary for AIH-induced respiratory LTF, and the relevant ROS appear to be localized near respiratory motor nuclei since cervical MnTMPyP injections impaired phrenic (and not XII) LTF. Phrenic LTF is a novel form of ROS-dependent neuroplasticity since its ROS-dependence resides in the spinal cord. PMID:18207649

  18. Superparamagnetic iron oxide nanoparticles as radiosensitizer via enhanced reactive oxygen species formation

    SciTech Connect

    Klein, Stefanie; Sommer, Anja; Distel, Luitpold V.R.; Neuhuber, Winfried; Kryschi, Carola

    2012-08-24

    Highlights: Black-Right-Pointing-Pointer Ultrasmall citrate-coated SPIONs with {gamma}Fe{sub 2}O{sub 3} and Fe{sub 3}O{sub 4} structure were prepared. Black-Right-Pointing-Pointer SPIONs uptaken by MCF-7 cells increase the ROS production for about 240%. Black-Right-Pointing-Pointer The SPION induced ROS production is due to released iron ions and catalytically active surfaces. Black-Right-Pointing-Pointer Released iron ions and SPION surfaces initiate the Fenton and Haber-Weiss reaction. Black-Right-Pointing-Pointer X-ray irradiation of internalized SPIONs leads to an increase of catalytically active surfaces. -- Abstract: Internalization of citrate-coated and uncoated superparamagnetic iron oxide nanoparticles by human breast cancer (MCF-7) cells was verified by transmission electron microscopy imaging. Cytotoxicity studies employing metabolic and trypan blue assays manifested their excellent biocompatibility. The production of reactive oxygen species in iron oxide nanoparticle loaded MCF-7 cells was explained to originate from both, the release of iron ions and their catalytically active surfaces. Both initiate the Fenton and Haber-Weiss reaction. Additional oxidative stress caused by X-ray irradiation of MCF-7 cells was attributed to the increase of catalytically active iron oxide nanoparticle surfaces.

  19. Drug 9AA reactivates p21/Waf1 and Inhibits HIV-1 progeny formation

    PubMed Central

    Wu, Weilin; Kehn-Hall, Kylene; Pedati, Caitlin; Zweier, Lynnsey; Castro, Iris; Klase, Zachary; Dowd, Cynthia S; Dubrovsky, Larisa; Bukrinsky, Michael; Kashanchi, Fatah

    2008-01-01

    It has been demonstrated that the p53 pathway plays an important role in HIV-1 infection. Previous work from our lab has established a model demonstrating how p53 could become inactivated in HIV-1 infected cells through binding to Tat. Subsequently, p53 was inactivated and lost its ability to transactivate its downstream target gene p21/waf1. P21/waf1 is a well-known cdk inhibitor (CKI) that can lead to cell cycle arrest upon DNA damage. Most recently, the p21/waf1 function was further investigated as a molecular barrier for HIV-1 infection of stem cells. Therefore, we reason that the restoration of the p53 and p21/waf1 pathways could be a possible theraputical arsenal for combating HIV-1 infection. In this current study, we show that a small chemical molecule, 9-aminoacridine (9AA) at low concentrations, could efficiently reactivate p53 pathway and thereby restoring the p21/waf1 function. Further, we show that the 9AA could significantly inhibit virus replication in activated PBMCs, likely through a mechanism of inhibiting the viral replication machinery. A mechanism study reveals that the phosphorylated p53ser15 may be dissociated from binding to HIV-1 Tat protein, thereby activating the p21/waf1 gene. Finally, we also show that the 9AA-activated p21/waf1 is recruited to HIV-1 preintegration complex, through a mechanism yet to be elucidated. PMID:18348731

  20. Neutrophil myeloperoxidase and its substrates: formation of specific markers and reactive compounds during inflammation

    PubMed Central

    Kato, Yoji

    2016-01-01

    Myeloperoxidase is an inflammatory enzyme that generates reactive hypochlorous acid in the presence of hydrogen peroxide and chloride ion. However, this enzyme also uses bromide ion or thiocyanate as a substrate to form hypobromous or hypothiocyanous acid, respectively. These species play important roles in host defense against the invasion of microorganisms. In contrast, these enzyme products modify biomolecules in hosts during excess inflammation, indicating that the action of myeloperoxidase is both beneficial and harmful. Myeloperoxidase uses other endogenous compounds, such as serotonin, urate, and l-tyrosine, as substrates. This broad-range specificity may have some biological implications. Target molecules of this enzyme and its products vary, including low-molecular weight thiols, proteins, nucleic acids, and lipids. The modified products represent biomarkers of myeloperoxidase action. Moderate inhibition of this enzyme might be critical for the prevention/modulation of excess, uncontrolled inflammatory events. Some phytochemicals inhibit myeloperoxidase, which might explain the reductive effect caused by the intake of vegetables and fruits on cardiovascular diseases. PMID:27013775

