System and method for regeneration and recirculation of a reducing agent using highly exothermic reactions induced by mixed industrial slags

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakano, Jinichiro; Bennett, James P.; Nakano, Anna

Embodiments relate to systems and methods for regenerating and recirculating a CO, H.sub.2 or combinations thereof utilized for metal oxide reduction in a reduction furnace. The reduction furnace receives the reducing agent, reduces the metal oxide, and generates an exhaust of the oxidized product. The oxidized product is transferred to a mixing vessel, where the oxidized product, a calcium oxide, and a vanadium oxide interact to regenerate the reducing agent from the oxidized product. The regenerated reducing agent is transferred back to the reduction furnace for continued metal oxide reductions.

Particle Image Velocimetry in an Isothermal and Exothermic High Speed Cavity (Postprint)

DTIC Science & Technology

2012-02-01

17 Oxides and Hydroxides of Aluminum, Alcoa Technical Paper No. 19, Revised...Karl Wefers and Chanakya Misra, Alcoa Laboratories, 1987. 18 CRC Handbook of Chemistry and Physics, David R. Lide, Ed. 80th Edition, CRC Press, Boca

Kinetic analysis of overlapping multistep thermal decomposition comprising exothermic and endothermic processes: thermolysis of ammonium dinitramide.

PubMed

Muravyev, Nikita V; Koga, Nobuyoshi; Meerov, Dmitry B; Pivkina, Alla N

2017-01-25

This study focused on kinetic modeling of a specific type of multistep heterogeneous reaction comprising exothermic and endothermic reaction steps, as exemplified by the practical kinetic analysis of the experimental kinetic curves for the thermal decomposition of molten ammonium dinitramide (ADN). It is known that the thermal decomposition of ADN occurs as a consecutive two step mass-loss process comprising the decomposition of ADN and subsequent evaporation/decomposition of in situ generated ammonium nitrate. These reaction steps provide exothermic and endothermic contributions, respectively, to the overall thermal effect. The overall reaction process was deconvoluted into two reaction steps using simultaneously recorded thermogravimetry and differential scanning calorimetry (TG-DSC) curves by considering the different physical meanings of the kinetic data derived from TG and DSC by P value analysis. The kinetic data thus separated into exothermic and endothermic reaction steps were kinetically characterized using kinetic computation methods including isoconversional method, combined kinetic analysis, and master plot method. The overall kinetic behavior was reproduced as the sum of the kinetic equations for each reaction step considering the contributions to the rate data derived from TG and DSC. During reproduction of the kinetic behavior, the kinetic parameters and contributions of each reaction step were optimized using kinetic deconvolution analysis. As a result, the thermal decomposition of ADN was successfully modeled as partially overlapping exothermic and endothermic reaction steps. The logic of the kinetic modeling was critically examined, and the practical usefulness of phenomenological modeling for the thermal decomposition of ADN was illustrated to demonstrate the validity of the methodology and its applicability to similar complex reaction processes.

Coupling of exothermic and endothermic reactions in oxidative conversion of natural gas into ethylene/olefins over diluted SrO/La{sub 2}O{sub 3}/SA5205 catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choudhary, V.R.; Mulla, S.A.R.

1997-09-01

In the oxidative conversion of natural gas to ethylene/lower olefins over SrO (17.3 wt.%)/La{sub 2}O{sub 3} (17.9 wt.%)/SA5205 catalyst diluted with inert solid particles (inerts/catalyst(w/w) = 2.0) in the presence of limited O{sub 2}, the exothermic oxidative conversion reactions of natural gas are coupled with the endothermic C{sub 2+} hydrocarbon thermal cracking reactions for avoiding hot spot formation and eliminating heat removal problems. Because of this, the process is operated in the most energy-efficient and safe manner. The influence of various process variables (viz. temperature, NG/O{sub 2} and steam/NG ratios in feed, and space velocity) on the conversion of carbonmore » and also of the individual hydrocarbons in natural gas, the selectivity for C{sub 2}-C{sub 4} olefins, and also on the net heat of reactions in the process has been thoroughly investigated. By carrying out the process at 800--850 C in the presence of steam (H{sub 2}O/NG {le} 0.2) and using limited O{sub 2} in the feed (NG/O{sub 2} = 12--18), high selectivity for ethylene (about 60%) or C{sub 2}-C{sub 4} olefins (above 80%) at the carbon conversion (>15%) of practical interest could be achieved at high space velocity ({ge}34,000 cm{sup 3}/g (catalyst) h), requiring no external energy and also without forming coke or tar-like products. The net heat of reactions can be controlled and the process can be made mildly exothermic or even close to thermoneutral by manipulating the O{sub 2} concentration in the feed.« less

Noncatalytic oxypyrolysis of C{sub 2+}-hydrocarbons from natural gas to ethylene and propylene in a most energy-efficient and safe manner

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choudhary, V.R.; Mulla, S.A.R.; Rajput, A.M.

1997-06-01

Noncatalytic oxypyrolysis of C{sub 2+}-hydrocarbons from natural gas at 700--850 C in the presence of steam and limited oxygen yields ethylene and propylene with appreciable conversion and high selectivity but with almost no coke or tarlike product formation. In this process, the exothermic oxidative hydrocarbon conversion reactions are coupled directly with the endothermic cracking of C{sub 2+}-hydrocarbons by their simultaneous occurrence. Hence, the process operates in a most energy-efficient and safe (or nonhazardous) manner and also can be made almost thermoneutral or mildly endothermic/exothermic, thus requiring little or no external energy for the hydrocarbon conversion reactions.

Anoxic and Oxic Oxidation of Rocks Containing Fe(II)Mg-Silicates and Fe(II)-Monosulfides as Source of Fe(III)-Minerals and Hydrogen. Geobiotropy.

PubMed

Bassez, Marie-Paule

2017-12-01

In this article, anoxic and oxic hydrolyses of rocks containing Fe (II) Mg-silicates and Fe (II)-monosulfides are analyzed at 25 °C and 250-350 °C. A table of the products is drawn. It is shown that magnetite and hydrogen can be produced during low-temperature (25 °C) anoxic hydrolysis/oxidation of ferrous silicates and during high-temperature (250 °C) anoxic hydrolysis/oxidation of ferrous monosulfides. The high-T (350 °C) anoxic hydrolysis of ferrous silicates leads mainly to ferric oxides/hydroxides such as the hydroxide ferric trihydroxide, the oxide hydroxide goethite/lepidocrocite and the oxide hematite, and to Fe(III)-phyllosilicates. Magnetite is not a primary product. While the low-T (25 °C) anoxic hydrolysis of ferrous monosulfides leads to pyrite. Thermodynamic functions are calculated for elementary reactions of hydrolysis and carbonation of olivine and pyroxene and E-pH diagrams are analyzed. It is shown that the hydrolysis of the iron endmember is endothermic and can proceed within the exothermic hydrolysis of the magnesium endmember and also within the exothermic reactions of carbonations. The distinction between three products of the iron hydrolysis, magnetite, goethite and hematite is determined with E-pH diagrams. The hydrolysis/oxidation of the sulfides mackinawite/troilite/pyrrhotite is highly endothermic but can proceed within the heat produced by the exothermic hydrolyses and carbonations of ferromagnesian silicates and also by other sources such as magma, hydrothermal sources, impacts. These theoretical results are confirmed by the products observed in several related laboratory experiments. The case of radiolyzed water is studied. It is shown that magnetite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite are formed in oxic hydrolysis of ferromagnesian silicates at 25 °C and 350 °C. Oxic oxidation of ferrous monosulfides at 25 °C leads mainly to pyrite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite and also to sulfates, and at 250 °C mainly to magnetite instead of pyrite, associated to the same ferric oxides/hydroxides and sulfates. Some examples of geological terrains, such as Mawrth Vallis on Mars, the Tagish Lake meteorite and hydrothermal venting fields, where hydrolysis/oxidation of ferromagnesian silicates and iron(II)-monosulfides may occur, are discussed. Considering the evolution of rocks during their interaction with water, in the absence of oxygen and in radiolyzed water, with hydrothermal release of H 2 and the plausible associated formation of components of life, geobiotropic signatures are proposed. They are mainly Fe(III)-phyllosilicates, magnetite, ferric trihydroxide, goethite/lepidocrocite, hematite, but not pyrite.

Anoxic and Oxic Oxidation of Rocks Containing Fe(II)Mg-Silicates and Fe(II)-Monosulfides as Source of Fe(III)-Minerals and Hydrogen. Geobiotropy.

NASA Astrophysics Data System (ADS)

Bassez, Marie-Paule

2017-12-01

In this article, anoxic and oxic hydrolyses of rocks containing Fe (II) Mg-silicates and Fe (II)-monosulfides are analyzed at 25 °C and 250-350 °C. A table of the products is drawn. It is shown that magnetite and hydrogen can be produced during low-temperature (25 °C) anoxic hydrolysis/oxidation of ferrous silicates and during high-temperature (250 °C) anoxic hydrolysis/oxidation of ferrous monosulfides. The high-T (350 °C) anoxic hydrolysis of ferrous silicates leads mainly to ferric oxides/hydroxides such as the hydroxide ferric trihydroxide, the oxide hydroxide goethite/lepidocrocite and the oxide hematite, and to Fe(III)-phyllosilicates. Magnetite is not a primary product. While the low-T (25 °C) anoxic hydrolysis of ferrous monosulfides leads to pyrite. Thermodynamic functions are calculated for elementary reactions of hydrolysis and carbonation of olivine and pyroxene and E-pH diagrams are analyzed. It is shown that the hydrolysis of the iron endmember is endothermic and can proceed within the exothermic hydrolysis of the magnesium endmember and also within the exothermic reactions of carbonations. The distinction between three products of the iron hydrolysis, magnetite, goethite and hematite is determined with E-pH diagrams. The hydrolysis/oxidation of the sulfides mackinawite/troilite/pyrrhotite is highly endothermic but can proceed within the heat produced by the exothermic hydrolyses and carbonations of ferromagnesian silicates and also by other sources such as magma, hydrothermal sources, impacts. These theoretical results are confirmed by the products observed in several related laboratory experiments. The case of radiolyzed water is studied. It is shown that magnetite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite are formed in oxic hydrolysis of ferromagnesian silicates at 25 °C and 350 °C. Oxic oxidation of ferrous monosulfides at 25 °C leads mainly to pyrite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite and also to sulfates, and at 250 °C mainly to magnetite instead of pyrite, associated to the same ferric oxides/hydroxides and sulfates. Some examples of geological terrains, such as Mawrth Vallis on Mars, the Tagish Lake meteorite and hydrothermal venting fields, where hydrolysis/oxidation of ferromagnesian silicates and iron(II)-monosulfides may occur, are discussed. Considering the evolution of rocks during their interaction with water, in the absence of oxygen and in radiolyzed water, with hydrothermal release of H2 and the plausible associated formation of components of life, geobiotropic signatures are proposed. They are mainly Fe(III)-phyllosilicates, magnetite, ferric trihydroxide, goethite/lepidocrocite, hematite, but not pyrite.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shepherd, James; Fairweather, Michael; Hanson, Bruce C.

The oxidation of spent uranium carbide fuel, a candidate fuel for Generation IV nuclear reactors, is an important process in its potential reprocessing cycle. However, the oxidation of uranium carbide in air is highly exothermic. A model has therefore been developed to predict the temperature rise, as well as other useful information such as reaction completion times, under different reaction conditions in order to help in deriving safe oxidation conditions. Finite difference-methods are used to model the heat and mass transfer processes occurring during the reaction in two dimensions and are coupled to kinetics found in the literature.

Chemical states of surface oxygen during CO oxidation on Pt(1 1 0) surface revealed by ambient pressure XPS

DOE PAGES

Yu, Youngseok; Koh, Yoobin Esther; Lim, Hojoon; ...

2017-10-20

Here, the study of CO oxidation on Pt(110) surface is revisited using ambient pressure x-ray photoemission spectroscopy. When the surface temperature reaches the activation temperature for CO oxidation under elevated pressure conditions, both the α-phase of PtO 2 oxide and chemisorbed oxygen are formed simultaneously on the surface. Due to the exothermic nature of CO oxidation, the temperature of the Pt surface increases as CO oxidation takes place. As the CO/O 2 ratio increases, the production of CO 2 increases continuously and the surface temperature also increases. Interestingly, within the diffusion limited regions, the amount of surface oxide changes littlemore » while the chemisorbed oxygen is reduced.« less

Chemical states of surface oxygen during CO oxidation on Pt(1 1 0) surface revealed by ambient pressure XPS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Youngseok; Koh, Yoobin Esther; Lim, Hojoon

Here, the study of CO oxidation on Pt(110) surface is revisited using ambient pressure x-ray photoemission spectroscopy. When the surface temperature reaches the activation temperature for CO oxidation under elevated pressure conditions, both the α-phase of PtO 2 oxide and chemisorbed oxygen are formed simultaneously on the surface. Due to the exothermic nature of CO oxidation, the temperature of the Pt surface increases as CO oxidation takes place. As the CO/O 2 ratio increases, the production of CO 2 increases continuously and the surface temperature also increases. Interestingly, within the diffusion limited regions, the amount of surface oxide changes littlemore » while the chemisorbed oxygen is reduced.« less

A two-dimensional, finite-difference model of the oxidation of a uranium carbide fuel pellet

NASA Astrophysics Data System (ADS)

Shepherd, James; Fairweather, Michael; Hanson, Bruce C.; Heggs, Peter J.

2015-12-01

The oxidation of spent uranium carbide fuel, a candidate fuel for Generation IV nuclear reactors, is an important process in its potential reprocessing cycle. However, the oxidation of uranium carbide in air is highly exothermic. A model has therefore been developed to predict the temperature rise, as well as other useful information such as reaction completion times, under different reaction conditions in order to help in deriving safe oxidation conditions. Finite difference-methods are used to model the heat and mass transfer processes occurring during the reaction in two dimensions and are coupled to kinetics found in the literature.

Exploring the synthesis and characterization of nanoenergetic materials from sol-gel chemistry

NASA Astrophysics Data System (ADS)

Walker, Jeremy D.

Nanoenergetic composite materials have been synthesized by a sol-gel chemical process where the addition of a weak base molecule induces the gelation of a hydrated metal salt solution. A proposed 'proton scavenging' mechanism, where a weak base molecule extracts a proton from the coordination sphere of the hydrated iron (III) complex in the gelation process to form iron (III) oxide/hydroxide, FeIIIxOyHz, has been confirmed for the weak base propylene oxide (PO), a 1,2 epoxide, as well as for the weak bases tetrahydrofuran (THF), a 1,4 epoxide, and pyridine, a heterocyclic nitrogen-containing compound. Gelation mechanisms for the formation of FeIIIxOyHz from THF and pyridine have been presented and confirmed through pH, XPS, and IR studies. THF follows a similar mechanism as PO, where the epoxide extracts a proton from the coordination sphere of the hydrated iron complex forming a protonated epoxide, which then undergoes irreversible ring-opening after reaction with a nucleophile in solution. Pyridine also extracts a proton from the hydrated metal complex, however, the stable six-membered molecule has low associated ring strain and does not endure ring-opening. Energetic properties for the Fe2O3/Al and RuO 2/Al sol-gel synthesized systems are also presented. Sol-gel chemistry synthesizes x-ray amorphous oxide matrices which contain substantial quantities of residual water and organic species. The iron (III) matrix, formed from the addition of a weak base epoxide molecule to a hydrated iron (III) nitrate solution, consists of stoichiometric Fe2O3, FeO(OH), and Fe(OH)3 and can only definitely be described as of Fe IIIxOyHz. XPS characterization of the metal oxide matrix synthesized from the addition of the weak base propylene oxide to a hydrated ruthenium (III) chloride solution corresponds to that of hydrous ruthenium (IV) oxide. Fe2O3/Al energetic systems were synthesized from the epoxides PO, trimethylene oxide (TMO) and 3,3 dimethyl oxetane (DMO). Energetic systems formed from each epoxide were each synthesized with different components, including: varying concentrations of nano-scale Al, micron Al, and carbon nanotubes. Surface area analysis of the synthesized matrices shows a direct correlation between the surface area of the iron (III) oxide matrix and the quantified exothermic heat of reaction of the energetic material due to the magnitude of the interfacial surface area contact between the iron (III) oxide matrix and the aluminum particles. The Fe2O3(PO)/Al systems possess the highest heat of reaction values due to the oxide surface area available for contact with the aluminum particles. Also, within systems, 1:1 Fe:nano Al samples possess the highest heat of reaction. Samples with nano-scale Al particles start reaction at 430°C, before the melting point of Al, whereas samples containing micron-Al do not react until ˜800°C, after the melting point of Al. The RuO2/Al energetic systems behave differently dependent on the atmosphere the sample is heated. Heating the RuO2/Al samples in an inert atmosphere results in the complete reduction of the ruthenium oxide matrix to Ru(0) before reaction with the aluminum particles. This results in the exothermic formation of RuxAly intermetallics, with the stoichiometry dependent on the initial Ru:Al concentration. However, heating the samples in an oxygen-rich atmosphere results in an exothermic reaction between RuO2 and Al. Post-reaction analysis of these samples reveals the sole existence of ruthenium (IV) oxide as the exothermic reaction vaporizes the aluminum particles.

Hexagonal boron nitride catalyst in a fixed-bed reactor for exothermic propane oxidation dehydrogenation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tian, Jinshu; Lin, Jinhan; Xu, Mingliang

Hexagonal boron nitride (h-BN) with high thermal conductivity is potentially an effective catalyst for highly exothermic propane oxidative dehydrogenation (ODH) reaction. Here, we report our experimental and theoretic studies of such a catalyst for propane ODH in a fixed-bed reactor. Based on the computational fluid dynamics calculation (CFD) results, the catalyst bed temperature increases by less than 1°C in the h-BN catalyst bed which is much smaller than that (8°C) in the VO x/γ-Al 2O 3 catalyst bed at a similar propane conversion (25%) using a micro-tubular reactor with a diameter of 6 mm. Even in an industrially relevant reactormore » with an inner diameter of 60 mm, a uniform temperature profile can still be maintained using the h-BN catalyst bed due to its excellent thermal conductivity as opposed to a temperature gradient of 47°C in the VO x/γ-Al 2O 3 catalyst bed. The results reported here provide useful information for potential application of h-BN catalyst in propane ODH.« less

Reaction Kinetics and Combustion Dynamics of I4O9 and Aluminum Mixtures

PubMed Central

Smith, Dylan K.; Pantoya, Michelle L.; Parkey, Jeffrey S.; Kesmez, Mehmet

2016-01-01

Tetraiodine nonoxide (I4O9) has been synthesized using a dry approach that combines elemental oxygen and iodine without the introduction of hydrated species. The synthesis approach inhibits the topochemical effect promoting rapid hydration when exposed to the relative humidity of ambient air. This stable, amorphous, nano-particle material was analyzed using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) and showed an exothermic energy release at low temperature (i.e., 180 °C) for the transformation of I4O9 into I2O5. This additional exothermic energy release contributes to an increase in overall reactivity of I4O9 when dry mixed with nano-aluminum (Al) powder, resulting in a minimum of 150% increase in flame speed compared to Al + I2O5. This study shows that as an oxidizer, I4O9 has more reactive potential than other forms of iodine(V) oxide when combined with Al, especially if I4O9 can be passivated to inhibit absorption of water from its surrounding environment. PMID:27842354

Hexagonal boron nitride catalyst in a fixed-bed reactor for exothermic propane oxidation dehydrogenation

DOE PAGES

Tian, Jinshu; Lin, Jinhan; Xu, Mingliang; ...

2018-04-17

Hexagonal boron nitride (h-BN) with high thermal conductivity is potentially an effective catalyst for highly exothermic propane oxidative dehydrogenation (ODH) reaction. Here, we report our experimental and theoretic studies of such a catalyst for propane ODH in a fixed-bed reactor. Based on the computational fluid dynamics calculation (CFD) results, the catalyst bed temperature increases by less than 1°C in the h-BN catalyst bed which is much smaller than that (8°C) in the VO x/γ-Al 2O 3 catalyst bed at a similar propane conversion (25%) using a micro-tubular reactor with a diameter of 6 mm. Even in an industrially relevant reactormore » with an inner diameter of 60 mm, a uniform temperature profile can still be maintained using the h-BN catalyst bed due to its excellent thermal conductivity as opposed to a temperature gradient of 47°C in the VO x/γ-Al 2O 3 catalyst bed. The results reported here provide useful information for potential application of h-BN catalyst in propane ODH.« less

Thermodynamic Stability of Transition Metal Substituted LiMn 2-xMxO 4 (M=Cr, Fe, Co, and Ni) Spinels

NASA Astrophysics Data System (ADS)

Lai, Chenying

The formation enthalpies from binary oxides of LiMn2O 4, LiMn2-xCrxO4 (x = 0.25, 0.5, 0.75 and 1), LiMn2-xFexO4 (x = 0.25 and 0.5), LiMn2-xCoxO4 (x = 0.25, 0.5, and 0.75) and LiMn1.75Ni 0.25O4 at 25 °C have been measured by high-temperature oxide-melt-solution calorimetry and were found to be strongly exothermic. Increasing Cr, Co and Ni content leads to more thermodynamically stable spinels, but increasing Fe content does not significantly affect the stability. The formation enthalpies from oxides of the fully substituted spinels, LiMnMO 4 (M = Cr, Fe and Co) become more exothermic (implying increasing stability) with decreasing ionic radius of the metal and lattice parameters of the spinel. The trend in enthalpy versus metal content is roughly linear, suggesting a close-to-zero heat of mixing in LiMn2O4 - LiMnMO 4 solid solutions. These data confirm that transition metal doping is beneficial for stabilizing these potential cathode materials for lithium-ion batteries.

Decomposition of nitric oxide in a hot nitrogen stream to synthesize air for hypersonic wind tunnel combustion testing

NASA Technical Reports Server (NTRS)

Zumdieck, J. F.; Zlatarich, S. A.

1974-01-01

A clean source of high enthalpy air was obtained from the exothermic decomposition of nitric oxide in the presence of strongly heated nitrogen. A nitric oxide jet was introduced into a confined coaxial nitrogen stream. Measurements were made of the extent of mixing and reaction. Experimental results are compared with one- and two-dimensional chemical kinetics computations. Both analyses predict much lower reactivity than was observed experimentally. Inlet nitrogen temperatures above 2400 K were sufficient to produce experimentally a completely reacted gas stream of synthetic air.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Putilov, L.P., E-mail: lev.putilov@gmail.com; Tsidilkovski, V.I.

The impact of deep acceptor centers on defect thermodynamics and oxidation of wide-band-gap acceptor-doped perovskites without mixed-valence cations is studied. These deep centers are formed by the acceptor-bound small hole polarons whose stabilization energy can be high enough (significantly higher than the hole-acceptor Coulomb interaction energy). It is shown that the oxidation enthalpy ΔH{sub ox} of oxide is determined by the energy ε{sub A} of acceptor-bound states along with the formation energy E{sub V} of oxygen vacancies. The oxidation reaction is demonstrated to be either endothermic or exothermic, and the regions of ε{sub A} and E{sub V} values corresponding tomore » the positive or negative ΔH{sub ox} are determined. The contribution of acceptor-bound holes to the defect thermodynamics strongly depends on the acceptor states depth ε{sub A}: it becomes negligible at ε{sub A} less than a certain value (at which the acceptor levels are still deep). With increasing ε{sub A}, the concentration of acceptor-bound small hole polarons can reach the values comparable to the dopant content. The results are illustrated with the acceptor-doped BaZrO{sub 3} as an example. It is shown that the experimental data on the bulk hole conductivity of barium zirconate can be described both in the band transport model and in the model of hopping small polarons localized on oxygen ions away from the acceptor centers. Depending on the ε{sub A} magnitude, the oxidation reaction can be either endothermic or exothermic for both mobility mechanisms.« less

Differences in the adsorption behaviour of poly(ethylene oxide) copolymers onto model polystyrene nanoparticles assessed by isothermal titration microcalorimetry correspond to the biological differences.

PubMed

Stolnik, S; Heald, C R; Garnett, M G; Illum, L; Davis, S S

2005-01-01

The adsorption behaviour of a tetrafunctional copolymer of poly (ethylene oxide)-poly (propylene oxide) ethylene diamine (commercially available as Poloxamine 908) and a diblock copolymer of poly (lactic acid)-poly (ethylene oxide) (PLA/PEG 2:5) onto a model colloidal drug carrier (156 nm sized polystyrene latex) is described. The adsorption isotherm, hydrodynamic thickness of the adsorbed layers and enthalpy of the adsorption were assessed. The close similarity in the conformation of the poly (ethylene oxide) (PEO) chains (molecular weight 5,000 Da) in the adsorbed layers of these two copolymers was demonstrated by combining the adsorption data with the adsorbed layer thickness data. In contrast, the results from isothermal titration microcalorimetry indicated a distinct difference in the interaction of the copolymers with the polystyrene colloid surface. Poloxamine 908 adsorption to polystyrene nanoparticles is dominated by an endothermic heat effect, whereas, PLA/PEG 2:5 adsorption is entirely an exothermic process. This difference in adsorption behaviour could provide an explanation for differences in the biodistribution of Poloxamine 908 and PLA/PEG 2:5 coated polystyrene nanoparticles observed in previous studies. A comparison with the interaction enthalpy for several other PEO-containing copolymers onto the same polystyrene colloid was made. The results demonstrate the importance of the nature of the anchoring moiety on the interaction of the adsorbing copolymer with the colloid surface. An endothermic contribution is found when an adsorbing molecule contains a poly (propylene oxide) (PPO) moiety (e.g. Poloxamine 908), whilst the adsorption is exothermic (i.e. enthalpy driven) for PEO copolymers with polylactide (PLA/PEG 2:5) or alkyl moieties.

Combined flame and electrodeposition synthesis of energetic coaxial tungsten-oxide/aluminum nanowire arrays.

PubMed

Dong, Zhizhong; Al-Sharab, Jafar F; Kear, Bernard H; Tse, Stephen D

2013-09-11

A nanostructured thermite composite comprising an array of tungsten-oxide (WO2.9) nanowires (diameters of 20-50 nm and lengths of >10 μm) coated with single-crystal aluminum (thickness of ~16 nm) has been fabricated. The method involves combined flame synthesis of tungsten-oxide nanowires and ionic-liquid electrodeposition of aluminum. The geometry not only presents an avenue to tailor heat-release characteristics due to anisotropic arrangement of fuel and oxidizer but also eliminates or minimizes the presence of an interfacial Al2O3 passivation layer. Upon ignition, the energetic nanocomposite exhibits strong exothermicity, thereby being useful for fundamental study of aluminothermic reactions as well as enhancing combustion characteristics.

Misconceptions in the Exploding Flask Demonstration Resolved through Students' Critical Thinking

ERIC Educational Resources Information Center

Spierenburg, Rick; Jacobse, Leon; de Bruin, Iris; van den Bos, Daan J.; Vis, Dominique M.; Juurlink, Ludo B. F.

2017-01-01

As it connects to a large set of important fundamental ideas in chemistry and analytical techniques discussed in high school chemistry curricula, we review the exploding flask demonstration. In this demonstration, methanol vapor is catalytically oxidized by a Pt wire catalyst in an open container. The exothermicity of reactions occurring at the…

Old Faithful Model for Radiolytic Gas-Driven Cryovolcanism at Enceladus

NASA Technical Reports Server (NTRS)

Cooper, John F.; Cooper, Paul D.; Sittler, Edward; Sturner, Steven J.; Rymer, Abigail M.

2009-01-01

A new model is presented on how chemically driven cryovolcanism might contribute to episodic outgassing at the icy moon Enceladus and potentially elsewhere including Europa and Kuiper Belt Objects. Exposed water ices can become oxidized from radiolytic chemical alteration of near-surface water ice by space environment irradiation. In contact with primordially abundant reductants such as NH3, CH4, and other hydrocarbons, the product oxidants can react exothermically to produce volatile gases driving cryovolcanism via gas-piston forces on any subsurface liquid reservoirs. Radiolytic oxidants such as H2O2 and O2 can continuously accumulate deep in icy regoliths and be conveyed by rheological flows to subsurface chemical reaction zones over million-year time scales indicated by cratering ages for active regions of Enceladus and Europa. Surface blanketing with cryovolcanic plume ejecta would further accelerate regolith burial of radiolytic oxidants. Episodic heating from transient gravitational tides, radioisotope decay, impacts, or other geologic events might occasionally accelerate chemical reaction rates and ignite the exothermic release of cumulative radiolytic oxidant energy. The time history for the suggested "Old Faithful" model of radiolytic gas-driven cryovolcanism at Enceladus and elsewhere therefore consists of long periods of chemical energy accumulation punctuated by much briefer episodes of cryovolcanic activity. The most probable sequence for detection of activity in the current epoch is a long evolutionary phase of slow but continuous oxidant accumulation over billions of years followed by continuous but variable high activity over the past 10(exp 7)-10(exp 8) years. Detectable cryovolcanic activity could then later decline due to near-total oxidation of the rheologically accessible ice crust and depletion the accessible reductant abundances, as may have already occurred for Europa in the more intense radiation environment of Jupiter's magnetosphere. Astrobiological potential of Enceladus could correspondingly be higher than at Europa due to a less extreme state of oxidation and greater residual abundance of organics.

Rapid solid-state metathesis route to transition-metal doped titanias

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coleman, Nathaniel; Perera, Sujith; Gillan, Edward G., E-mail: edward-gillan@uiowa.edu

2015-12-15

Rapid solid-state metathesis (SSM) reactions are often short-lived highly exothermic reactions that yield a molten alkali halide salt that aids in product growth and crystallization. SSM reactions may also produce kinetically stabilized structures due to the short (seconds) reaction times. This report describes the investigation of rapid SSM reactions in the synthesis of transition-metal doped titanias (M–TiO{sub 2}). The dopant targeted compositions were ten mol percent and based on elemental analysis, many of the M–TiO{sub 2} samples were close to this targeted level. Based on surface analysis, some samples showed large enrichment in surface dopant content, particularly chromium and manganesemore » doped samples. Due to the highly exothermic nature of these reactions, rutile structured TiO{sub 2} was observed in all cases. The M–TiO{sub 2} samples are visible colored and show magnetic and optical properties consistent with the dopant in an oxide environment. UV and visible photocatalytic experiments with these visibly colored rutile M–TiO{sub 2} powders showed that many of them are strongly absorbent for methylene blue dye and degrade the dye under both UV and visible light illumination. This work may open up SSM reactions as an alternate non-thermodynamic reaction strategy for dopant incorporation into a wide range of oxide and non-oxides.« less

Electroplating of aluminium microparticles with nickel to synthesise reactive core-shell structures for thermal joining applications

NASA Astrophysics Data System (ADS)

Schreiber, S.; Zaeh, M. F.

2018-06-01

Reactive particles represent a promising alternative for effectively joining components with freeform surfaces and different material properties. While the primary application of reactive systems is combustion synthesis for the production of high-performance alloys, the highly exothermic reaction can also be used to firmly bond thermosensitive joining partners. Core-shell structures are of special interest, since they function as separate microreactors. In this paper, a method to synthesise reactive nickel-aluminium core-shell structures via a two-step plating process is described. Based on an electroless process, the natural oxide layer of the aluminium particles is removed and substituted with a thin layer of nickel. Subsequently, the pre-treated particles are electroplated with nickel. The high reactivity of aluminium and the oxide layer play a significant role in adjusting the process parameters of the Watts bath. Additionally, the developed experimental set-up is introduced and the importance of process control is shown. In order to achieve reproducible results, the electroplating process was automated. Ignition tests with electromagnetic waves demonstrated that the particles undergo an exothermic reaction. Therefore, they can be used as a heat source in thermal joining applications.

Sustainable synthesis of aldehydes, ketones or acids from neat alcohols using nitrogen dioxide gas, and related reactions.

PubMed

Naimi-Jamal, M Reza; Hamzeali, Hamideh; Mokhtari, Javad; Boy, Jürgen; Kaupp, Gerd

2009-01-01

Benzylic alcohols are quantitatively oxidized by gaseous nitrogen dioxide to give pure aromatic aldehydes. The reaction gas mixtures are transformed to nitric acid, which renders the processes free of waste. The exothermic gas-liquid or gas-solid reactions profit from the solubility of nitrogen dioxide in the neat benzylic alcohols. The acid formed impedes further oxidation of the benzaldehydes. The neat isolated benzaldehydes and nitrogen dioxide quantitatively give the benzoic acids. Solid long-chain primary alcohols are directly and quantitatively oxidized with nitrogen dioxide gas to give the fatty acids in the solid state. The oxidations with ubiquitous nitrogen dioxide are extended to solid heterocyclic thioamides, which gives disulfides, and to diphenylamine, which gives tetraphenylhydrazine. These sustainable (green) specific oxidation procedures produce no dangerous residues from the oxidizing agent or from auxiliaries.

SUNgas: Thermochemical Approaches to Solar Fuels

NASA Astrophysics Data System (ADS)

Davidson, Jane

2013-04-01

Solar energy offers an intelligent solution to reduce anthropogenic emissions of greenhouse gases and to meet an expanding global demand for energy. A transformative change from fossil to solar energy requires collection, storage, and transport of the earth's most abundant but diffuse and intermittent source of energy. One intriguing approach for harvest and storage of solar energy is production of clean fuels via high temperature thermochemical processes. Concentrated solar energy is the heat source and biomass or water and carbon dioxide are the feedstocks. Two routes to produce fuels using concentrated solar energy and a renewable feed stock will be discussed: gasification of biomass or other carbonaceous materials and metal oxide cycles to produce synthesis gas. The first and most near term route to solar fuels is to gasify biomass. With conventional gasification, air or oxygen is supplied at fuel-rich levels to combust some of the feedstock and in this manner generate the energy required for conversion to H2 and CO. The partial-combustion consumes up to 40% of the energetic value of the feedstock. With air combustion, the product gas is diluted by high levels of CO2 and N2. Using oxygen reduces the product dilution, but at the expense of adding an oxygen plant. Supplying the required heat with concentrated solar radiation eliminates the need for partial combustion of the biomass feedstock. As a result, the product gas has an energetic value greater than that of the feedstock and it is not contaminated by the byproducts of combustion. The second promising route to solar fuels splits water and carbon dioxide. Two-step metal-oxide redox cycles hold out great potential because they the temperature required to achieve a reasonable degree of dissociation is lower than direct thermal dissociation and O2 and the fuel are produced in separate steps. The 1^st step is the endothermic thermal dissociation of the metal oxide to the metal or lower-valence metal oxide. The 2^nd exothermic step is the hydrolysis of the reduced metal to form H2 and the corresponding metal oxide. Two promising options for 2-step cycles, the Zn/ZnO and non-stoichiometric ceria redox cycles, will be compared with a focus on efficiency and state of the art achievements.

The mechanisms of hydrothermal deconstruction of lignocellulose: New insights from thermal–analytical and complementary studies

PubMed Central

Ibbett, Roger; Gaddipati, Sanyasi; Davies, Scott; Hill, Sandra; Tucker, Greg

2011-01-01

Differential Scanning Calorimetry, Dynamic Mechanical Thermal Analysis, gravimetric and chemical techniques have been used to study hydrothermal reactions of straw biomass. Exothermic degradation initiates above 195 °C, due to breakdown of the xylose ring from hemicellulose, which may be similar to reactions occurring during the early stage pyrolysis of dry biomass, though activated at lower temperature through water mediation. The temperature and magnitude of the exotherm reduce with increasing acid concentration, suggesting a reduction in activation energy and a change in the balance of reaction pathways. The presence of xylan oligomers in auto-catalytic hydrolysates is believed to be due to a low rate constant rather than a specific reaction mechanism. The loss of the lignin glass transition indicates that the lignin phase is reorganised under high temperature auto-catalytic conditions, but remains partially intact under lower temperature acid-catalytic conditions. This shows that lignin degradation reactions are activated thermally but are not effectively catalysed by aqueous acid. PMID:21763128

Laboratory Annealing Experiments Of Refractory Silicate Grain Analogs Using Differential Scanning Calorimetry

NASA Technical Reports Server (NTRS)

Kimura, Yuki; Nuth, Joseph A., III; Tsukamota, Katsuo; Kaito, Chihiro

2010-01-01

Exothermic reactions during the annealing of laboratory synthesized amorphous magnesium-bearing silicate particles used as grain analogs of cosmic dust were detected by differential scanning calorimetry (DSC) in air. With infrared spectroscopy and transmission electron microscopy, we show that cosmic dust could possibly undergo fusion to larger particles, with oxidation of magnesium silicide and crystallization of forsterite as exothermic reactions in the early solar system. The reactions begin at approximately 425, approximately 625, and approximately 1000 K, respectively, and the reaction energies (enthalpies) are at least 727, 4151, and 160.22 J per gram, respectively. During the crystallization of forsterite particles, the spectral evolution of the 10 micrometer feature from amorphous to crystalline was observed to begin at lower temperature than the crystallization temperature of 1003 K. During spectral evolution at lower temperature, nucleation and/or the formation of nanocrystallites of forsterite at the surface of the grain analogs was observed.

Modeling of Water-Breathing Propulsion Systems Utilizing the Aluminum-Seawater Reaction and Solid-Oxide Fuel Cells

DTIC Science & Technology

2011-01-01

ABSTRACT Title of Document: MODELING OF WATER-BREATHING PROPULSION SYSTEMS UTILIZING THE ALUMINUM-SEAWATER REACTION AND SOLID...Hybrid Aluminum Combustor (HAC): a novel underwater power system based on the exothermic reaction of aluminum with seawater. The system is modeled ...using a NASA-developed framework called Numerical Propulsion System Simulation (NPSS) by assembling thermodynamic models developed for each component

Adsorption of arsenic(V) by iron-oxide-coated diatomite (IOCD).

PubMed

Pan, Yi-Fong; Chiou, Cary T; Lin, Tsair-Fuh

2010-09-01

PURPOSES AND AIMS: Economically efficient methods for removing arsenic from the drinking water supply are urgently needed in many parts of the world. Iron oxides are known to have a strong affinity for arsenic in water. However, they are commonly present in the forms of fine powder or floc, which limits their utility in water treatment. In this study, a novel granular adsorbent, iron-oxide-coated diatomite (IOCD), was developed and examined for its adsorption of arsenic from water. An industrial-grade diatomite was used as the iron oxide support. The diatomite was first acidified and dried and then coated with iron oxide up to five times. The prepared IOCD samples were characterized for their morphology, composition, elemental content, and crystal properties by various instruments. Experiments of equilibrium and kinetic adsorption of As(V) on IOCD were conducted using 0.1- and 2-L polyethylene bottles, respectively, at different pH and temperatures. Iron oxide (alpha-Fe(2)O(3) hematite) coated onto diatomite greatly improves (by about 30 times) the adsorption of As(V) from water by IOCD as compared to using raw diatomite. This improvement was attributed to increases in both surface affinity and surface area of the IOCD. The surface area of IOCD increased to an optimal value. However, as the IOCD surface area (93 m(2)/g) was only 45% higher than that of raw diatomite (51 m(2)/g), the enhanced As(V) adsorption resulted primarily from the enhanced association of negatively charged As(V) ions with the partial positive surface charge of the iron oxide. The As(V) adsorption decreased when the solution pH was increased from 3.5 to 9.5, as expected from the partial charge interaction between As(V) and IOCD. The adsorption data at pH 5.5 and 7.5 could be well fitted to the Freundlich equation. A moderately high exothermic heat was observed for the As(V) adsorption, with the calculated molar isosteric heat ranging from -4 to -9 kcal/mol. The observed heats fall between those for physical adsorption and chemisorption and are indicative of the formation of a series of ion-pair complexes of As(V) ions with iron oxide surface groups. This study demonstrated that the granular IOCD was successfully developed and employed to remove the As(V) in aqueous solution. The Freundlich isotherm well fitted the equilibrium adsorption data of As(V) onto IOCD, and both the pseudo-second-order model and the pore diffusion model simulated well the adsorption kinetics. Compared to other iron-oxide-based adsorbents reported in the literatures, the adsorption capacity of IOCD is relatively high and its kinetics is fast.