  1. Reactive magnetron sputtering of Cu2O: Dependence on oxygen pressure and interface formation with indium tin oxide

    NASA Astrophysics Data System (ADS)

    Deuermeier, Jonas; Gassmann, Jürgen; Brötz, Joachim; Klein, Andreas

    2011-06-01

    Thin films of copper oxides were prepared by reactive magnetron sputtering and structural, morphological, chemical, and electronic properties were analyzed using x-ray diffraction, atomic force microscopy, in situ photoelectron spectroscopy, and electrical resistance measurements. The deposition conditions for preparation of Cu(I)-oxide (Cu2O) are identified. In addition, the interface formation between Cu2O and Sn-doped In2O3 (ITO) was studied by stepwise deposition of Cu2O onto ITO and vice versa. A type II (staggered) band alignment with a valence band offset ΔEVB = 2.1-2.6 eV depending on interface preparation is observed. The band alignment explains the nonrectifying behavior of p-Cu2O/n-ITO junctions, which have been investigated for thin film solar cells.

  2. Reactive magnetron sputtering of Cu{sub 2}O: Dependence on oxygen pressure and interface formation with indium tin oxide

    SciTech Connect

    Deuermeier, Jonas; Gassmann, Juergen; Broetz, Joachim; Klein, Andreas

    2011-06-01

    Thin films of copper oxides were prepared by reactive magnetron sputtering and structural, morphological, chemical, and electronic properties were analyzed using x-ray diffraction, atomic force microscopy, in situ photoelectron spectroscopy, and electrical resistance measurements. The deposition conditions for preparation of Cu(I)-oxide (Cu{sub 2}O) are identified. In addition, the interface formation between Cu{sub 2}O and Sn-doped In{sub 2}O{sub 3} (ITO) was studied by stepwise deposition of Cu{sub 2}O onto ITO and vice versa. A type II (staggered) band alignment with a valence band offset {Delta}E{sub VB} 2.1-2.6 eV depending on interface preparation is observed. The band alignment explains the nonrectifying behavior of p-Cu{sub 2}O/n-ITO junctions, which have been investigated for thin film solar cells.

  3. Fuel Spray and Flame Formation in a Compression-Ignition Engine Employing Air Flow

    NASA Technical Reports Server (NTRS)

    Rothrock, A M; Waldron, C D

    1937-01-01

    The effects of air flow on fuel spray and flame formation in a high-speed compression-ignition engine have been investigated by means of the NACA combustion apparatus. The process was studied by examining high-speed motion pictures taken at the rate of 2,200 frames a second. The combustion chamber was of the flat-disk type used in previous experiments with this apparatus. The air flow was produced by a rectangular displacer mounted on top of the engine piston. Three fuel-injection nozzles were tested: a 0.020-inch single-orifice nozzle, a 6-orifice nozzle, and a slit nozzle. The air velocity within the combustion chamber was estimated to reach a value of 425 feet a second. The results show that in no case was the form of the fuel spray completely destroyed by the air jet although in some cases the direction of the spray was changed and the spray envelope was carried away by the moving air. The distribution of the fuel in the combustion chamber of a compression-ignition engine can be regulated to some extent by the design of the combustion chamber, by the design of the fuel-injection nozzle, and by the use of air flow.

  4. Reactive uptake of ammonia to secondary organic aerosols: kinetics of organonitrogen formation

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Liggio, J.; Staebler, R.; Li, S.-M.

    2015-06-01

    As a class of brown carbon, organonitrogen compounds originating from the heterogeneous uptake of NH3 by secondary organic aerosol (SOA) have received significant attention recently. In the current work, particulate organonitrogen formation during the ozonolysis of α-pinene and the OH oxidation of m-xylene in the presence of ammonia (34-125 ppb) is studied in a smog chamber equipped with a High Resolution Time-of-Flight Aerosol Mass Spectrometer and a Quantum Cascade Laser instrument. A large diversity of nitrogen containing organic (NOC) fragments was observed which were consistent with the reaction of ammonia with carbonyl containing SOA. The uptake coefficients of NH3 to SOA leading to organonitrogen compounds are reported for the first time and were in the range of ∼ 10-3-10-2, decreasing significantly to < 10-5 after 6 h of reaction. At the end of experiments (∼ 6 h) the NOC mass contributed 8.9 ± 1.7 and 31.5 ± 4.4 wt% to the total α-pinene and m-xylene derived SOA, and 4-15 wt% of the total nitrogen in the system. Uptake coefficients were also found to be positively correlated with particle acidity and negatively correlated with NH3 concentration, indicating that heterogeneous reactions were responsible for the observed NOC mass, possibly limited by liquid phase diffusion. Under these conditions, the data also indicate that the formation of NOC can compete kinetically with inorganic acid neutralization. The formation of NOC in this study suggests that a significant portion of the ambient particle associated N may be derived from NH3 heterogeneous reactions with SOA. NOC from such a mechanism may be an important and unaccounted for source of PM associated nitrogen, and a mechanism for medium or long-range transport and dry/wet deposition of atmospheric nitrogen.