Exothermic Surface Reactions in Alumina-Aluminum Shell-Core Nanoparticles with Iodine Oxide Decomposition Fragments

DTIC Science & Technology

2014-02-22

substantially high heat of combustion 6.22 kJ/g in comparison to other thermite reactions such as Al/CuO (4.09 kJ/g), Al/MoO3 (4.72 kJ/g), and Al/Fe2O3 (3.97 kJ...oxide shell growth on nano aluminum thermite propagation rates. Combust Flame 159:3448 3453 Granier JJ, Pantoya ML (2004) Laser ignition of...nanocomposite thermites . Combust Flame 138:373 383 2310 Page 8 of 9 J Nanopart Res (2014) 16:2310 1 3 Hlavacek V, Pranda P, Prandova K (2005) Reactivity, stored

A DFT study of permanganate oxidation of toluene and its ortho-nitroderivatives.

PubMed

Adamczyk, Paweł; Wijker, Reto S; Hofstetter, Thomas B; Paneth, Piotr

2014-02-01

Calculations of alternative oxidation pathways of toluene and its ortho-substituted nitro derivatives by permanganate anion have been performed. The competition between methyl group and ring oxidation has been addressed. Acceptable results have been obtained using IEFPCM/B3LYP/6-31+G(d,p) calculations with zero-point (ZPC) and thermal corrections, as validated by comparison with the experimental data. It has been shown that ring oxidation reactions proceed via relatively early transition states that become quite unsymmetrical for reactions involving ortho-nitrosubstituted derivatives. Transition states for the hydrogen atom abstraction reactions, on the other hand, are late. All favored reactions are characterized by the Gibbs free energy of activation, ΔG(≠), of about 25 kcal mol(-1). Methyl group oxidations are exothermic by about 20 kcal mol(-1) while ring oxidations are around thermoneutrality.

Biologically tunable reactivity of energetic nanomaterials using protein cages.

PubMed

Slocik, Joseph M; Crouse, Christopher A; Spowart, Jonathan E; Naik, Rajesh R

2013-06-12

The performance of aluminum nanomaterial based energetic formulations is dependent on the mass transport, diffusion distance, and stability of reactive components. Here we use a biologically inspired approach to direct the assembly of oxidizer loaded protein cages onto the surface of aluminum nanoparticles to improve reaction kinetics by reducing the diffusion distance between the reactants. Ferritin protein cages were loaded with ammonium perchlorate (AP) or iron oxide and assembled with nAl to create an oxidation-reduction based energetic reaction and the first demonstration of a nanoscale biobased thermite material. Both materials showed enhanced exothermic behavior in comparison to nanothermite mixtures of bulk free AP or synthesized iron oxide nanopowders prepared without the use of ferritin. In addition, by utilizing a layer-by-layer (LbL) process to build multiple layers of protein cages containing iron oxide and iron oxide/AP on nAl, stoichiometric conditions and energetic performance can be optimized.

Methylene blue adsorption on graphene oxide/calcium alginate composites.

PubMed

Li, Yanhui; Du, Qiuju; Liu, Tonghao; Sun, Jiankun; Wang, Yonghao; Wu, Shaoling; Wang, Zonghua; Xia, Yanzhi; Xia, Linhua

2013-06-05

Graphene oxide has been used as an adsorbent in wastewater treatment. However, the dispersibility in aqueous solution and the biotoxicity to human cells of graphene oxide limits its practical application in environmental protection. In this research, a novel environmental friendly adsorbent, calcium alginate immobilized graphene oxide composites was prepared. The effects of pH, contact time, temperature and dosage on the adsorption properties of methylene blue onto calcium alginate immobilized graphene oxide composites were investigated. The equilibrium adsorption data were described by the Langmuir and Freundlich isotherms. The maximum adsorption capacity obtained from Langmuir isotherm equation was 181.81 mg/g. The pseudo-first order, pseudo-second order, and intraparticle diffusion equation were used to evaluate the kinetic data. Thermodynamic analysis of equilibriums indicated that the adsorption reaction of methylene blue onto calcium alginate immobilized graphene oxide composites was exothermic and spontaneous in nature. Copyright © 2013 Elsevier Ltd. All rights reserved.

Methanol from CO2 by organo-cocatalysis: CO2 capture and hydrogenation in one process step.

PubMed

Reller, Christian; Pöge, Matthias; Lißner, Andreas; Mertens, Florian O R L

2014-12-16

Carbon dioxide chemically bound to alcohol-amines was hydrogenated to methanol under retrieval of these industrially used CO2 capturing reagents. The energetics of the process can be seen as a partial cancellation of the exothermic heat of reaction of the hydrogenation with the endothermic one of the CO2 release from the capturing reagent. The process provides a means to significantly improve the energy efficiency of CO2 to methanol conversions.

Development of chemically bonded phosphate ceramics for stabilizing low-level mixed wastes

NASA Astrophysics Data System (ADS)

Jeong, Seung-Young

1997-11-01

Novel chemically bonded phosphate ceramics have been developed by acid-base reactions between magnesium oxide and an acid phosphate at room temperature for stabilizing U.S. Department of Energy's low-level mixed waste streams that include hazardous chemicals and radioactive elements. Newberyite (MgHPOsb4.3Hsb2O)-rich magnesium phosphate ceramic was formed by an acid-base reaction between phosphoric acid and magnesium oxide. The reaction slurry, formed at room-temperature, sets rapidly and forms stable mineral phases of newberyite, lunebergite, and residual MgO. Rapid setting also generates heat due to exothermic acid-base reaction. The reaction was retarded by partially neutralizing the phosphoric acid solution by adding sodium or potassium hydroxide. This reduced the rate of reaction and heat generation and led to a practical way of producing novel magnesium potassium phosphate ceramic. This ceramic was formed by reacting stoichiometric amount of monopotassium dihydrogen phosphate crystals, MgO, and water, forming pure-phase of MgKPOsb4.6Hsb2O (MKP) with moderate exothermic reaction. Using this chemically bonded phosphate ceramic matrix, low-level mixed waste streams were stabilized, and superior waste forms in a monolithic structure were developed. The final waste forms showed low open porosity and permeability, and higher compression strength than the Land Disposal Requirements (LDRs). The novel MKP ceramic technology allowed us to develop operational size waste forms of 55 gal with good physical integrity. In this improved waste form, the hazardous contaminants such as RCRA heavy metals (Hg, Pb, Cd, Cr, Ni, etc) were chemically fixed by their conversion into insoluble phosphate forms and physically encapsulated by the phosphate ceramic. In addition, chemically bonded phosphate ceramics stabilized radioactive elements such U and Pu. This was demonstrated with a detailed stabilization study on cerium used as a surrogate (chemically equivalent but nonradioactive) of U and Pu as well as on actual U-contaminated waste water. In particular, the leaching level of mercury in the Toxicity Characteristic Leaching Procedure (TCLP) test was reduced from 5000 to 0.00085 ppm, and the leaching level of cerium in the long term leaching test (ANS 16.1 test) was below the detection limit. These results show that the chemically bonded phosphate ceramics process may be a simple, inexpensive, and efficient method for stabilizing low-level mixed waste streams.

Review on Thermal Decomposition of Ammonium Nitrate

NASA Astrophysics Data System (ADS)

Chaturvedi, Shalini; Dave, Pragnesh N.

2013-01-01

In this review data from the literature on thermal decomposition of ammonium nitrate (AN) and the effect of additives to their thermal decomposition are summarized. The effect of additives like oxides, cations, inorganic acids, organic compounds, phase-stablized CuO, etc., is discussed. The effect of an additive mainly occurs at the exothermic peak of pure AN in a temperature range of 200°C to 140°C.

Benzylpyrazinium Salts as Photo-Initiators in the Polymerization of Epoxide Monomers

PubMed Central

Kim, Moon Suk; Lee, Sang Bong

2014-01-01

In order to study the capability of pyrazinium salt derivatives to act as photo-initiators of epoxide monomers, benzyl pyrazinium hexafluoroantimonate (BPH), benzyl 3,5-dimethyl pyrazine hexafluoroantimonate (BDH) and benzyl quinoxalinium hexafluoroantimonate (BQH) were synthesized by the Menschutkin reaction of benzyl bromide with pyrazine, 2,6-dimethyl pyrazine, and quinoxaline, followed by exchanging with hexafluoroantimonate (SbF6). BPH, BDH, and BQH exhibited characteristic ultraviolet (UV) absorbance as well as exothermic peaks as a function of irradiation time in a differential photo-calorimeter (DPC). In the absence of photo-irradiation, cyclohexene oxide (CHO) underwent slow polymerization at 25 °C using BPH derivatives, but quantitative conversion was achieved even after a 5-min photo-irradiation. In addition, photo-irradiation was required for the photo-polymerization of CHO and styrene oxide (STO), which was characterized by a short induction period followed by a very rapid and exothermic polymerization. While glycidyl methyl ether (GME) required long induction periods, glycidyl phenyl ether (GPE) underwent rather slow and/or no photo-polymerization. The reactivity order of the monomers was CHO > STO >> GME >>> GPE, and the reactivity order for the photo-polymerization of CHO was BPH > BQH > BDH. It was found that BPH, BDH, and BQH could serve as photo-latent initiators for CHO, STO and GME, respectively. PMID:28788147

Benzylpyrazinium Salts as Photo-Initiators in the Polymerization of Epoxide Monomers.

PubMed

Kim, Moon Suk; Lee, Sang Bong

2014-07-31

In order to study the capability of pyrazinium salt derivatives to act as photo-initiators of epoxide monomers, benzyl pyrazinium hexafluoroantimonate (BPH), benzyl 3,5-dimethyl pyrazine hexafluoroantimonate (BDH) and benzyl quinoxalinium hexafluoroantimonate (BQH) were synthesized by the Menschutkin reaction of benzyl bromide with pyrazine, 2,6-dimethyl pyrazine, and quinoxaline, followed by exchanging with hexafluoroantimonate (SbF₆). BPH, BDH, and BQH exhibited characteristic ultraviolet (UV) absorbance as well as exothermic peaks as a function of irradiation time in a differential photo-calorimeter (DPC). In the absence of photo-irradiation, cyclohexene oxide (CHO) underwent slow polymerization at 25 °C using BPH derivatives, but quantitative conversion was achieved even after a 5-min photo-irradiation. In addition, photo-irradiation was required for the photo-polymerization of CHO and styrene oxide (STO), which was characterized by a short induction period followed by a very rapid and exothermic polymerization. While glycidyl methyl ether (GME) required long induction periods, glycidyl phenyl ether (GPE) underwent rather slow and/or no photo-polymerization. The reactivity order of the monomers was CHO > STO > GME > GPE, and the reactivity order for the photo-polymerization of CHO was BPH > BQH > BDH. It was found that BPH, BDH, and BQH could serve as photo-latent initiators for CHO, STO and GME, respectively.

Density-functional theory study of dimethyl carbonate synthesis by methanol oxidative carbonylation on single-atom Cu1/graphene catalyst

NASA Astrophysics Data System (ADS)

Sun, Wei; Shi, Ruina; Wang, Xuhui; Liu, Shusen; Han, Xiaoxia; Zhao, Chaofan; Li, Zhong; Ren, Jun

2017-12-01

The mechanism for dimethyl carbonate (DMC) synthesis by oxidation carbonylation of methanol on a single-atom Cu1/graphene catalyst was investigated by density-functional theory calculations. Carbon vacancies in graphene can significantly enhance the interaction between Cu atoms and graphene supports, and provide an increased transfer of electrons from Cu atoms to the graphene sheet. Compared with Cu-doped divacancy graphene (Cu/DG), Cu-doped monovacancy graphene (Cu/MG) provides a stronger interaction between adsorbents and the catalyst surface. Among the reaction processes over Cu1/graphene catalysts, CO insertion into methoxide was more favorable than dimethoxide. The rate-limiting step on the Cu/DG surface is the carbomethoxide reaction with methoxide, which is exothermic by 164.6 kJ mol-1 and has an activation barrier of 190.9 kJ mol-1 energy. Compared with that on the Cu crystal surface, Cu4 and Cu3Rh clusters, and the Cu2O(111) surface, the rate-determining step for DMC formation on Cu/MG, which is CO insertion into methoxide, needs to overcome the lowest barrier of 73.5 kJ mol-1 and is exothermic by 44.6 kJ mol-1. Therefore, Cu/MG was beneficial to the formation of DMC as a single-atom catalyst.

Self-heating of dried industrial tannery wastewater sludge induced by pyrophoric iron sulfides formation.

PubMed

Bertani, R; Biasin, A; Canu, P; Della Zassa, M; Refosco, D; Simionato, F; Zerlottin, M

2016-03-15

Similarly to many powders of solids, dried sludge originated from tannery wastewater may result in a self-heating process, under given circumstances. In most cases, it causes a moderate heating (reaching 70-90°C), but larger, off-design residence times in the drier, in a suboxic atmosphere, extremely reactive solids can be produced. Tannery waste contains several chemicals that mostly end up in the wastewater treatment sludge. Unexpected and uncontrolled self heating could lead to a combustion and even to environmental problems. Elaborating on previous studies, with the addition of several analytical determinations, before and after the self-heating, we attempted to formulate a mechanism for the onset of heating. We demonstrated that the system Fe/S/O has been involved in the process. We proved that the formation of small quantities of pyrophoric iron sulfides is the key. They are converted to sulfated by reaction with water and oxygen with exothermic processes. The pyrite/pyrrhotite production depends on the sludge drying process. The oxidation of sulfides to oxides and sulfates through exothermic steps, reasonably catalyzed by metals in the sludge, occurs preferentially in a moist environment. The mechanism has been proved by reproducing in the laboratory prolonged heating under anoxic/suboxic atmosphere. Copyright © 2015 Elsevier B.V. All rights reserved.

The oxidation of aluminum at high temperature studied by Thermogravimetric Analysis and Differential Scanning Calorimetry.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coker, Eric Nicholas

2013-10-01

The oxidation in air of high-purity Al foil was studied as a function of temperature using Thermogravimetric Analysis with Differential Scanning Calorimetry (TGA/DSC). The rate and/or extent of oxidation was found to be a non-linear function of the temperature. Between 650 and 750 ÀC very little oxidation took place; at 850 ÀC oxidation occurred after an induction period, while at 950 ÀC oxidation occurred without an induction period. At oxidation temperatures between 1050 and 1150 ÀC rapid passivation of the surface of the aluminum foil occurred, while at 1250 ÀC and above, an initial rapid mass increase was observed, followedmore » by a more gradual increase in mass. The initial rapid increase was accompanied by a significant exotherm. Cross-sections of oxidized specimens were characterized by scanning electron microscopy (SEM); the observed alumina skin thicknesses correlated qualitatively with the observed mass increases.« less

Combustible structural composites and methods of forming combustible structural composites

DOEpatents

Daniels, Michael A [Idaho Falls, ID; Heaps, Ronald J [Idaho Falls, ID; Steffler, Eric D [Idaho Falls, ID; Swank, William D [Idaho Falls, ID

2011-08-30

Combustible structural composites and methods of forming same are disclosed. In an embodiment, a combustible structural composite includes combustible material comprising a fuel metal and a metal oxide. The fuel metal is present in the combustible material at a weight ratio from 1:9 to 1:1 of the fuel metal to the metal oxide. The fuel metal and the metal oxide are capable of exothermically reacting upon application of energy at or above a threshold value to support self-sustaining combustion of the combustible material within the combustible structural composite. Structural-reinforcing fibers are present in the composite at a weight ratio from 1:20 to 10:1 of the structural-reinforcing fibers to the combustible material. Other embodiments and aspects are disclosed.

Combustible structural composites and methods of forming combustible structural composites

DOEpatents

Daniels, Michael A.; Heaps, Ronald J.; Steffler, Eric D.; Swank, W. David

2013-04-02

Combustible structural composites and methods of forming same are disclosed. In an embodiment, a combustible structural composite includes combustible material comprising a fuel metal and a metal oxide. The fuel metal is present in the combustible material at a weight ratio from 1:9 to 1:1 of the fuel metal to the metal oxide. The fuel metal and the metal oxide are capable of exothermically reacting upon application of energy at or above a threshold value to support self-sustaining combustion of the combustible material within the combustible structural composite. Structural-reinforcing fibers are present in the composite at a weight ratio from 1:20 to 10:1 of the structural-reinforcing fibers to the combustible material. Other embodiments and aspects are disclosed.

Oxygen transport and pyrite oxidation in unsaturated coal-mine spoil

USGS Publications Warehouse

Guo, Weixing; Cravotta, Charles A.

1996-01-01

An understanding of the mechanisms of oxygen (02) transport in unsaturated mine spoil is necessary to design and implement effective measures to exclude 02 from pyritic materials and to control the formation of acidic mine drainage. Partial pressure of oxygen (Po2) in pore gas, chemistry of pore water, and temperature were measured at different depths in unsaturated spoil at two reclaimed surface coal mines in Pennsylvania. At mine 1, where spoil was loose, blocky sandstone, Po2 changed little with depth, decreasing from 21 volume percent (vol%) at the ground surface to a minimum of about 18 vol% at 10 m depth. At mine 2, where spoil was compacted, friable shale, Po2 decreased to less than 2 vol% at depth of about 10 m. Although pore-water chemistry and temperature data indicate that acid-forming reactions were active at both mines, the pore-gas data indicate that mechanisms for 0 2 transport were different at each mine. A numerical model was developed to simulate 02 transport and pyrite oxidation in unsaturated mine spoil. The results of the numerical simulations indicate that differences in 02 transport at the two mines can be explained by differences in the air permeability of spoil. Po2 changes little with depth if advective transport of 02 dominates as at mine 1, but decreases greatly with depth if diffusive transport of 02 dominates, as in mine 2. Model results also indicate that advective transport becomes significant if the air permeability of spoil is greater than 10-9 m2, which is expected for blocky sandstone spoil. In the advective-dominant system, thermally-induced convective air flow, as a consequence of the exothermic oxidation of pyrite, supplies the 02 to maintain high Po2 within the deep unsaturated zone.

URANIUM DIOXIDE OXIDATION WITH FORMING INTERMEDIATE PHASES (in German)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scheibe, H.; Ermischer, W.

1964-02-01

An experimental study was made of the UO/sub 2/ to U/sub 3/O/sub 8/ oxidation process. At low temperatures, depending on the activity of the powder, the oxidation of UO/sub 2/ yield a U/sub 3/O/sub 7/ shell around the UO/sub 2/ grain (160 to 220 deg C). Further oxidation is determined by the diffusion of oxygen through this shell and yields U/sub 5/O/sub 12/ (280 to 290 deg C). Their follows U/sub 5/O/sub (375 to 400 deg C) and finally U/sub 3/O/sub 8/ as more oxigen is absorbed. No further increase of the oxygen content occurs up to 800 deg C.more » The exothermal effects established through differential thermal analysis may be due to lattice transformation. (OTS)« less

Cyclical Annealing Technique To Enhance Reliability of Amorphous Metal Oxide Thin Film Transistors.

PubMed

Chen, Hong-Chih; Chang, Ting-Chang; Lai, Wei-Chih; Chen, Guan-Fu; Chen, Bo-Wei; Hung, Yu-Ju; Chang, Kuo-Jui; Cheng, Kai-Chung; Huang, Chen-Shuo; Chen, Kuo-Kuang; Lu, Hsueh-Hsing; Lin, Yu-Hsin

2018-02-26

This study introduces a cyclical annealing technique that enhances the reliability of amorphous indium-gallium-zinc-oxide (a-IGZO) via-type structure thin film transistors (TFTs). By utilizing this treatment, negative gate-bias illumination stress (NBIS)-induced instabilities can be effectively alleviated. The cyclical annealing provides several cooling steps, which are exothermic processes that can form stronger ionic bonds. An additional advantage is that the total annealing time is much shorter than when using conventional long-term annealing. With the use of cyclical annealing, the reliability of the a-IGZO can be effectively optimized, and the shorter process time can increase fabrication efficiency.

Solid State Carbon Monoxide Sensor

NASA Technical Reports Server (NTRS)

Upchurch, Billy T. (Inventor); Wood, George M. (Inventor); Schryer, David R. (Inventor); Leighty, Bradley D. (Inventor); Oglesby, Donald M. (Inventor); Kielin, Erik J. (Inventor); Brown, Kenneth G. (Inventor); DAmbrosia, Christine M. (Inventor)

1999-01-01

A means for detecting carbon monoxide which utilizes an un-heated catalytic material to oxidize carbon monoxide at ambient temperatures. Because this reaction is exothermic, a thermistor in contact with the catalytic material is used as a sensing element to detect the heat evolved as carbon monoxide is oxidized to carbon dioxide at the catalyst surface, without any heaters or external heating elements for the ambient air or catalytic element material. Upon comparison to a reference thermistor, relative increases in the temperature of the sensing thermistor correspond positively with an increased concentration of carbon monoxide in the ambient medium and are thus used as an indicator of the presence of carbon monoxide.

Diclofenac salts. III. Alkaline and earth alkaline salts.

PubMed

Fini, Adamo; Fazio, Giuseppe; Rosetti, Francesca; Angeles Holgado, M; Iruín, Ana; Alvarez-Fuentes, Josefa

2005-11-01

Diclofenac salts containing the alkaline and two earth alkaline cations have been prepared and characterized by scanning electron microscopy (SEM) and EDAX spectroscopy; and by thermal and thermogravimetric analysis (TGA): all of them crystallize as hydrate when precipitated from water. The salts dehydrate at room temperature and more easily on heating, but recovery the hydration, when placed in a humid environment. X-ray diffraction spectra suggest that on dehydration new peaks appear on diffractograms and the lattice of the salts partially looses crystallinity. This phenomenon is readily visible in the case of the calcium and magnesium salts, whose thermograms display a crystallization exotherm, before melting or decomposing at temperatures near or above 200 degrees C; these last salts appear to form solvates, when prepared from methanol. The thermogram of each salt shows a complex endotherm of dehydration about 100 degrees C; the calcium salt displays two endotherms, well separated at about 120 and 160 degrees C, which disappear after prolonged heating. Decomposition exotherms, before or soon after the melting, appear below 300 degrees C. The ammonium salt is thermally unstable and, when heated to start dehydration, dissociates and leaves acidic diclofenac.

Analysis of solid propellant combustion in a closed vessel including secondary reaction

NASA Technical Reports Server (NTRS)

Benreuven, M.; Summerfield, M.

1980-01-01

A theory for combustion of solid propellants in a closed vessel is presented allowing for residual exothermic chemical reaction in the bulk of the gas in the vessel. Particular attention is given to propellants exhibiting thick gaseous flame zones such as nitrocellulose, double-base and nitramine propellants. For these, the reaction at high pressures is assumed to involve mainly the oxidation of residual hydrocarbons by NO. It is shown that the direct dynamic coupling between the exothermicity, the molecular weight reduction and the changing pressure can influence the dp/dt-p traces obtained, in a manner not directly related to mass burning rate of the solid. Energy and species conservation equations are derived for the bulk of the vessel in differential form; the system is solved numerically. The results show the effect of extended chemical reaction upon measurable combustion characteristics such as dp/dt-p and burn rate pressure exponent, demonstrating its potential importance in interpretation of closed vessel firing data, depending on the pace of the residual gas phase reactions.

Antioxidant activity of omega-3 derivatives and their delivery via nanocages and nanocones: DFT and experimental in vivo investigation.

PubMed

Najafi, Houshang; Changizi-Ashtiyani, Saeed; Najafi, Meysam

2017-10-28

The antioxidant properties of omega-3 were investigated via experimental in vivo and theoretical methods. For experimental evaluation, oxidative stress was induced by 30 min bilateral renal ischemia and 24 h of reperfusion in male Sprague Dawley rats. The oxidative stress was evaluated through measuring malondialdehyde (MDA) and ferric reducing/antioxidant power (FRAP) levels in renal tissue. In theoretical methods, the reaction enthalpies of antioxidant mechanisms of omega-3 were calculated and the effects of NHMe, OMe, OH, Cl, and Me substituents on its antioxidant activity were investigated. Moreover, the omega-3 delivery potential by carbon and boron nitride nanocages and naocones were evaluated. The experimental results showed that omega-3 administration decreases MDA and increases FRAP levels after their changes by ischemia/reperfusion. Theoretical results indicated that NHMe and OMe substituents can significantly improve the antioxidant activity of omega-3. Also, boron nitride nanocone (BNNC) has higher |∆E ad | values, so it has higher potential for omega-3 delivery. Taken together, the new findings presented here indicate that omega-3 has anti-oxidative properties and NHMe and OMe substituents can improve its antioxidant activity. Moreover, adsorption of omega-3 on the surface of the studied nanostructures was exothermic, and BNNC with higher |∆Ead| values has higher potential for omega-3 delivery. Graphical abstract The interaction and adsorption of BNNC with omega-3 is exothermic and experimentally possible from the energetic viewpoint, so the BNNC with higher |∆E ad | and |∆G ad | values has higher potential for omega-3 delivery.

Partial oxidation power plant with reheating and method thereof

DOEpatents

Newby, Richard A.; Yang, Wen-Ching; Bannister, Ronald L.

1999-01-01

A system and method for generating power having an air compression/partial oxidation system, a turbine, and a primary combustion system. The air compression/partial oxidation system receives a first air stream and a fuel stream and produces a first partially oxidized fuel stream and a first compressed air stream therefrom. The turbine expands the first partially oxidized fuel stream while being cooled by the first compressed air stream to produce a heated air stream. The heated air stream is injected into the expanding first partially oxidized fuel stream, thereby reheating it in the turbine. A second partially oxidized fuel stream is emitted from the turbine. The primary combustion system receives said second partially oxidized fuel stream and a second air stream, combusts said second partially oxidized fuel stream, and produces rotating shaft power and an emission stream therefrom.

Partial oxidation power plant with reheating and method thereof

DOEpatents

Newby, R.A.; Yang, W.C.; Bannister, R.L.

1999-08-10

A system and method are disclosed for generating power having an air compression/partial oxidation system, a turbine, and a primary combustion system. The air compression/partial oxidation system receives a first air stream and a fuel stream and produces a first partially oxidized fuel stream and a first compressed air stream therefrom. The turbine expands the first partially oxidized fuel stream while being cooled by the first compressed air stream to produce a heated air stream. The heated air stream is injected into the expanding first partially oxidized fuel stream, thereby reheating it in the turbine. A second partially oxidized fuel stream is emitted from the turbine. The primary combustion system receives said second partially oxidized fuel stream and a second air stream, combusts said second partially oxidized fuel stream, and produces rotating shaft power and an emission stream therefrom. 2 figs.

Thermal Investigations of Nanoaluminum/Perfluoropolyether Core-Shell Impregnated Composites for Structural Energetics

DTIC Science & Technology

2014-07-19

that undergo an oxidation reduction thermite reaction releasing energy. Advances in the field have generated diverse material platforms ranging from bulk...This is a pre ignition reaction (PIR) similar to the one observed by Pantoya and Dean in n Al/Teflon thermite based reactions [14]. PIR exotherms were...2010) 2560–2569. [5] S. Yan, G. Jian, M.R. Zachariah, Electrospun nanofiber-based thermite textiles and their reactive properties, ACS Appl. Mater

Crystallographic Oxide Phase Identification of Char Deposits Obtained from Space Shuttle Columbia Window Debris

NASA Technical Reports Server (NTRS)

Olivas, J. D.; Wright, M. C.; Christoffersen, R.; Cone, D. M.; McDanels, S. J.

2009-01-01

Analyzing the remains of Space Shuttle Columbia has proven technically beneficial years after the vehicle breakup. This investigation focused on charred deposits on fragments of Columbia overhead windowpanes. Results were unexpected relative to the engineering understanding of material performance in a reentry environment. The TEM analysis demonstrated that the oxides of aluminum and titanium mixed with silicon oxides to preserve a history of thermal conditions to which portions of the vehicle were exposed. The presence of Ti during the beginning of the deposition process, along with the thermodynamic phase precipitation upon cool down, indicate that temperatures well above the Ti melt point were experienced. The stratified observations implied that additional exothermic reaction, expectedly metal combustion of a Ti structure, had to be present for oxide formation. Results are significant for aerospace vehicles where thermal protection system (TPS) breaches cause substructures to be in direct path with the reentry plasma. 1

The Mechanism of Freezing Injury in Xylem of Winter Apple Twigs 1

PubMed Central

Quamme, H.; Weiser, C. J.; Stushnoff, C.

1973-01-01

In acclimated winter twigs of Haralson apple (Pyrus Malus L.), a lag in temperature during cooling at a constant rate was observed at about −41 C by differential thermal analysis. The temperature at which this low temperature exotherm occurred was essentially unaffected by the cooling rate. During thawing there was no lag in temperature (endotherm) near the temperature at which the low temperature exotherm occurred, but upon subsequent refreezing the exotherm reappeared at a somewhat higher temperature when twigs were rewarmed to at least −5 C before refreezing. These observations indicate that a small fraction of water may remain unfrozen to as low as −42 C after freezing of the bulk water in stems. The low temperature exotherm was not present in twigs freeze-dried to a water content below 8.5% (per unit fresh weight), but it reappeared when twigs were rehydrated to 20% water. When freeze-dried twigs were ground to a fine powder prior to rehydration, no exotherm was observed. Previous work has shown that the low temperature exotherm arises from xylem and pith tissues, and that injury to living cells in these tissues invariably occurs only when twigs are cooled below, but not above the temperature of the low temperature exotherm. This study revealed that the low temperature exotherm resulted from the freezing of a water fraction, that the freezing of this water was independent of the freezing of the bulk water, that the exotherm was associated with some gross structural feature but not the viability of the tissue, and that injury to living cells in the xylem and pith was closely and perhaps causally related to the initial freezing of this water. PMID:16658314

Mechanical and dye adsorption properties of graphene oxide/chitosan composite fibers prepared by wet spinning.

PubMed

Li, Yanhui; Sun, Jiankun; Du, Qiuju; Zhang, Luhui; Yang, Xiaoxia; Wu, Shaoling; Xia, Yanzhi; Wang, Zonghua; Xia, Linhua; Cao, Anyuan

2014-02-15

Graphene oxide/chitosan composite fibers were prepared by a wet spinning method, and their mechanical properties were investigated. Experimental results showed that the introduction of graphene oxide at 4 wt% loading can improve the tensile strengths of chitosan fibers. Batch adsorption experiments were carried out to study the effect of various parameters, such as the initial pH value, adsorbent dosage, contact time and temperature on adsorption of fuchsin acid dye. The Langmuir model was used to fit the experimental data of adsorption isotherm, and kinetic studies showed that the adsorption data followed the pseudo-second order model. Thermodynamic studies indicated that the adsorption of fuchsin acid dye on graphene oxide/chitosan fibers was a spontaneous and exothermic process. Our results indicate that the graphene oxide/chitosan fibers have excellent mechanical properties and can serve as a promising adsorbent for the removal of dyes from aqueous solutions. Copyright © 2013 Elsevier Ltd. All rights reserved.

High temperature two component explosive

DOEpatents

Mars, James E.; Poole, Donald R.; Schmidt, Eckart W.; Wang, Charles

1981-01-01

A two component, high temperature, thermally stable explosive composition comprises a liquid or low melting oxidizer and a liquid or low melting organic fuel. The oxidizer and fuel in admixture are incapable of substantial spontaneous exothermic reaction at temperatures on the order of 475.degree. K. At temperatures on the order of 475.degree. K., the oxidizer and fuel in admixture have an activation energy of at least about 40 kcal/mol. As a result of the high activation energy, the preferred explosive compositions are nondetonable as solids at ambient temperature, and become detonable only when heated beyond the melting point. Preferable oxidizers are selected from alkali or alkaline earth metal nitrates, nitrites, perchlorates, and/or mixtures thereof. Preferred fuels are organic compounds having polar hydrophilic groups. The most preferred fuels are guanidinium nitrate, acetamide and mixtures of the two. Most preferred oxidizers are eutectic mixtures of lithium nitrate, potassium nitrate and sodium nitrate, of sodium nitrite, sodium nitrate and potassium nitrate, and of potassium nitrate, calcium nitrate and sodium nitrate.

Theoretical description of the 2A/double prime/ and 2A/prime/ states of the peroxyformyl radical. [for air pollution and Mars atmospheric studies

NASA Technical Reports Server (NTRS)

Winter, N. W.; Goddard, W. A., III; Bender, C. F.

1975-01-01

Simple orbital ideas are used to describe the lowest two states of the peroxyformyl radical, and ab initio Hartree-Fock calculations in these states are reported. It is found that both states may be formed exothermically by association of O2 and HCO in their ground states; however, the excited state may decompose readily to OH and CO2. The possible role of such processes in oxidation of aldelydes is discussed.

Investigation of La xSr 1-xCo yM 1-yO 3-δ (M = Mn Fe) perovskite materials as thermochemical energy storage media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Babiniec, Sean Michael; Coker, Eric Nicholas; Miller, James E.

2015-06-23

Materials in the La xSr 1–xCo yMn 1–yO 3–δ (LSCM) and La xSr 1–xCo yFe 1–yO 3–δ (LSCF) families are candidates for high-temperature thermochemical energy storage due to their facility for cyclic endothermic reduction and exothermic oxidation. A set of 16 LSCM and 21 LSCF compositions were synthesized by a modified Pechini method and characterized by powder X-ray diffraction and thermogravimetric analysis. All materials were found to be various symmetries of the perovskite phase. LSCM was indexed as tetragonal, cubic, rhombohedral, or orthorhombic as a function of increased lanthanum content. For LSCF, compositions containing low lanthanum content were indexed asmore » cubic while materials with high lanthanum content were indexed as rhombohedral. An initial screening of redox activity was completed by thermogravimetric analysis for each composition. The top three compositions with the greatest recoverable redox capacity for each family were further characterized in equilibrium thermogravimetric experiments over a range of temperatures and oxygen partial pressures. As a result, these equilibrium experiments allowed the extraction of thermodynamic parameters for LSCM and LSCF compositions operated in thermochemical energy storage conditions.« less

Influence of uranium hydride oxidation on uranium metal behaviour

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patel, N.; Hambley, D.; Clarke, S.A.

2013-07-01

This work addresses concerns that the rapid, exothermic oxidation of active uranium hydride in air could stimulate an exothermic reaction (burning) involving any adjacent uranium metal, so as to increase the potential hazard arising from a hydride reaction. The effect of the thermal reaction of active uranium hydride, especially in contact with uranium metal, does not increase in proportion with hydride mass, particularly when considering large quantities of hydride. Whether uranium metal continues to burn in the long term is a function of the uranium metal and its surroundings. The source of the initial heat input to the uranium, ifmore » sufficient to cause ignition, is not important. Sustained burning of uranium requires the rate of heat generation to be sufficient to offset the total rate of heat loss so as to maintain an elevated temperature. For dense uranium, this is very difficult to achieve in naturally occurring circumstances. Areas of the uranium surface can lose heat but not generate heat. Heat can be lost by conduction, through contact with other materials, and by convection and radiation, e.g. from areas where the uranium surface is covered with a layer of oxidised material, such as burned-out hydride or from fuel cladding. These rates of heat loss are highly significant in relation to the rate of heat generation by sustained oxidation of uranium in air. Finite volume modelling has been used to examine the behaviour of a magnesium-clad uranium metal fuel element within a bottle surrounded by other un-bottled fuel elements. In the event that the bottle is breached, suddenly, in air, it can be concluded that the bulk uranium metal oxidation reaction will not reach a self-sustaining level and the mass of uranium oxidised will likely to be small in relation to mass of uranium hydride oxidised. (authors)« less

Glass transition and crystallization kinetics of a barium borosilicate glass by a non-isothermal method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopes, Andreia A. S.; Soares, Roque S.; Lima, Maria M. A.

2014-01-28

The glass transition and crystallization kinetics of a glass with a molar composition 60BaO-30B{sub 2}O{sub 3}-10SiO{sub 2} were investigated by differential scanning calorimetry (DSC) under non-isothermal conditions. DSC curves exhibited an endothermic peak associated with the glass transition and two partially overlapped exothermic peaks associated with the crystallization of the glass. The dependence of the glass transition temperature (T{sub g}) and of the maximum crystallization temperature (T{sub p}) on the heating rate was used to determine the activation energy associated with the glass transition (E{sub g}), the activation energy for crystallization (E{sub c}), and the Avrami exponent (n). X-ray diffractionmore » (XRD) revealed that barium borate (β-BaB{sub 2}O{sub 4}) was the first crystalline phase to be formed followed by the formation of barium silicate (Ba{sub 5}Si{sub 8}O{sub 21}). The variations of activation energy for crystallization and of Avrami exponent with the fraction of crystallization (χ) were also examined. When the crystallization fraction (χ) increased from 0.1 to 0.9, the value of local activation energy (E{sub c}(χ)) decreased from 554 to 458 kJ/mol for the first exothermic peak and from 1104 to 831 kJ/mol for the second exothermic peak. The value determined for the Avrami exponent was near 2 indicating a similar one-dimensional crystallization mechanism for both crystalline phases. This was confirmed by the morphological studies performed by scanning electron microscopy (SEM) on glass samples heat-treated at the first and at the second crystallization temperatures.« less

Thermochemistry of rare earth doped uranium oxides LnxU1-xO2-0.5x+y (Ln = La, Y, Nd)

NASA Astrophysics Data System (ADS)

Zhang, Lei; Navrotsky, Alexandra

2015-10-01

Lanthanum, yttrium, and neodymium doped uranium dioxide samples in the fluorite structure have been synthesized, characterized in terms of metal ratio and oxygen content, and their enthalpies of formation measured by high temperature oxide melt solution calorimetry. For oxides doped with 10-50 mol % rare earth (Ln) cations, the formation enthalpies from constituent oxides (LnO1.5, UO2 and UO3 in a reaction not involving oxidation or reduction) become increasingly exothermic with increasing rare earth content, while showing no significant dependence on the varying uranium oxidation state. The oxidation enthalpy of LnxU1-xO2-0.5x+y is similar to that of UO2 to UO3 for all three rare earth doped systems. Though this may suggest that the oxidized uranium in these systems is energetically similar to that in the hexavalent state, thermochemical data alone can not constrain whether the uranium is present as U5+, U6+, or a mixture of oxidation states. The formation enthalpies from elements calculated from the calorimetric data are generally consistent with those from free energy measurements.