  5. Reactive uptake of ammonia to secondary organic aerosols: kinetics of organonitrogen formation

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Liggio, J.; Staebler, R.; Li, S.-M.

    2015-12-01

    As a class of brown carbon, organonitrogen compounds originating from the heterogeneous uptake of NH3 by secondary organic aerosol (SOA) have received significant attention recently. In the current work, particulate organonitrogen formation during the ozonolysis of α-pinene and the OH oxidation of m-xylene in the presence of ammonia (34-125 ppb) was studied in a smog chamber equipped with a high resolution time-of-flight aerosol mass spectrometer and a quantum cascade laser instrument. A large diversity of nitrogen-containing organic (NOC) fragments was observed which were consistent with the reactions between ammonia and carbonyl-containing SOA. Ammonia uptake coefficients onto SOA which led to organonitrogen compounds were reported for the first time, and were in the range of ∼ 10-3-10-2, decreasing significantly to < 10-5 after 6 h of reaction. At the end of experiments (~ 6 h) the NOC mass contributed 8.9 ± 1.7 and 31.5 ± 4.4 wt % to the total α-pinene- and m-xylene-derived SOA, respectively, and 4-15 wt % of the total nitrogen in the system. Uptake coefficients were also found to be positively correlated with particle acidity and negatively correlated with NH3 concentration, indicating that heterogeneous reactions were responsible for the observed NOC mass, possibly limited by liquid phase diffusion. Under these conditions, the data also indicate that the formation of NOC can compete kinetically with inorganic acid neutralization. The formation of NOC in this study suggests that a significant portion of the ambient particle associated N may be derived from NH3 heterogeneous reactions with SOA. NOC from such a mechanism may be an important and unaccounted for source of PM associated nitrogen. This mechanism may also contribute to the medium or long-range transport and wet/dry deposition of atmospheric nitrogen.

  6. Evaluating temperature and fuel stratification for heat-release rate control in a reactivity-controlled compression-ignition engine using optical diagnostics and chemical kinetics modeling

    SciTech Connect

    Musculus, Mark P. B.; Kokjohn, Sage L.; Reitz, Rolf D.

    2015-04-23

    We investigated the combustion process in a dual-fuel, reactivity-controlled compression-ignition (RCCI) engine using a combination of optical diagnostics and chemical kinetics modeling to explain the role of equivalence ratio, temperature, and fuel reactivity stratification for heat-release rate control. An optically accessible engine is operated in the RCCI combustion mode using gasoline primary reference fuels (PRF). A well-mixed charge of iso-octane (PRF = 100) is created by injecting fuel into the engine cylinder during the intake stroke using a gasoline-type direct injector. Later in the cycle, n-heptane (PRF = 0) is delivered through a centrally mounted diesel-type common-rail injector. This injection strategy generates stratification in equivalence ratio, fuel blend, and temperature. The first part of this study uses a high-speed camera to image the injection events and record high-temperature combustion chemiluminescence. Moreover, the chemiluminescence imaging showed that, at the operating condition studied in the present work, mixtures in the squish region ignite first, and the reaction zone proceeds inward toward the center of the combustion chamber. The second part of this study investigates the charge preparation of the RCCI strategy using planar laser-induced fluorescence (PLIF) of a fuel tracer under non-reacting conditions to quantify fuel concentration distributions prior to ignition. The fuel-tracer PLIF data show that the combustion event proceeds down gradients in the n-heptane distribution. The third part of the study uses chemical kinetics modeling over a range of mixtures spanning the distributions observed from the fuel-tracer fluorescence imaging to isolate the roles of temperature, equivalence ratio, and PRF number stratification. The simulations predict that PRF number stratification is the dominant factor controlling the ignition location and growth rate of the reaction zone. Equivalence ratio has a smaller, but still significant

  7. The Role of Reactive Oxygen Species (ROS) in the Formation of Extracellular Traps (ETs) in Humans

    PubMed Central

    Stoiber, Walter; Obermayer, Astrid; Steinbacher, Peter; Krautgartner, Wolf-Dietrich