Catalytic decomposition of nitrous oxide monopropellant for hybrid motor ignition

NASA Astrophysics Data System (ADS)

Wilson, Matthew

Nitrous oxide (N2O) is an inexpensive and readily available non-toxic rocket motor oxidizer. It is the most commonly used oxidizer for hybrid bipropellant rocket systems, and several bipropellant liquid rocket designs have also used nitrous oxide. In liquid form, N2O is highly stable, but in vapor form it has the potential to decompose exothermically, releasing up to 1865 Joules per gram of vapor as it dissociates into nitrogen and oxygen. Consequently, it has long been considered as a potential "green" replacement for existing highly toxic and dangerous monopropellants. This project investigates the feasibility of using the nitrous oxide decomposition reaction as a monopropellant energy source for igniting liquid bipropellant and hybrid rockets that already use nitrous oxide as the primary oxidizer. Because nitrous oxide is such a stable propellant, the energy barrier to dissociation is quite high; normal thermal decomposition of the vapor phase does not occur until temperatures are above 800 C. The use of a ruthenium catalyst decreases the activation energy for this reaction to allow rapid decomposition below 400 C. This research investigates the design for a prototype device that channels the energy of dissociation to ignite a laboratory scale hybrid rocket motor.

The densification, crystallization and mechanical properties of allylhydridopolycarbosilane-derived silicon carbide

NASA Astrophysics Data System (ADS)

Moraes, Kevin V.

Allylhydridopolycarbosilane is a precursor of growing importance in the fabrication of silicon carbide ceramics. However, prior to this study few details were available about the processing-structure-property relationships for this material. In Part 1 of this study the processes of densification and microstructural transformation of the partially pyrolysed amorphous AHPCS-SiC was investigated in the temperature region of 800°C to 1600°C. In Part 2 of this study, mechanical properties, specifically fracture toughness (K1c) and Vickers hardness, were measured on bulk specimens in the temperature range of 1000°C to 1600°C. A combination of X-Ray diffraction (XRD), Transmission Electron Microscopy (TEM), 29Si Nuclear Magnetic Resonance (NMR) and micro Raman spectroscopy, along with simultaneous Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA) were used to follow the structural transformation of the partially pyrolysed AHPCS-SiC on several length scales between the temperature of 800 to 1600°C. It was determined that the rate of densification of amorphous AHPCS-SiC, partially pyrolysed to 600°C, depends on the surface to volume ratio. Calculations were preformed that suggested that nucleation of the SiC crystals should occur preferentially on the surface of the powder particles rather than in the bulk. However, TEM on samples heat-treated to 1600°C did not show a preponderance of crystals on the surface of the particles compared to their bulk. Crystallization of beta-SiC occurs at ca. 1250°C, as determined by DSC and supported by NMR and electron diffraction. The average size of the beta-SiC crystallites, as determined by XRD, was ca. 5 nm at 1600°C. Prior to the crystallization of beta-SiC, Raman spectroscopy indicates the presence of carbon clusters in the otherwise amorphous matrix. These carbon clusters have predominantly sp3 bonding at 1100°C that gradually converts to predominantly sp 2 bonded carbon at higher temperatures, with average basal plane sizes of 20--25 A between 1100 in addition to 1600°C. The amorphous structure formed at temperatures below the crystallization temperature is unstable. It is seen from DSC that amorphous AHPCS-SiC undergoes two distinct exothermic events: a broad, irreversible, exotherm that corresponds to structural relaxation and chemical condensation and a second, much sharper, exotherm that corresponds to crystallization. Fracture toughness values measured on cold-pressed and infiltrated AHPCS-SiC samples were in the range of 1.4 to 1.67 MPam1/2. It appears that toughness increases with increasing heat treatment temperature. The Vickers hardness at 10 N was ca. 8.7 to 12.6 MPa. The Vickers hardness does not appear to vary significantly with the heat-treatment temperature.

Synthesis of Nano-Polycrystalline Synroc-B Powders as a High Level Radioactive Wastes Ceramic Forms by a Solution Combustion Synthesis.

PubMed

Han, Young-Min; Lee, Sang-Jin; Kim, Yeon-Ku; Jung, Choong-Hwan

2016-02-01

Synroc (Synthetic Rock) consists of four main titanate phases: peroveskite (CaTiO3), zirconolite (CaZrTi2O7), hollandite (BaAl2Ti6O16) and rutile (TiO2). Nano-polycrystalline synroc powders were made by a synthesis combustion process. The combustion process, an externally initiated reaction is self-sustained owing to the exothermic reaction. A significant volume of gas is evolved during the combustion reaction and leads to loosely agglomerated powders. This exothermic reaction provides necessary heat to further carry the reaction in forward direction to produce nanocrystalline powders as the final product. Glycine is used as a fuel, being oxidized by nitrate ions. It is inexpensive, has high energy efficiency, fast heating rates, short reaction times and high compositional homogeneity. In this study, combustion synthesis of nano-sized synroc-B powder is introduced. The fabrication of synroc-B powder result of observation XRD were prepared for polycrystalline (perovskite, zirconolite, hollandite, rutile) structures. The characterization of the synthesized powders is conducted by using XRD, SEM/EDS and TEM.

An Experiment to Illustrate the Hazards of Exothermic Reaction Scale-Up

ERIC Educational Resources Information Center

Clark, William; Lei, Melinda; Kirichenko, Erika; Dickerson, Kellie; Prytko, Robert

2017-01-01

Exothermic reactions can present safety hazards and there is a recognized need for reaction safety education at the undergraduate level. We present an experiment that illustrates the pitfall of direct scale-up of an exothermic reaction that can lead to thermal runaway. The iodide-catalyzed hydrogen peroxide decomposition reaction yields…

Combustion synthesis of complex oxides

NASA Astrophysics Data System (ADS)

Ming, Qimin

Advanced ceramic materials have numerous applications in electronic engineering, chemical engineering, and semiconductor industry. The synthesis of these materials at an economical cost is the bottleneck in the application of these materials. Self-propagating High-temperature Synthesis (SHS) is a new technique for producing these materials for exothermic systems by a combustion wave that propagates and produces high purity products. The full potential of SHS to produce advanced materials has not yet been utilized. In this study, we used SHS to prepare two types of complex oxides: La 1-xSrxCrO3, La0.89Sr0.1 MnO3, powders, used to make interconnect and cathode of solid oxide fuel cells; and chromium- and gallium-doped La1-xSr xFeO3-delta, mixed ionic and electronic conductive powders used to manufacture ceramic membranes for oxygen separation. A thermodynamic feasibility analysis shows that the oxidation of Cr is the main source of heat generation of La1-xSrxCrO 3, which maintains a stable reaction front. Replacing part of the metallic Cr in the reaction mixture by its oxides decreases the combustion temperature and front propagating velocity and modifies the product morphology. The oxygen needed for the Cr oxidation is provided by the decomposition of CrO3 , SrO2, or NaClO4. The predicted and observed combustion temperatures are in reasonable agreement. TG/DTA analyses of La1-xSrxCrO3 indicated that SHS stability was strongly affected by the transport of oxygen between the two regions, in which oxygen was generated by the decomposition of either NaClO4 or CrO3 and that in which it was consumed by the oxidation of Cr. Partial melting at the high combustion temperature during SHS of La 1-xSrxMnO3 increased product homogeneity. The electrical conductivity at 1000°C in air of SHS-produced cathode material (of 180 O-1·cm-1) matches that of the commercial product made by other processes. However, the SHS process provides much higher productivity and decreases processing time and the consumption of the electrical power. SrFeO3-x and LaCrO3 were the main intermediates and products for SHS of chromium-doped La0.2Sr0.8FeO 3-delta. The final structure was a solid solution of Fe and Sr rich oxides and La and Cr rich oxides. Decreasing the reactant particle size increased the homogeneity of the SHS product and increased the velocity of the propagating combustion front. The SHS produced La0.2Sr 0.8Cr0.2Fe0.8O3-delta had a maximal electrical conductivity of 8.8 O-1·cm -1 at 560°C in a pure oxygen. The material, having the highest stability in reducing conditions, had a moderate oxygen permeation rate of 3.35 x 10-9 mol/s·cm2 at 980°C in an oxygen partial pressure gradient from air to 4 x 10 -5 atm. The homogeneity and particle size of the combustion product of gallium-doped La0.5Sr0.5FeO3-delta may be increased by decreasing the cooling rate of the sample, either by increasing the sample diameter or by controlling the post-combustion temperature. The perovskite oxide maintained its cubic structure at all temperatures (from 20 to 1000°C) in air. However, decomposition occurred at 860°C under a simulated synthesis gas environment (22%CH4+21%CO2+57%H2, oxygen partial pressure of about 10-21 atm). Its maximal electrical conductivity was 142 O-1·cm-1 at 580°C under oxygen pressure of 1 atm. This material is suitable for use as a membrane in synthesis gas production, since the thermal expansions in air and reducing conditions are rather close at high temperatures.

Low-temperature metal-oxide thin-film transistors formed by directly photopatternable and combustible solution synthesis.

PubMed

Rim, You Seung; Lim, Hyun Soo; Kim, Hyun Jae

2013-05-01

We investigated the formation of ultraviolet (UV)-assisted directly patternable solution-processed oxide semiconductor films and successfully fabricated thin-film transistors (TFTs) based on these films. An InGaZnO (IGZO) solution that was modified chemically with benzoylacetone (BzAc), whose chelate rings decomposed via a π-π* transition as result of UV irradiation, was used for the direct patterning. A TFT was fabricated using the directly patterned IGZO film, and it had better electrical characteristics than those of conventional photoresist (PR)-patterned TFTs. In addition, the nitric acid (HNO3) and acetylacetone (AcAc) modified In2O3 (NAc-In2O3) solution exhibited both strong UV absorption and high exothermic reaction. This method not only resulted in the formation of a low-energy path because of the combustion of the chemically modified metal-oxide solution but also allowed for photoreaction-induced direct patterning at low temperatures.

Boosting hot electron flux and catalytic activity at metal-oxide interfaces of PtCo bimetallic nanoparticles.

PubMed

Lee, Hyosun; Lim, Juhyung; Lee, Changhwan; Back, Seoin; An, Kwangjin; Shin, Jae Won; Ryoo, Ryong; Jung, Yousung; Park, Jeong Young

2018-06-08

Despite numerous studies, the origin of the enhanced catalytic performance of bimetallic nanoparticles (NPs) remains elusive because of the ever-changing surface structures, compositions, and oxidation states of NPs under reaction conditions. An effective strategy for obtaining critical clues for the phenomenon is real-time quantitative detection of hot electrons induced by a chemical reaction on the catalysts. Here, we investigate hot electrons excited on PtCo bimetallic NPs during H 2 oxidation by measuring the chemicurrent on a catalytic nanodiode while changing the Pt composition of the NPs. We reveal that the presence of a CoO/Pt interface enables efficient transport of electrons and higher catalytic activity for PtCo NPs. These results are consistent with theoretical calculations suggesting that lower activation energy and higher exothermicity are required for the reaction at the CoO/Pt interface.

Enhanced photothermal effect in reduced graphene oxide in solid-state

NASA Astrophysics Data System (ADS)

Sahadev, Nishaina; Anappara, Aji A.

2017-11-01

We report on a giant photothermal effect in few-layer Reduced Graphene Oxide (RGO) in powder form. Graphite oxide synthesized following modified Hummer's method was thermally exfoliated and reduced to obtain RGO consisting of ˜8-10 layers. Upon irradiation with an incoherent, broad-band light source (wavelengths ranging from 250 to 450 nm), an enormous photothermal effect was observed. The heat generated by RGO determined from the isothermal differential photocalorimetric technique is as high as ˜319 W/g resulting from the dominant non-radiative de-excitation of photoexcited electrons due to the absence of a radiative pathway. A practical applicability was demonstrated using a commercial thermoelectric generator wherein upon illumination from a solar-simulator, an open voltage in the mV range was developed, giving a direct proof of the exothermic effect in powder RGO upon light illumination. Herewith, we have demonstrated a proof-of-concept of photothermal effects in solid-state RGO.

Apollo 16 Mission Anomaly Report No. 1: Oxidizer Deservicing Tank Failure

NASA Technical Reports Server (NTRS)

1972-01-01

The command module reaction control system is emptied of all remaining propellant using ground support equipment designed to provide an acid/base neutralization of the propellant in both the liquid and gaseous phases so that it may be disposed of safely. During the deactivation operation of the oxidizer from the Apollo 16 command module on 7 May 1972, the scrubber tank of the decontamination unit exploded, destroying the ground support equipment unit and damaging the building that housed the operation. Only minor injuries were received by the personnel in the area and the command module was not damaged. Test results show that the failure was caused by an insufficient quantity of neutralizer for the quantity of oxidizer. This insufficiency lead to exothermic nitration-type reactions which produced large quantities of gas at a very high rate and failed the decontamination tank.

Energetics of a uranothorite (Th 1–xU xSiO 4) solid solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Xiaofeng; Szenknect, Stephanie; Mesbah, Adel

High-temperature oxide melt solution calorimetric measurements were completed to determine the enthalpies of formation of the uranothorite, (USiO 4) x–(ThSiO 4) 1–x, solid solution. Phase-pure samples with x values of 0, 0.11, 0.21, 0.35, 0.71, and 0.84 were prepared, purified, and characterized by powder X-ray diffraction, electron probe microanalysis, thermogravimetric analysis and differential scanning calorimetry coupled with in situ mass spectrometry, and high-temperature oxide melt solution calorimetry. This work confirms the energetic metastability of coffinite, USiO 4, and U-rich intermediate silicate phases with respect to a mixture of binary oxides. Furthermore, variations in unit cell parameters and negative excess volumesmore » of mixing, coupled with strongly exothermic enthalpies of mixing in the solid solution, suggest short-range cation ordering that can stabilize intermediate compositions, especially near x = 0.5.« less

Energetics of a uranothorite (Th 1–xU xSiO 4) solid solution

DOE PAGES

Guo, Xiaofeng; Szenknect, Stephanie; Mesbah, Adel; ...

2016-10-11

High-temperature oxide melt solution calorimetric measurements were completed to determine the enthalpies of formation of the uranothorite, (USiO 4) x–(ThSiO 4) 1–x, solid solution. Phase-pure samples with x values of 0, 0.11, 0.21, 0.35, 0.71, and 0.84 were prepared, purified, and characterized by powder X-ray diffraction, electron probe microanalysis, thermogravimetric analysis and differential scanning calorimetry coupled with in situ mass spectrometry, and high-temperature oxide melt solution calorimetry. This work confirms the energetic metastability of coffinite, USiO 4, and U-rich intermediate silicate phases with respect to a mixture of binary oxides. Furthermore, variations in unit cell parameters and negative excess volumesmore » of mixing, coupled with strongly exothermic enthalpies of mixing in the solid solution, suggest short-range cation ordering that can stabilize intermediate compositions, especially near x = 0.5.« less

Glass transition behavior of the vitrification solutions containing propanediol, dimethyl sulfoxide and polyvinyl alcohol.

PubMed

Wang, Hai-Yan; Lu, Shu-Shen; Lun, Zhao-Rong

2009-02-01

Knowledge of the glass transition behavior of vitrification solutions is important for research and planning of the cryopreservation of biological materials by vitrification. This brief communication shows the analysis for the glass transition and glass stability of the multi-component vitrification solutions containing propanediol (PE), dimethyl sulfoxide (Me2SO) and polyvinyl alcohol (PVA) by using differential scanning calorimetry (DSC) during the cooling and subsequent warming between 25 and -150 degrees C. The glass formation of the solutions was enhanced by introduction of PVA. Partial glass formed during cooling and the fractions of free water in the partial glass matrix increased with the increasing of PVA concentration, which caused slight decline of glass transition temperature, T(g). Exothermic peaks of devitrification were delayed and broadened, which may result from the inhibition of ice nucleation or recrystallization of PVA.

Availability of surface boron species in improved oxygen reduction activity of Pt catalysts: A first-principles study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Libo; Zhou, Gang, E-mail: gzhou@mail.buct.edu.cn

2016-04-14

The oxidation process of boron (B) species on the Pt(111) surface and the beneficial effects of boron oxides on the oxygen reduction activity are investigated by first-principles calculations. The single-atom B anchored on the Pt surface has a great attraction for the oxygen species in the immediate environment. With the dissociation of molecular oxygen, a series of boron oxides is formed in succession, both indicating exothermic oxidation reactions. After BO{sub 2} is formed, the subsequent O atom immediately participates in the oxygen reduction reaction. The calculated O adsorption energy is appreciably decreased as compared to Pt catalysts, and more approximatemore » to the optimal value of the volcano plot, from which is clear that O hydrogenation kinetics is improved. The modulation mechanism is mainly based on the electron-deficient nature of stable boron oxides, which normally reduces available electronic states of surface Pt atoms that bind the O by facilitating more electron transfer. This modification strategy from the exterior opens the new way, different from the alloying, to efficient electrocatalyst design for PEMFCs.« less

Improved Energetic-Behaviors of Spontaneously Surface-Mediated Al Particles.

PubMed

Kim, Dong Won; Kim, Kyung Tae; Min, Tae Sik; Kim, Kyung Ju; Kim, Soo Hyung

2017-07-05

Surface-mediated Al particles are synthesized by incorporating the stable fluoride reaction of Al-F on a pure Al surface in place of natural oxides. Al particles with fluoro-polymer directly adsorbed on the surface show a considerable capability to overcome limitations caused by the surface oxide. Here, we report that Al fluoride when spontaneously formed at the poly(vinylidene fluoride)/Al interface serves as an oxidation-protecting layer while also providing an efficient combustion path along which the internal Al rapidly reacts with external oxygen atoms. Both thermal oxidation and explosion tests of the poly(vinylidene fluoride)/Al particles show superior exothermic enthalpy energy and simultaneously rapid oxidation reactivity compared to those of Al 2 O 3 passivated Al particles. It is clearly elucidated that the enhanced energetic properties of Al particles mediated by poly(vinylidene fluoride) originate from the extraordinary pyrolytic process of Al fluoride occurring at a low temperature compared to Al 2 O 3 passivated Al. Hence, these results clarify that the surface mediation of Al particles can be significantly considered as advanced technology for many energetic applications.

Hot-electron-mediated surface chemistry: toward electronic control of catalytic activity.

PubMed

Park, Jeong Young; Kim, Sun Mi; Lee, Hyosun; Nedrygailov, Ievgen I

2015-08-18

Energy dissipation at surfaces and interfaces is mediated by excitation of elementary processes, including phonons and electronic excitation, once external energy is deposited to the surface during exothermic chemical processes. Nonadiabatic electronic excitation in exothermic catalytic reactions results in the flow of energetic electrons with an energy of 1-3 eV when chemical energy is converted to electron flow on a short (femtosecond) time scale before atomic vibration adiabatically dissipates the energy (in picoseconds). These energetic electrons that are not in thermal equilibrium with the metal atoms are called "hot electrons". The detection of hot electron flow under atomic or molecular processes and understanding its role in chemical reactions have been major topics in surface chemistry. Recent studies have demonstrated electronic excitation produced during atomic or molecular processes on surfaces, and the influence of hot electrons on atomic and molecular processes. We outline research efforts aimed at identification of the intrinsic relation between the flow of hot electrons and catalytic reactions. We show various strategies for detection and use of hot electrons generated by the energy dissipation processes in surface chemical reactions and photon absorption. A Schottky barrier localized at the metal-oxide interface of either catalytic nanodiodes or hybrid nanocatalysts allows hot electrons to irreversibly transport through the interface. We show that the chemicurrent, composed of hot electrons excited by the surface reaction of CO oxidation or hydrogen oxidation, correlates well with the turnover rate measured separately by gas chromatography. Furthermore, we show that hot electron flows generated on a gold thin film by photon absorption (or internal photoemission) can be amplified by localized surface plasmon resonance. The influence of hot charge carriers on the chemistry at the metal-oxide interface are discussed for the cases of Au, Ag, and Pt nanoparticles on oxide supports and Pt-CdSe-Pt nanodumbbells. We show that the accumulation or depletion of hot electrons on metal nanoparticles, in turn, can also influence catalytic reactions. Mechanisms suggested for hot-electron-induced chemical reactions on a photoexcited plasmonic metal are discussed. We propose that the manipulation of the flow of hot electrons by changing the electrical characteristics of metal-oxide and metal-semiconductor interfaces can give rise to the intriguing capability of tuning the catalytic activity of hybrid nanocatalysts.

Accelerating rate calorimetry: A new technique for safety studies in lithium systems

NASA Technical Reports Server (NTRS)

Ebner, W. B.

1982-01-01

The role of exothermic reactions in battery test modes is discussed. The exothermic reactions are characterized with respect to their time-temperature and time-pressure behavior. Reactions occuring for any major exotherm were examined. The accelerating rate calorimetry methods was developed to study lithium cells susceptibility to thermal runaway reactions following certain abuse modes such as forced discharge into reversal and charging.

Combustion synthesis of low exothermic component rich composites

DOEpatents

Halverson, Danny C.; Lum, Beverly Y.; Munir, Zuhair A.

1991-01-01

A self-sustaining combustion synthesis process for producing hard, tough, lightweight, low exothermic potential product (LEPP)/high exothermic potential product (HEPP) composites is based on the thermodynamic dependence of adiabatic temperature and product composition on the stoichiometry of the LEPP and HEPP reactants. For lightweight products the composition must be relatively rich in the LEPP component. LEPP rich composites are obtained by varying the initial temperature of the reactants. The product is hard, porous material whose toughness can be enhanced by filling the pores with aluminum or other metal phases using a liquid metal infiltration process. The process can be extended to the formation of other composites having a low exothermic component.

Active microchannel heat exchanger

DOEpatents

Tonkovich, Anna Lee Y [Pasco, WA; Roberts, Gary L [West Richland, WA; Call, Charles J [Pasco, WA; Wegeng, Robert S [Richland, WA; Wang, Yong [Richland, WA

2001-01-01

The present invention is an active microchannel heat exchanger with an active heat source and with microchannel architecture. The microchannel heat exchanger has (a) an exothermic reaction chamber; (b) an exhaust chamber; and (c) a heat exchanger chamber in thermal contact with the exhaust chamber, wherein (d) heat from the exothermic reaction chamber is convected by an exothermic reaction exhaust through the exhaust chamber and by conduction through a containment wall to the working fluid in the heat exchanger chamber thereby raising a temperature of the working fluid. The invention is particularly useful as a liquid fuel vaporizer and/or a steam generator for fuel cell power systems, and as a heat source for sustaining endothermic chemical reactions and initiating exothermic reactions.

Fabrication of high temperature materials by exothermic synthesis and subsequent dynamic consolidation

DOEpatents

Rabin, Barry H.; Korth, Gary E.; Wright, Richard N.; Williamson, Richard L.

1992-01-01

An apparatus for synthesizing a composite material such as titanium carbide and alumina from exothermic reaction of a sample followed by explosive induced consolidation of the reacted sample. The apparatus includes a lower base for holding a powdered composite sample, an igniter and igniter powder for igniting the sample to initiate an exothermic reaction and a piston for dynamically compressing the sample utilizing an explosive reaction.

Hydrolysis of ZrCl4 and HfCl4: The Initial Steps in the High-Temperature Oxidation of Metal Chlorides to Produce ZrO2 and HfO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fang, Zongtang; Dixon, David A.

2013-03-08

The gas-phase hydrolysis of MCl4 (M = Zr, Hf) to produce the initial particles on the way to zirconia and hafnia nanoparticles has been studied with electronic structure theory. The potential energy surfaces, the themochemistry of the reaction species, and the reaction paths for the initial steps of MCl4 reacting with H2O have been calculated. The hydrolysis of MCl4 at higher temperatures begins with the formation of oxychlorohydroxides followed by the elimination of HCl instead of the direct production of MOCl2 and HCl or MO2 and HCl due to the substantial endothermicities associated with the formation of gas-phase MO2. Themore » structural properties and heats of formation of the reactants and products are consistent with the available experimental results. A number of metal oxychlorides (oxychlorohydroxides) intermediate clusters have been studied to assess their role in the production of MO2 nanoparticles. The calculated clustering reaction energies of those intermediates are highly exothermic, so they could be readily formed in the hydrolysis process. These intermediate clusters can be formed exothermically from metal oxychlorohydroxides by the elimination of one HCl or H2O molecule. Our calculations show that the mechanisms leading to the formation of MO2 nanoparticles are complicated and are accompanied by the potential production of a wide range of intermediates, as found for the production of TiO2 particles from the high-temperature oxidation of TiCl4.« less

Powder metallurgy technology of NiTi shape memory alloy

NASA Astrophysics Data System (ADS)

Dutkiewicz, J. M.; Maziarz, W.; Czeppe, T.; Lityńska, L.; Nowacki, W. K.; Gadaj, S. P.; Luckner, J.; Pieczyska, E. A.

2008-05-01

Powder metallurgy technology was elaborated for consolidation of shape memory NiTi powders. The shape memory alloy was compacted from the prealloyed powder delivered by Memry SA. The powder shows Ms = 10°C and As = -34°C as results from DSC measurements. The samples were hot pressed in the as delivered spherical particle's state. The hot compaction was performed in a specially constructed vacuum press, at temperature of 680°C and pressure of 400 MPa. The alloy powder was encapsulated in copper capsules prior to hot pressing to avoid oxidation or carbides formation. The alloy after hot vacuum compaction at 680°C (i.e. within the B2 NiTi stability range) has shown similar transformation range as the powder. The porosity of samples compacted in the as delivered state was only 1%. The samples tested in compression up to ɛ = 0.06 have shown partial superelastic effect due to martensitic reversible transform- ation which started at the stress above 300 MPa and returned back to ɛ = 0.015 after unloading. They have shown also a high ultimate compression strength of 1600 MPa. Measurements of the samples temperature changes during the process allowed to detect the temperature increase above 12°C for the strain rate 10-2 s-1 accompanied the exothermic martensite transformation during loading and the temperature decrease related to the reverse endothermic transformation during unloading.

Understanding the Intrinsic Electrochemistry of Ni-Rich Layered Cathodes

NASA Astrophysics Data System (ADS)

Sallis, Shawn

The demand for energy is continually increasing overtime and the key to meeting future demand in a sustainable way is with energy storage. Li-ion batteries employing layered transition metal oxide cathodes are one of the most technologically important energy storage technologies. However, current Li-ion batteries are unable to access their full theoretical capacity and suffer from performance limiting degradation over time partially originating from the cathode and partially from the interface with the electrolyte. Understanding the fundamental limitations of layered transition metal oxide cathodes requires a complete understanding of the surface and bulk of the materials in their most delithiated state. In this thesis, we employ LiNi0.8Co0.15Al 0.05O2 (NCA) as a model system for Ni-rich layered oxide cathodes. Unlike its parent compound, LiCoO2, NCA is capable of high states of delithiation with minimal structural transitions. Furthermore, commercially available NCA has little to no transition metals in the Li layer. X-ray spectroscopies are an ideal tool for studying cathodes at high states of delithiation due their elemental selectivity, range of probing depths, and sensitivity to both chemical and electronic state information. The oxidation state of the transition metals at the surface can be probed via X-ray photoelectron spectroscopy (XPS) while both bulk and surface oxidation states as well as changes in metal oxygen bonding can be probed using X-ray absorption spectroscopy (XAS). Using X-ray spectroscopy in tandem with electrochemical, transport and microscopy measurements of the same materials, the impedance growth with increasing delithiation was correlated with the formation of a disordered NiO phase on the surface of NCA which was precipitated by the release of oxygen. Furthermore, the surface degradation was strongly impacted by the type of Li salt used in the electrolyte, with the standard commercial salt LiPF6 suffering from exothermic decomposition at high voltages and temperatures. Substituting LiPF6with LiBF4 suppressed NCA surface degradation and the dissolution of the transition metals into the electrolyte which is responsible for the impedance growth. Even in the most extreme conditions (4.75V vs Li +/Li0 at 60 °C for > 100 hrs) the degradation (i.e. metal reduction) was restricted to the first 10-30 nm and no evidence of oxygen loss was observed in the bulk. However, the transition metal ions were found to cease oxidizing above 4.25 V vs Li+/Li0 despite it being possible to extract 20% more lithium. Using a newly developed high efficiency resonant inelastic x-ray scattering (RIXS) spectrometer to probe the O K-edge of NCA electrodes at various conditions, it was concluded that oxygen participates in the charge compensation at the highest states of delithiation instead of the transition metals. These results are intrinsic to the physical and electronic structure of NCA and appear general to the other layered transition metal oxides currently under consideration for use as cathodes in Li-ion batteries.

Synthesis and thermal behavior of tin-based alloy (Sn-Ag-Cu) nanoparticles

NASA Astrophysics Data System (ADS)

Roshanghias, Ali; Yakymovych, Andriy; Bernardi, Johannes; Ipser, Herbert

2015-03-01

The prominent melting point depression of nanoparticles has been the subject of a considerable amount of research. For their promising applications in electronics, tin-based nano-alloys such as near-eutectic Sn-Ag-Cu (SAC) alloys have been synthesized via various techniques. However, due to issues such as particle aggregation and oxidation or introduced impurities, the application of these nano-size particles has been confined or aborted. For instance, thermal investigations by DTA/DSC in a large number of studies revealed exothermic peaks in the range of 240-500 °C, i.e. above the melting point of SAC nanoparticles, with different and quite controversial explanations for this unclear phenomenon. This represents a considerable drawback for the application of nanoparticles. Correspondingly, in the current study, the thermal stability of SAC nanoparticles has been investigated via electron microscopy, XRD, FTIR, and DSC/TG analysis. It was found that the nanoparticles consist mainly of a metallic β-Sn core and an amorphous tin hydroxide shell structure. The SnO crystalline phase formation from this amorphous shell has been associated with the exothermic peaks on the first heating cycle of the nanoparticles, followed by a disproportionation reaction into metallic Sn and SnO2.The results also revealed that the surfactant and reducing agent cannot only affect the size and size distribution of the nanoparticles, they might also alter the ratio between the amorphous shell and the crystalline core in the structure of particles.The prominent melting point depression of nanoparticles has been the subject of a considerable amount of research. For their promising applications in electronics, tin-based nano-alloys such as near-eutectic Sn-Ag-Cu (SAC) alloys have been synthesized via various techniques. However, due to issues such as particle aggregation and oxidation or introduced impurities, the application of these nano-size particles has been confined or aborted. For instance, thermal investigations by DTA/DSC in a large number of studies revealed exothermic peaks in the range of 240-500 °C, i.e. above the melting point of SAC nanoparticles, with different and quite controversial explanations for this unclear phenomenon. This represents a considerable drawback for the application of nanoparticles. Correspondingly, in the current study, the thermal stability of SAC nanoparticles has been investigated via electron microscopy, XRD, FTIR, and DSC/TG analysis. It was found that the nanoparticles consist mainly of a metallic β-Sn core and an amorphous tin hydroxide shell structure. The SnO crystalline phase formation from this amorphous shell has been associated with the exothermic peaks on the first heating cycle of the nanoparticles, followed by a disproportionation reaction into metallic Sn and SnO2.The results also revealed that the surfactant and reducing agent cannot only affect the size and size distribution of the nanoparticles, they might also alter the ratio between the amorphous shell and the crystalline core in the structure of particles. Dedicated to Prof. Brigitte Weiss.

Evaluating operating conditions for outcompeting nitrite oxidizers and maintaining partial nitrification in biofilm systems using biofilm modeling and Monte Carlo filtering.

PubMed

Brockmann, D; Morgenroth, E

2010-03-01

In practice, partial nitrification to nitrite in biofilms has been achieved with a range of different operating conditions, but mechanisms resulting in reliable partial nitrification in biofilms are not well understood. In this study, mathematical biofilm modeling combined with Monte Carlo filtering was used to evaluate operating conditions that (1) lead to outcompetition of nitrite oxidizers from the biofilm, and (2) allow to maintain partial nitrification during long-term operation. Competition for oxygen was found to be the main mechanism for displacing nitrite oxidizers from the biofilm, and preventing re-growth of nitrite oxidizers in the long-term. To maintain partial nitrification in the model, a larger oxygen affinity (i.e., smaller half saturation constant) for ammonium oxidizers compared to nitrite oxidizers was required, while the difference in maximum growth rate was not important for competition under steady state conditions. Thus, mechanisms for washout of nitrite oxidizing bacteria from biofilms are different from suspended cultures where the difference in maximum growth rate is a key mechanism. Inhibition of nitrite oxidizers by free ammonia was not required to outcompete nitrite oxidizers from the biofilm, and to maintain partial nitrification to nitrite. But inhibition by free ammonia resulted in faster washout of nitrite oxidizers. Copyright 2009 Elsevier Ltd. All rights reserved.

Preparation and magnetic properties of multiferroic CuMnO2 nanoparticles.

PubMed

Kurokawa, Akinobu; Yanoh, Tkuya; Yano, Shinya; Ichiyanagi, Yuko

2014-03-01

CuMnO2 nanoparticles with diameters of 64 nm were synthesized by a novel wet chemical method. An optimized two-step annealing method was developed through the analysis of thermogravimetric differential thermal analysis (TG-DTA) measurements in order to obtain single-phase CuMnO2. A sharp exothermic peak was observed in the DTA curve at approximately 500 K where structural changes of the copper oxides and manganese oxides in the precursor are expected to occur. It is believed that Cu+ ions were oxidized to Cu2+ ions and that Mn2+ ions were oxidized to Mn3+ ions in the Cu-Mn-O system. Deoxidization reactions were also found at approximately 1200 K. The optimized annealing temperature for the first step was determined to be 623 K in air. The optimized annealing temperature for the second step was 1173 K in an Ar atmosphere. Magnetization measurements suggested an antiferromagnetic spin ordering at approximately 50 K. It was expected that Mn3+ spin interactions induced magnetic phase transition affected by definite temperature.

High-temperature thermochemical energy storage based on redox reactions using Co-Fe and Mn-Fe mixed metal oxides

NASA Astrophysics Data System (ADS)

André, Laurie; Abanades, Stéphane; Cassayre, Laurent

2017-09-01

Metal oxides are potential materials for thermochemical heat storage via reversible endothermal/exothermal redox reactions, and among them, cobalt oxide and manganese oxide are attracting attention. The synthesis of mixed oxides is considered as a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering issues, and the materials potential for thermochemical heat storage application needs to be assessed. This work proposes a study combining thermodynamic calculations and experimental measurements by simultaneous thermogravimetric analysis and calorimetry, in order to identify the impact of iron oxide addition to Co and Mn-based oxides. Fe addition decreased the redox activity and energy storage capacity of Co3O4/CoO, whereas the reaction rate, reversibility and cycling stability of Mn2O3/Mn3O4 was significantly enhanced with added Fe amounts above 15 mol%, and the energy storage capacity was slightly improved. The formation of a reactive cubic spinel explained the improved re-oxidation yield of Mn-based oxides that could be cycled between bixbyite and cubic spinel phases, whereas a low reactive tetragonal spinel phase showing poor re-oxidation was formed below 15 mol% Fe. Thermodynamic equilibrium calculations predict accurately the behavior of both systems. The possibility to identify other suitable mixed oxides becomes conceivable, by enabling the selection of transition metal additives for tuning the redox properties of mixed metal oxides destined for thermochemical energy storage applications.

Modeling of oxidation of aluminum nanoparticles by using Cabrera Mott Model

NASA Astrophysics Data System (ADS)

Ramazanova, Zamart; Zyskin, Maxim; Martirosyan, Karen

2012-10-01

Our research focuses on modeling new Nanoenergetic Gas-Generator (NGG) formulations that rapidly release a large amount of gaseous products and generates shock and pressure waves. Nanoenergetic thermite reagents include mixtures of Al and metal oxides such as bismuth trioxide and iodine pentoxide. The research problem is considered a spherically symmetric case and used the Cabrera Mott oxidation model to describe the kinetics of oxide growth on spherical Al nanoparticles for evaluating reaction time which a process of the reaction with oxidizer happens on the outer part of oxide layer of aluminum ions are getting in contact with an oxidizing agent and react. We assumed that a ball of Al of radius 20 to 50 nm is covered by a thin oxide layer 2-4 nm and is surrounded by abundant amount of oxygen stored by oxidizers. The ball is rapidly heated up to ignition temperature to initiate self-sustaining oxidation reaction. As a result highly exothermic reaction is generated. In the oxide layer of excess concentrations of electrons and ions are dependent on the electric field potential with the corresponding of the Gibbs factors and that it conducts to the solution of a nonlinear Poisson equation for the electric field potential in a moving boundary domain. Motion of the boundary is determined by the gradient of a solution on the boundary. We investigated oxidation model numerically, using the COMSOL software utilizing finite element analysis. The computing results demonstrate that oxidation rate increases with the decreasing particle radius.

A Study on the Application of New Shaft System for VLCC

NASA Astrophysics Data System (ADS)

Ko, Dae-Eun; Shin, Sang-Hoon

2017-11-01

Some of the most frequent damages in the ship-mounted machinery occur in the propeller shaft system, and the most frequent damage is due to the exothermic accident occurs in the after stern tube bearing (STB). Recently, engine power and shaft diameter of very large crude-oil carriers (VLCCs) tend to increase whereas the distance between forward and after STB becomes shorter. In this study, the applicability of new shaft system for VLCCs adopting single STB system was investigated. The study results show that single STB system is quite possible by applying proper shaft arrangement and partial slope at the white metal. Also, a considerable economic effect is expected by simplifying related shaft system.

Method for improving catalyst function in auto-thermal and partial oxidation reformer-based processors

DOEpatents

Ahmed, Shabbir; Papadias, Dionissios D.; Lee, Sheldon H.D.; Ahluwalia, Rajesh K.

2014-08-26

The invention provides a method for reforming fuel, the method comprising contacting the fuel to an oxidation catalyst so as to partially oxidize the fuel and generate heat; warming incoming fuel with the heat while simultaneously warming a reforming catalyst with the heat; and reacting the partially oxidized fuel with steam using the reforming catalyst.

Structural, luminescence, thermodynamic and theoretical studies on mononuclear complexes of Eu(III) with pyridine monocarboxylate-N-oxides in aqueous solution

NASA Astrophysics Data System (ADS)

Dumpala, Rama Mohana Rao; Rawat, Neetika; Boda, Anil; Ali, Sk. Musharaf; Tomar, B. S.

2018-02-01

The mononuclear complexes formed by Eu(III) with three isomeric pyridine monocarboxylate-N-oxides namely picolinic acid-N-oxide (PANO), nicotinic acid-N-oxide (NANO) and isonicotinic acid-N-oxide (IANO) in aqueous solutions were studied by potentiometry, luminescence spectroscopy and isothermal titration calorimetry (ITC) to determine the speciation, coordination, luminescence properties and thermodynamic parameters of the complexes formed during the course of the reaction. More stable six membered chelate complexes with stoichiometry (MLi, i = 1-4) are formed by Eu(III) with PANO while non chelating ML and ML2 complexes are formed by NANO and IANO. The stability of Eu(III) complexes follow the order PANO > IANO > NANO. The ITC studies inferred an endothermic and innersphere complex formation of Eu(III)-PANO and Eu(III)-IANO whereas an exothermic and outer-sphere complex formation for Eu(III)-NANO. The luminescence life time data further supported the ITC results. Density functional theoretical calculations were carried out to optimize geometries of the complexes and to estimate the energies, structural parameters (bond distances, bond angles) and charges on individual atoms of the same. Theoretical approximations are found to be in good agreement with the experimental observations.

Thermochemistry of paddle wheel MOFs: Cu-HKUST-1 and Zn-HKUST-1.