    2015-01-01

    Extracellular traps (ETs) are reticulate structures of extracellular DNA associated with antimicrobial molecules. Their formation by phagocytes (mainly by neutrophils: NETs) has been identified as an essential element of vertebrate innate immune defense. However, as ETs are also toxic to host cells and potent triggers of autoimmunity, their role between pathogen defense and human pathogenesis is ambiguous, and they contribute to a variety of acute and chronic inflammatory diseases. Since the discovery of ET formation (ETosis) a decade ago, evidence has accumulated that most reaction cascades leading to ET release involve ROS. An important new facet was added when it became apparent that ETosis might be directly linked to, or be a variant of, the autophagy cell death pathway. The present review analyzes the evidence to date on the interplay between ROS, autophagy and ETosis, and highlights and discusses several further aspects of the ROS-ET relationship that are incompletely understood. These aspects include the role of NADPH oxidase-derived ROS, the molecular requirements of NADPH oxidase-dependent ETosis, the roles of NADPH oxidase subtypes, extracellular ROS and of ROS from sources other than NADPH oxidase, and the present evidence for ROS-independent ETosis. We conclude that ROS interact with ETosis in a multidimensional manner, with influence on whether ETosis shows beneficial or detrimental effects. PMID:25946076

  8. Control of Reactivity and Regioselectivity for On-Surface Dehydrogenative Aryl-Aryl Bond Formation.

    PubMed

    Kocić, Nemanja; Liu, Xunshan; Chen, Songjie; Decurtins, Silvio; Krejčí, Ondřej; Jelínek, Pavel; Repp, Jascha; Liu, Shi-Xia

    2016-05-01

    Regioselectivity is of fundamental importance in chemical synthesis. Although many concepts for site-selective reactions are well established for solution chemistry, it is not a priori clear whether they can easily be transferred to reactions taking place on a metal surface. A metal will fix the chemical potential of the electrons and perturb the electronic states of the reactants because of hybridization. Additionally, techniques to characterize chemical reactions in solution are generally not applicable to on-surface reactions. Only recent developments in resolving chemical structures by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) paved the way for identifying individual reaction products on surfaces. Here we exploit a combined STM/AFM technique to demonstrate the on-surface formation of complex molecular architectures built up from a heteroaromatic precursor, the tetracyclic pyrazino[2,3-f][4,7]phenanthroline (pap) molecule. Selective intermolecular aryl-aryl coupling via dehydrogenative C-H activation occurs on Au(111) upon thermal annealing under ultrahigh vacuum (UHV) conditions. A full atomistic description of the different reaction products based on an unambiguous discrimination between pyrazine and pyridine moieties is presented. Our work not only elucidates that ortho-hydrogen atoms of the pyrazine rings are preferentially activated over their pyridine equivalents, but also sheds new light onto the participation of substrate atoms in metal-organic coordination bonding during covalent C-C bond formation. PMID:27059121

  9. Nanostructured diffusion-limited-aggregation crystal pattern formation in a reactive microemulsion system

    NASA Astrophysics Data System (ADS)

    Srivastava, Rohit; Srivastava, P. K.

    2014-03-01

    Nanostructured diffusion-limited-aggregation (DLA) crystal pattern formation in microemulsion consisting of water, styrene, cetyltrimethylammonium chloride (CTACl), potassium persulphate and an oscillating Belousov-Zhabotinsky (BZ) reactant is reported. A variety of spatiotemporal patterns like concentric wave, spatial (stripe) and chaotic patterns appear. A colloidal phase composed of numerous nano-sized particles has been observed. The solid phase nucleation has been found to occur in the colloidal phase and has been found to grow in a symmetric crystal pattern with the progress of the reaction finally exhibiting DLA structures. We show that the formation of a nanostructured DLA crystal pattern is governed by spatial structures emerging in the BZ microemulsion system. Without any spatial structure in the microemulsion system only hydrogel of high viscosity is formed. A nano-sized branched crystal pattern was formed with a particle diameter in the range of 60-100 nm, as evident by transmission electron microscope, powder x-ray diffraction and particle size analyser studies.

  10. Measurement of the atmospheric reactivity of emissions from gasoline and alternative-fueled vehicles: Assessment of available methodologies. Part 1. Indoor smog chamber study of reactivity. Part 2. Assessment of airtrak as a reactivity analyzer. Final report for the second year, March 1, 1994-February 28, 1995

    SciTech Connect

    Kelly, N.A.; Wang, P.; Hurley, M.D.; Japar, S.M.; Chang, T.

    1996-06-13

    During the second year of the GM smog chamber study of incremental reactivity the authors performed smog chamber experiments to measure three important properties of incremental reactivity. First, they challenged the linear relationship between the Carter factors and the chamber-measured reactivities found during the first-year smog chamber study. Second, they compared the predicted and measured smog formation in simple and complex mixtures. Third, they measured the incremental reactivities of three hydrocarbons (n-butane, propene, and p-xylene) as well as the urban-surrogate mixture at three different temperatures, 22 deg C, 32 deg C (the default), and 42 deg C, to determine how temperature affects both the absolute and the relative reactivity. Finally, they conducted experiments in which the incremental reactivity of NO2 was measured in order to test the Integrated Empirical Rate (IER) model.