PubMed

Bhunia, Manas K; Hughes, James T; Fettinger, James C; Navrotsky, Alexandra

2013-06-25

Metal-organic framework (MOF) porosity relies upon robust metal-organic bonds to retain structural rigidity upon solvent removal. Both the as-synthesized and activated Cu and Zn polymorphs of HKUST-1 were studied by room temperature acid solution calorimetry. Their enthalpies of formation from dense assemblages (metal oxide (ZnO or CuO), trimesic acid (TMA), and N,N-dimethylformamide (DMF)) were calculated from the calorimetric data. The enthalpy of formation (ΔHf) of the as-synthesized Cu-HKUST-H2O ([Cu3TMA2·3H2O]·5DMF) is -52.70 ± 0.34 kJ per mole of Cu. The ΔHf for Zn-HKUST-DMF ([Zn3TMA2·3DMF]·2DMF) is -54.22 ± 0.57 kJ per mole of Zn. The desolvated Cu-HKUST-dg [Cu3TMA2] has a ΔHf of 16.66 ± 0.51 kJ/mol per mole Cu. The ΔHf for Zn-HKUST-amorph [Zn3TMA2·2DMF] is -3.57 ± 0.21 kJ per mole of Zn. Solvent stabilizes the Cu-HKUST-H2O by -69.4 kJ per mole of Cu and Zn-HKUST-DMF by at least -50.7 kJ per mole of Zn. Such strong chemisorption of solvent is similar in magnitude to the strongly exothermic binding at low coverage for chemisorbed H2O on transition metal oxide nanoparticle surfaces. The strongly exothermic solvent-framework interaction suggests that solvent can play a critical role in obtaining a specific secondary building unit (SBU) topology.

Violent oxidation of lithium-containing aluminum alloys in liquid oxygen

NASA Astrophysics Data System (ADS)

Dalins, Ilmars; Karimi, Majid; Ila, Daryush

1991-06-01

A strong exothermic and quite well known thermite reaction involving aluminum, oxygen and transition metals (Fe, Cr, Ni, etc.) has apparently been initiated during impact testing of Alcoa aluminum alloy #2090 in liquid oxygen at NASA-MSFC. In some instances, this reaction, essentially an oxidation process, has been so intense that the Inconel 718 cup containing the aluminum alloy disk and associated impacter has melted raising certain safety concerns in the use of this alloy. Reaction products as well as the test specimen surfaces have been studied with surface science techniques like XPS/ESCA, SIMS and AES. Typically, in order to initiate the thermite reaction a temperature of approximately 1000°C is necessary. The mechanism responsible for this oxidation is of great interest. The analysis of the reaction products together with a theoretical analysis, including digital modeling has been pursued. There is strong evidence that the large relaxation energy of the aluminum oxide coating, formed during the aluminum alloy cleaning process, is causing a highly localized energy release during fracture or lattice deformation which is enhancing the oxidation process to a runaway condition. The presence of alkali atoms (Li) enhances the likelihood and intensity of the oxidation reaction. The details of the surface studies will be discussed.

Chromium Vaporization Reduction by Nickel Coatings For SOEC Interconnect Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Michael V. Glazoff; Sergey N. Rashkeev; J. Stephen Herring

2014-09-01

The vaporization of Cr-rich volatile species from interconnect materials is a major source of degradation that limits the lifetime of planar solid oxide devices systems with metallic interconnects, including Solid Oxide Electrolysis Cells, or SOECs. Some metallic coatings (Ni, Co, and Cu) significantly reduce the Cr release from interconnects and slow down the oxide scale growth on the steel substrate. To shed additional light upon the mechanisms of such protection and find a suitable coating material for ferritic stainless steel materials, we used a combination of first-principles calculations, thermodynamics, and diffusion modeling to investigate which factors determine the quality ofmore » the Ni metallic coating at stainless steel interconnector. We found that the Cr migration in Ni coating is determined by a delicate combination of the nickel oxidation, Cr diffusion, and phase transformation processes. Although the formation of Cr2O3 oxide is more exothermic than that of NiO, the kinetic rate of the chromia formation in the coating layer and its surface is significantly reduced by the low mobility of Cr in nickel oxide and in NiCr2O4 spinel. These results are in a good agreement with diffusion modeling for Cr diffusion through Ni coating layer on the ferritic 441 steel substrate.« less

Composition and method for storing and releasing hydrogen

DOEpatents

Thorn, David L.; Tumas, William; Ott, Kevin C.; Burrell, Anthony K.

2010-06-15

A chemical system for storing and releasing hydrogen utilizes an endothermic reaction that releases hydrogen coupled to an exothermic reaction to drive the process thermodynamically, or an exothermic reaction that releases hydrogen coupled to an endothermic reaction.

Plane wave density functional molecular dynamics study of exothermic reactions of Al/CuO thermites

NASA Astrophysics Data System (ADS)

Oloriegbe, Suleiman; Sewell, Thomas; Chen, Zhen; Jiang, Shan; Gan, Yong

2014-03-01

Exothermic reactions between nanosize aluminum (Al) and copper oxide (CuO) structures are of current interest because of their high reaction enthalpy and energy density which exceed those of traditional monomolecular energetic compounds such as TNT, RDX, and HMX. In this work, molecular dynamics simulations with forces obtained from plane wave density functional theory are used to investigate the atomic-scale and electronic processes that occur during the fast thermite reactions between Al and CuO nanostructures under adiabatic conditions. Aluminum surfaces in contact with O-exposed and Cu-exposed CuO surfaces are studied. Starting from initial temperature T = 800 K, we have observed: faster chemical reaction at the oxygen-rich interface during the initial 0.5 ps, linear temperature rise, and fast oxygen diffusion into the Al region with the rate 1.87 X 10-3 cm2/s. The density-derived electrostatic and chemical method is used to evaluate the net atomic charges and charge transfer during the important redox processes. High charge density around the oxygen-exposed interface may be responsible for the faster initial reactions at that interface. The overall reaction rate, determined using the time evolution of Cu-O charge orbital overlap population, is approximately first order.

Autothermal and partial oxidation reformer-based fuel processor, method for improving catalyst function in autothermal and partial oxidation reformer-based processors

DOEpatents

Ahmed, Shabbir; Papadias, Dionissios D.; Lee, Sheldon H. D.; Ahluwalia, Rajesh K.

2013-01-08

The invention provides a fuel processor comprising a linear flow structure having an upstream portion and a downstream portion; a first catalyst supported at the upstream portion; and a second catalyst supported at the downstream portion, wherein the first catalyst is in fluid communication with the second catalyst. Also provided is a method for reforming fuel, the method comprising contacting the fuel to an oxidation catalyst so as to partially oxidize the fuel and generate heat; warming incoming fuel with the heat while simultaneously warming a reforming catalyst with the heat; and reacting the partially oxidized fuel with steam using the reforming catalyst.

75 FR 50941 - Airworthiness Directives; B/E Aerospace Protective Breathing Equipment Part Number 119003-11...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-18

... used in PBE units, which could result in an exothermic reaction and ignition. We are proposing this AD..., which could result in an exothermic reaction and ignition. The Federal Aviation Administration is...

Comparisons of kinetics, thermodynamics and regeneration of tetramethylammonium hydroxide adsorption in aqueous solution with graphene oxide, zeolite and activated carbon

NASA Astrophysics Data System (ADS)

Chang, Shenteng; Lu, Chungsying; Lin, Kun-Yi Andrew

2015-01-01

Graphene oxide (GO), sodium Y-type zeolite (NaY) and granular activated carbon (GAC) are selected as adsorbents to study their kinetics, thermodynamics and regeneration of tetramethylammonium hydroxide (TMAH) adsorption from water. The adsorption kinetics follows the pseudo-second-order rate law while the adsorption thermodynamics shows an exothermic reaction with GO and GAC but displays an endothermic reaction with NaY. The adsorbed TMAH can be readily desorbed from the surface of GO and NaY by 0.05 M NaCl solution. A comparative study on the cyclic TMAH adsorption with GO, NaY and GAC is also conducted and the results reveal that GO exhibits the greatest TMAH adsorption capacity as well as superior reversibility of TMAH adsorption over 10 cycles of adsorption and desorption process. These features indicate that GO is a promising and efficient adsorbent for TMAH removal in wastewater treatment.

Theoretical Investigation of the Reactivity of Sodium Dicyanamide with Nitric Acid.

PubMed

Vogelhuber, Kristen M; Booth, Ryan S; Annesley, Christopher J

2018-03-01

There is a need to replace current hydrazine fuels with safer propellants, and dicyanamide (DCA - )-based systems have emerged as promising alternatives because they autoignite when mixed with some oxidizers. Previous studies of the hypergolic reaction mechanism have focused on the reaction between DCA - and the oxidizer HNO 3 ; here, we compare the calculated pathway of DCA - + HNO 3 with the reaction coordinate of the ion pair sodium dicyanamide with nitric acid, Na[DCA] + HNO 3 . Enthalpies and free energies are calculated in the gas phase and in solution using a quantum mechanical continuum solvation model, SMD-GIL. The barriers to the Na[DCA] + HNO 3 reaction are dramatically lowered relative to those of the reaction with the bare anion, and an exothermic exit channel to produce NaNO 3 and the reactive intermediate HDCA appears. These results suggest that Na[DCA] may accelerate the ignition reaction.

Thermoplasmonic Ignition of Metal Nanoparticles.

PubMed

Mutlu, Mehmet; Kang, Ju-Hyung; Raza, Søren; Schoen, David; Zheng, Xiaolin; Kik, Pieter G; Brongersma, Mark L

2018-03-14

Explosives, propellants, and pyrotechnics are energetic materials that can store and quickly release tremendous amounts of chemical energy. Aluminum (Al) is a particularly important fuel in many applications because of its high energy density, which can be released in a highly exothermic oxidation process. The diffusive oxidation mechanism (DOM) and melt-dispersion mechanism (MDM) explain the ways powders of Al nanoparticles (NPs) can burn, but little is known about the possible use of plasmonic resonances in NPs to manipulate photoignition. This is complicated by the inhomogeneous nature of powders and very fast heating and burning rates. Here, we generate Al NPs with well-defined sizes, shapes, and spacings by electron beam lithography and demonstrate that their plasmonic resonances can be exploited to heat and ignite them with a laser. By combining simulations with thermal-emission, electron-, and optical-microscopy studies, we reveal how an improved control over NP ignition can be attained.

Activation barriers for series of exothermic homologous reactions. VI. Reactions of lanthanide and transition metal atoms.

NASA Astrophysics Data System (ADS)

Blue, Alan S.; Fontijn, Arthur

2001-09-01

Semiempirical configuration interaction (SECI) theory to predict activation barriers, E, as given by k(T)=ATn exp(-E(RT), has been applied to homologous series of lanthanide (LN) and transition metal (TM) atom oxidation reactions. This was achieved by considering as homologous series reactions of elements differing only by the number of electrons in one subshell. Comparison between SECI and experimental results leads to an average deviation for the LN+N2O reactions of 0.66 kJ mol-1, and up to 5.5 kJ mol-1 for other series. Thirty-one activation barriers are reported.

Calorimetric determination of energetics of solid solutions of UO 2+ x with CaO and Y 2O 3

NASA Astrophysics Data System (ADS)

Mazeina, Lena; Navrotsky, Alexandra; Greenblatt, Martha

2008-02-01

Quantitative study of thermodynamic properties of solid solutions of UO 2+ x with divalent and trivalent oxides is important for predicting the behavior of oxide fuel. Although early literature work measured vapor pressure in some of these solid solutions, direct calorimetric measurements of enthalpies of formation have been hampered by the refractory nature of such oxides. First measurements of the enthalpies of formation in the systems UO 2+ x-CaO and UO 2+ x-YO 1.5, obtained by high-temperature oxide melt solution calorimetry, are reported. Both systems show significantly negative (exothermic) heats of formation from binary oxides (UO 2, plus O 2 and CaO or YO 1.5, as well as from UO 2 plus UO 3 and CaO or YO 1.5), consistent with reported free energy measurements in the urania-yttria system. The energetic contributions of oxygen content (oxidation of U 4+) and of charge balanced ionic substitution as well as defect clustering are discussed. Behavior of urania-yttria is compared to that of corresponding systems in which the tetravalent ion is Ce, Zr, or Hf. The substantial additional stability in the solid solutions compared to pure UO 2+ x may retard, in both thermodynamic and kinetic sense, the oxidation and leaching of spent fuel to form aqueous U 6+ and solid uranyl phases.

First-principles calculations of the indigo encapsulation and adsorption by MgO nanotubes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sánchez-Ochoa, F., E-mail: fsanchez@ifuap.buap.mx; Cocoletzi, Gregorio H.; Canto, Gabriel I.

2014-06-07

We have performed ab-initio calculations to investigate the structural and electronic properties of (m,m) chiral magnesium oxide nanotubes, (m,m)MgONTs, to explore the encapsulation, inclusion, and adsorption of dyes (organic molecules) such as Indigo (IND). Studies start by determining the structural parameters of the MgO nanotubes with different diameters and the IND. The indigo encapsulation into the MgONT is studied considering four (m,m) chiralities which yield 4 different NT diameters. In the endohedral functionalization, the indigo is within the NT at a tilt angle as in previous theoretical studies of organic molecules inside carbon and boron-nitride nanotubes. Results show that themore » encapsulation is a strong exothermic process with the m = 6 case exhibiting the largest encapsulation energy. It is also explored the indigo adsorption on the NT surface in the parallel and perpendicular configurations. The perpendicular configuration of the IND adsorption on the (8,8)MgONT exhibits the largest energy. The indigo inclusion within the NTs meets a potential barrier when m < 6, however this barrier diminishes as the index increases. Additionally, we have determined the total density of states (DOS), partial DOS, electron charge redistributions, and the highest occupied molecular orbital–lowest unoccupied molecular orbital levels for the NTs with m = 6. Very strong binding energies and electron charge transfer from the IND to NTs is present in the atomic structures.« less

Influence of N-Oxide Introduction on the Stability of Nitrogen-Rich Heteroaromatic Rings: A Quantum Chemical Study.

PubMed

Yuan, Jia; Long, Xinping; Zhang, Chaoyang

2016-12-01

N-Oxidization is an important strategy for enhancing the density and energy of energetic materials. Nevertheless, the influence of N + -O - introduction on molecular stability remains relatively unknown. Thus, the present work comprehensively studied 102 basic N-rich ring structures, including azoles, furazans, and azines, as well as their N-oxides by quantum chemical calculations. The introduction of N + -O - weakens molecular stability in most cases because the process elongates chemical bonds, decreases ring aromaticity, narrows the gaps between the highest occupied and lowest unoccupied molecular orbitals, and increases the photochemical reactivity. Besides, the easy H transfer to the neighboring O atom, which forms a N-OH isomer in azoles, renders the stabilization by N-oxide introduction ineffective. However, N-oxide introduction can enhance the molecular stability of 1,2,3,4-tetrazine-1,3-dioxide and tetrazino-tetrazine 1,3,6,8-tetraoxide by promoting σ-π separation and relieving lone-pair repulsion. Moreover, the alternate arrangement of positive and negative charges is another factor stabilizing the 1,2,3,4-tetrazine ring by 1,3-dioxidation. Finally, we assess the accessibility of N-oxidized azoles and azines by regarding N 2 O and H 2 O 2 as oxidizers. We find that all the oxidations were exothermic, thermodynamically spontaneous, and kinetically feasible. After an overall evaluation, we propose 19 N-oxides as basic structures for high-energy materials with considerable stability.

Coupling of exothermic and endothermic hydrogen storage materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brooks, Kriston P.; Bowden, Mark E.; Karkamkar, Abhijeet J.

2016-08-01

Chemical hydrogen storage (CHS) materials are a high-storage-density alternative to the gaseous compressed hydrogen currently used to provide hydrogen for fuel cell vehicles. One of the challenges of CHS materials is addressing the thermodynamic and kinetic barriers required to break the chemical bonds and release the hydrogen. Coupling CHS reactions that are endothermic and exothermic during the dehydrogenation can improve the system on-board energy efficiency and thermal control, making such materials viable. Acceptable coupling between reactions requires both thermodynamic and kinetics considerations. Models were developed to predict the reaction enthalpy and rate required to achieve high conversions for both reactionsmore » based on experimental measurements. These modeling results show that the efficiency of coupling of an exothermic and endothermic reaction is more sensitive the magnitude of the ratio of the exothermic and endothermic enthalpies than the ratio of the rates of the two steps. The modeling shows further that a slower rate of the endothermic step is desirable to permit sufficient heating of the reactor by the exothermic step. We look at two examples of a sequential and parallel reaction scheme and provide some of the first insight into the required temperature range to maximize the H2 release from 1,2-BN cyclohexane and indoline.« less

Oxidation Behavior of Carbon Fiber-Reinforced Composites

NASA Technical Reports Server (NTRS)

Sullivan, Roy M.

2008-01-01

OXIMAP is a numerical (FEA-based) solution tool capable of calculating the carbon fiber and fiber coating oxidation patterns within any arbitrarily shaped carbon silicon carbide composite structure as a function of time, temperature, and the environmental oxygen partial pressure. The mathematical formulation is derived from the mechanics of the flow of ideal gases through a chemically reacting, porous solid. The result of the formulation is a set of two coupled, non-linear differential equations written in terms of the oxidant and oxide partial pressures. The differential equations are solved simultaneously to obtain the partial vapor pressures of the oxidant and oxides as a function of the spatial location and time. The local rate of carbon oxidation is determined at each time step using the map of the local oxidant partial vapor pressure along with the Arrhenius rate equation. The non-linear differential equations are cast into matrix equations by applying the Bubnov-Galerkin weighted residual finite element method, allowing for the solution of the differential equations numerically.

Titanium-Oxygen Reactivity Study

NASA Technical Reports Server (NTRS)

Chafey, J. E.; Scheck, W. G.; Witzell, W. E.

1962-01-01

A program has been conducted at Astronautics to investigate the likelihood of occurrence of the catastrophic oxidation of titanium alloy sheet under conditions which simulate certain cases of accidental failure of the metal while it is in contact with liquid or gaseous oxygen. Three methods of fracturing the metal were used; they consisted of mechanical puncture, tensile fracture of welded joints, and perforation by very high velocity particles. The results of the tests which have been conducted provide further evidence of the reactivity of titanium with liquid and gaseous oxygen. The evidence indicates that the rapid fracturing of titanium sheet while it is in contact with oxygen initiates the catastrophic oxidation reaction. Initiation occurred when the speed of the fracture was some few feet per second, as in both the drop-weight puncture tests and the static tensile fracture tests of welded joints, as well as when the speed was several thousand feet per second, as in the simulated micrometeoroid penetration tests. The slow propagation of a crack, however, did not initiate the reaction. It may logically be concluded that the localized frictional heat of rapid fracture and/or spontaneous oxidation (exothermic) of minute particles emanating from the fracture cause initiation of the reaction. Under conditions of slow fracture, however, the small heat generated may be adequately dissipated and the reaction is not initiated. A portion of the study conducted consisted of investigating various means by which the reaction might be retarded or prevented. Providing a "barrier" at the titanium-oxygen interface consisting of either aluminum metal or a coating of a petroleum base corrosion inhibitor appeared to be only partially effective in retarding the reaction. The accidental puncturing or similar rupturing of thin-walled pressurized oxygen tanks on missiles and space vehicle will usually constitute loss of function, and may sometimes cause their catastrophic destruction by explosive decompression regardless of the type of material used for their construction. In the case of tanks constructed of titanium alloys the added risk is incurred of catastrophic burning of the tanks. In view of this it is recommended that thin-walled tanks constructed of titanium alloys should not be used to contain liquid or gaseous oxygen.

Highly efficient one-step synthesis of carbon encapsulated nanocrystals by the oxidation of metal π-complexes

NASA Astrophysics Data System (ADS)

Liu, Boyang; Shao, Yingfeng; Xiang, Xin; Zhang, Fuhua; Yan, Shengchang; Li, Wenge

2017-08-01

Various carbon encapsulated nanocrystals, including MnS and MnO, Cr2O3, MoO2, Fe7S8 and Fe3O4, and ZrO2, are prepared in one step and in situ by a simple and highly efficient synthesis approach. The nanocrystals have an equiaxed morphology and a median size smaller than 30 nm. Tens and hundreds of these nanocrystals are entirely encapsulated by a wormlike amorphous carbon shell. The formation of a core-shell structure depends on the strongly exothermic reaction of metal π-complexes with ammonium persulfate in an autoclave at below 200 °C. During the oxidation process, the generated significant amounts of heat will destroy the molecular structure of the metal π-complex and cleave the ligands into small carbon fragments, which further transform into an amorphous carbon shell. The central metal atoms are oxidized to metal oxide/sulfide nanocrystals. The formation of a core-shell structure is independent of the numbers of ligands and carbon atoms as well as the metal types, implying that any metal π-complex can serve as a precursor and that various carbon encapsulated nanocrystals can be synthesized by this method.

A combined calorimetric and computational study of the energetics of rare earth substituted UO 2 systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Lei; Solomon, Jonathan M.; Asta, Mark

2015-09-01

The energetics of rare earth substituted UO2 solid solutions (U1-xLnxO2-0.5x+y, where Ln = La, Y, and Nd) are investigated employing a combination of calorimetric measurements and density functional theory based computations. Calculated and measured formation enthalpies agree within 10 kJ/mol for stoichiometric oxygen/metal compositions. To better understand the factors governing the stability and defect binding in rare earth substituted urania solid solutions, systematic trends in the energetics are investigated based on the present results and previous computational and experimental thermochemical studies of rare earth substituted fluorite oxides (A1-xLnxO2-0.5x, where A = Hf, Zr, Ce, and Th). A consistent trend towardsmore » increased energetic stability with larger size mismatch between the smaller host tetravalent cation and the larger rare earth trivalent cation is found for both actinide and non-actinide fluorite oxide systems where aliovalent substitution of Ln cations is compensated by oxygen vacancies. However, the large exothermic oxidation enthalpy in the UO2 based systems favors oxygen rich compositions where charge compensation occurs through the formation of uranium cations with higher oxidation states.« less

Energetics of alkali and alkaline earth ion-exchanged zeolite A

DOE PAGES

Sun, Hui; Wu, Di; Liu, Kefeng; ...

2016-06-30

Alkali and alkaline earth ion-exchanged zeolite A samples were synthesized in aqueous exchange media. They were thoroughly studied by powder X-ray diffraction (XRD), electron microprobe (EMPA), thermogravimetric analysis and differential scanning calorimetry (TG-DSC), and high temperature oxide melt solution calorimetry. The hydration energetics and enthalpies of formation of these zeolite A materials from constituent oxides were determined. Specifically, the hydration level of zeolite A has a linear dependence on the average ionic potential ( Z/r) of the cation, from 0.894 (Rb-A) to 1.317 per TO 2 (Mg-A). The formation enthalpies from oxides (25 °C) range from –93.71 ± 1.77 (K-A)more » to –48.02 ± 1.85 kJ/mol per TO 2 (Li-A) for hydrated alkali ion-exchanged zeolite A, and from –47.99 ± 1.20 (Ba-A) to –26.41 ± 1.71 kJ/mol per TO 2 (Mg-A) for hydrated alkaline earth ion-exchanged zeolite A. As a result, the formation enthalpy from oxides generally becomes less exothermic as Z/r increases, but a distinct difference in slope is observed between the alkali and the alkaline earth series.« less

Microwave assisted preparation of magnesium phosphate cement (MPC) for orthopedic applications: a novel solution to the exothermicity problem.

PubMed

Zhou, Huan; Agarwal, Anand K; Goel, Vijay K; Bhaduri, Sarit B

2013-10-01

There are two interesting features of this paper. First, we report herein a novel microwave assisted technique to prepare phosphate based orthopedic cements, which do not generate any exothermicity during setting. The exothermic reactions during the setting of phosphate cements can cause tissue damage during the administration of injectable compositions and hence a solution to the problem is sought via microwave processing. This solution through microwave exposure is based on a phenomenon that microwave irradiation can remove all water molecules from the alkaline earth phosphate cement paste to temporarily stop the setting reaction while preserving the active precursor phase in the formulation. The setting reaction can be initiated a second time by adding aqueous medium, but without any exothermicity. Second, a special emphasis is placed on using this technique to synthesize magnesium phosphate cements for orthopedic applications with their enhanced mechanical properties and possible uses as drug and protein delivery vehicles. The as-synthesized cements were evaluated for the occurrences of exothermic reactions, setting times, presence of Mg-phosphate phases, compressive strength levels, microstructural features before and after soaking in (simulated body fluid) SBF, and in vitro cytocompatibility responses. The major results show that exposure to microwaves solves the exothermicity problem, while simultaneously improving the mechanical performance of hardened cements and reducing the setting times. As expected, the cements are also found to be cytocompatible. Finally, it is observed that this process can be applied to calcium phosphate cements system (CPCs) as well. Based on the results, this microwave exposure provides a novel technique for the processing of injectable phosphate bone cement compositions. © 2013.

Modeling of the steam hydrolysis in a two-step process for hydrogen production by solar concentrated energy

NASA Astrophysics Data System (ADS)

Valle-Hernández, Julio; Romero-Paredes, Hernando; Pacheco-Reyes, Alejandro

2017-06-01

In this paper the simulation of the steam hydrolysis for hydrogen production through the decomposition of cerium oxide is presented. The thermochemical cycle for hydrogen production consists of the endothermic reduction of CeO2 to lower-valence cerium oxide, at high temperature, where concentrated solar energy is used as a source of heat; and of the subsequent steam hydrolysis of the resulting cerium oxide to produce hydrogen. The modeling of endothermic reduction step was presented at the Solar Paces 2015. This work shows the modeling of the exothermic step; the hydrolysis of the cerium oxide (III) to form H2 and the corresponding initial cerium oxide made at lower temperature inside the solar reactor. For this model, three sections of the pipe where the reaction occurs were considered; the steam water inlet, the porous medium and the hydrogen outlet produced. The mathematical model describes the fluid mechanics; mass and energy transfer occurring therein inside the tungsten pipe. Thermochemical process model was simulated in CFD. The results show a temperature distribution in the solar reaction pipe and allow obtaining the fluid dynamics and the heat transfer within the pipe. This work is part of the project "Solar Fuels and Industrial Processes" from the Mexican Center for Innovation in Solar Energy (CEMIE-Sol).

A Role-Play to Illustrate the Energy Changes Occurring in an Exothermic Reaction.

ERIC Educational Resources Information Center

Tyas, Toby; Cabot, John

1999-01-01

Describes a role-play activity designed to help students understand the energy changes involved in an exothermic reaction by modeling the concepts of bond-breaking takes in energy, activation energy, temperature rise, and bond breaking gives out energy. (WRM)

Influence of the volumes of bis-acryl and poly(methyl methacrylate) resins on their exothermic behavior during polymerization.

PubMed

Ha, Jung-Yun; Kim, Sung-Hun; Kim, Kyo-Han; Kwon, Tae-Yub

2011-01-01

This study aimed to evaluate the influence of the volumes of a bis-acryl resin (Luxatemp) and a poly(methyl methacrylate) resin (Jet) on their exothermic behaviors during polymerization based on vinyl group conversion. The number of vinyl groups reacted and exotherm were determined based on weight percent of methacrylate groups using FTIR spectroscopy. Temperature changes during polymerization at 23°C were recorded for 20 minutes using a multiple cavity mold overlying a thermocouple. The number of vinyl groups reacted and exotherm of Luxatemp were consistently lower than those of Jet at each resin volume. Mean peak temperature rises of Luxatemp and Jet were in the range of 2.0-6.6°C and 4.2-11.6°C respectively, with Luxatemp and Jet taking 2 and 10 minutes respectively to reach their peak temperatures. As their resin volumes increased, their peak temperatures and total peak areas were also observed to increase significantly (p<0.01).

Surprisingly facile CO2 insertion into cobalt alkoxide bonds: A theoretical investigation.

PubMed

Offermans, Willem K; Bizzarri, Claudia; Leitner, Walter; Müller, Thomas E

2015-01-01

Exploiting carbon dioxide as co-monomer with epoxides in the production of polycarbonates is economically highly attractive. More effective catalysts for this reaction are intensively being sought. To promote better understanding of the catalytic pathways, this study uses density functional theory calculations to elucidate the reaction step of CO2 insertion into cobalt(III)-alkoxide bonds, which is also the central step of metal catalysed carboxylation reactions. It was found that CO2 insertion into the cobalt(III)-alkoxide bond of [(2-hydroxyethoxy)Co(III)(salen)(L)] complexes (salen = N,N"-bis(salicyliden-1,6-diaminophenyl)) is exothermic, whereby the exothermicity depends on the trans-ligand L. The more electron-donating this ligand is, the more exothermic the insertion step is. Interestingly, we found that the activation barrier decreases with increasing exothermicity of the CO2 insertion. Hereby, a linear Brønsted-Evans-Polanyi relationship was found between the activation energy and the reaction energy.

Patterning of magnetic thin films and multilayers using nanostructured tantalum gettering templates.

PubMed

Qiu, Wenlan; Chang, Long; Lee, Dahye; Dannangoda, Chamath; Martirosyan, Karen; Litvinov, Dmitri

2015-03-25

This work demonstrates that a nonmagnetic thin film of cobalt oxide (CoO) sandwiched between Ta seed and capping layers can be effectively reduced to a magnetic cobalt thin film by annealing at 200 °C, whereas CoO does not exhibit ferromagnetic properties at room temperature and is stable at up to ∼400 °C. The CoO reduction is attributed to the thermodynamically driven gettering of oxygen by tantalum, similar to the exothermic reduction-oxidation reaction observed in thermite systems. Similarly, annealing at 200 °C of a nonmagnetic [CoO/Pd]N multilayer thin film sandwiched between Ta seed and Ta capping layers results in the conversion into a magnetic [Co/Pd]N multilayer, a material with perpendicular magnetic anisotropy that is of interest for magnetic data storage applications. A nanopatterning approach is introduced where [CoO/Pd]N multilayers is locally reduced into [Co/Pd]N multilayers to achieve perpendicular magnetic anisotropy nanostructured array. This technique can potentially be adapted to nanoscale patterning of other systems for which thermodynamically favorable combination of oxide and gettering layers can be identified.

Zirconia-molybdenum disilicide composites

DOEpatents

Petrovic, John J.; Honnell, Richard E.

1991-01-01

Compositions of matter comprised of molybdenum disilicide and zirconium oxide in one of three forms: pure, partially stabilized, or fully stabilized and methods of making the compositions. The stabilized zirconia is crystallographically stabilized by mixing it with yttrium oxide, calcium oxide, cerium oxide, or magnesium oxide and it may be partially stabilized or fully stabilized depending on the amount of stabilizing agent in the mixture.

Self-contained exothermic applicator and process

DOEpatents

Koehmstedt, Paul L.

1984-01-01

An adhesive resin application system which requires no external heating apparatus, and which is operative in the absence of a reactive atmosphere, is disclosed. The system provides its own heat by employing an adhesive material containing reactants which react exothermally when electrically ignited. After ignition of the reactants, sufficient heat energy is liberated by the exothermic reaction either to plasticize a thermoplastic resin or to cure a thermosetting resin and therby bond together two closely spaced objects. This application is a continuation-in-part of application Ser. No. 489,006, filed Apr. 27, 1983, which is a continuation-in-part of application, Ser. No. 929,120, filed July 28, 1978, both now abandoned.

Ventilation equations for improved exothermic process control.

PubMed

McKernan, John L; Ellenbecker, Michael J

2007-04-01

Exothermic or heated processes create potentially unsafe work environments for an estimated 5-10 million American workers each year. Excessive heat and process contaminants have the potential to cause acute health effects such as heat stroke, and chronic effects such as manganism in welders. Although millions of workers are exposed to exothermic processes, insufficient attention has been given to continuously improving engineering technologies for these processes to provide effective and efficient control. Currently there is no specific occupational standard established by OSHA regarding exposure to heat from exothermic processes, therefore it is important to investigate techniques that can mitigate known and potential adverse occupational health effects. The current understanding of engineering controls for exothermic processes is primarily based on a book chapter written by W. C. L. Hemeon in 1955. Improvements in heat transfer and meteorological theory necessary to design improved process controls have occurred since this time. The research presented involved a review of the physical properties, heat transfer and meteorological theories governing buoyant air flow created by exothermic processes. These properties and theories were used to identify parameters and develop equations required for the determination of buoyant volumetric flow to assist in improving ventilation controls. Goals of this research were to develop and describe a new (i.e. proposed) flow equation, and compare it to currently accepted ones by Hemeon and the American Conference of Governmental Industrial Hygienists (ACGIH). Numerical assessments were conducted to compare solutions from the proposed equations for plume area, mean velocity and flow to those from the ACGIH and Hemeon. Parameters were varied for the dependent variables and solutions from the proposed, ACGIH, and Hemeon equations for plume area, mean velocity and flow were analyzed using a randomized complete block statistical design (ANOVA). Results indicate that the proposed plume mean velocity equation provides significantly greater means than either the ACGIH or Hemeon equations throughout the range of parameters investigated. The proposed equations for plume area and flow also provide significantly greater means than either the ACGIH or Hemeon equations at distances >1 m above exothermic processes. With an accurate solution for the total volumetric flow, ventilation engineers and practicing industrial hygienists are equipped with the necessary information to design and size hoods, as well as place them at an optimal distance from the source to provide adequate control of the rising plume. The equations developed will allow researchers and practitioners to determine the critical control parameters for exothermic processes, such as the exhaust flow necessary to improve efficacy and efficiency, while ensuring adequate worker protection.

Energy Landscape of Water and Ethanol on Silica Surfaces

DOE PAGES

Wu, Di; Guo, Xiaofeng; Sun, Hui; ...

2015-06-26

Fundamental understanding of small molecule–silica surface interactions at their interfaces is essential for the scientific, technological, and medical communities. We report direct enthalpy of adsorption (Δh ads) measurements for ethanol and water vapor on porous silica glass (CPG-10), in both hydroxylated and dehydroxylated (hydrophobic) forms. Results suggest a spectrum of energetics as a function of coverage, stepwise for ethanol but continuous for water. The zero-coverage enthalpy of adsorption for hydroxylated silica shows the most exothermic enthalpies for both water (-72.7 ± 3.1 kJ/mol water) and ethanol (-78.0 ± 1.9 kJ/mol ethanol). The water adsorption enthalpy becomes less exothermic gradually untilmore » reaching its only plateau (-20.7 ± 2.2 kJ/mol water) reflecting water clustering on a largely hydrophobic surface, while the enthalpy of ethanol adsorption profile presents two well separated plateaus, corresponding to strong chemisorption of ethanol on adsorbate-free silica surface (-66.4 ± 4.8 kJ/mol ethanol), and weak physisorption of ethanol on ethanol covered silica (-4.0 ± 1.6 kJ/mol ethanol). On the other hand, dehydroxylation leads to missing water–silica interactions, whereas the number of ethanol binding sites is not impacted. The isotherms and partial molar properties of adsorption suggest that water may only bind strongly onto the silanols (which are a minor species on silica glass), whereas ethanol can interact strongly with both silanols and the hydrophobic areas of the silica surface.« less

Oxidation of C/SiC Composites at Reduced Oxygen Partial Pressures

NASA Technical Reports Server (NTRS)

Opila, E. J.; Serra, J. L.

2007-01-01

T-300 carbon fibers and T-300 carbon fiber reinforced silicon carbide composites (C/SiC) were oxidized in flowing reduced oxygen partial pressure environments at a total pressure of one atmosphere (0.5 atm O2, 0.05 atm O2 and 0.005 atm O2, balance argon). Experiments were conducted at four temperatures (816deg, 1149deg, 1343deg, and 1538 C). The oxidation kinetics were monitored using thermogravimetric analysis. T-300 fibers were oxidized to completion for times between 0.6 and 90 h. Results indicated that fiber oxidation kinetics were gas phase diffusion controlled. Oxidation rates had an oxygen partial pressure dependence with a power law exponent close to one. In addition, oxidation rates were only weakly dependent on temperature. The C/SiC coupon oxidation kinetics showed some variability, attributed to differences in the number and width of cracks in the SiC seal coat. In general, weight losses were observed indicating oxidation of the carbon fibers dominated the oxidation behavior. Low temperatures and high oxygen pressures resulted in the most rapid consumption of the carbon fibers. At higher temperatures, the lower oxidation rates were primarily attributed to crack closure due to SiC thermal expansion, rather than oxidation of SiC since these reduced rates were observed even at the lowest oxygen partial pressures where SiC oxidation is minimal.

Synthesis of TiCr2 intermetallic compound from mechanically activated starting powders via calcio-thermic co-reduction

NASA Astrophysics Data System (ADS)

Bayat, O.; Khavandi, A. R.; Ghasemzadeh, R.

2017-05-01

Effect of mechanical activation of TiO2 and Cr2O3 oxides as starting materials was investigated for direct synthesis of TiCr2. Differential thermal analysis (DTA) indicated that increasing the ball milling time resulted in lower exothermic reaction temperatures between molten Ca-Cr2O3 and molten Ca-TiO2. A model-free Kissinger type method was applied to DTA data to evaluate the reaction kinetics. The results reveal that the activation energy of the exothermic reactions decreased with increasing the milling time. The structure, oxygen content, and average particle sizes of the obtained TiCr2 product were affected by the ball milling time of the starting materials. Increasing the milling time from 10 to 40 h decreased the average particle size and oxygen content of the obtained TiCr2 from 10 to 2 μm and from 1690 to 1290 ppm, respectively. The X-ray diffraction (XRD) results showed that TiCr2 compounds with metastable bcc phase can be produced using nano-sized starting materials, while only a slight amount of bcc phase can be obtained in the TiCr2 compounds, using micron-sized starting materials. The TiCr2 obtained by this method had a hydrogen absorption capability of 0.63 wt % and the kinetics of the hydrogen absorption increased for the 40 h milled sample.

Oxygen partial pressure sensor

DOEpatents

Dees, D.W.

1994-09-06

A method for detecting oxygen partial pressure and an oxygen partial pressure sensor are provided. The method for measuring oxygen partial pressure includes contacting oxygen to a solid oxide electrolyte and measuring the subsequent change in electrical conductivity of the solid oxide electrolyte. A solid oxide electrolyte is utilized that contacts both a porous electrode and a nonporous electrode. The electrical conductivity of the solid oxide electrolyte is affected when oxygen from an exhaust stream permeates through the porous electrode to establish an equilibrium of oxygen anions in the electrolyte, thereby displacing electrons throughout the electrolyte to form an electron gradient. By adapting the two electrodes to sense a voltage potential between them, the change in electrolyte conductivity due to oxygen presence can be measured. 1 fig.

Oxygen partial pressure sensor

DOEpatents

Dees, Dennis W.

1994-01-01

A method for detecting oxygen partial pressure and an oxygen partial pressure sensor are provided. The method for measuring oxygen partial pressure includes contacting oxygen to a solid oxide electrolyte and measuring the subsequent change in electrical conductivity of the solid oxide electrolyte. A solid oxide electrolyte is utilized that contacts both a porous electrode and a nonporous electrode. The electrical conductivity of the solid oxide electrolyte is affected when oxygen from an exhaust stream permeates through the porous electrode to establish an equilibrium of oxygen anions in the electrolyte, thereby displacing electrons throughout the electrolyte to form an electron gradient. By adapting the two electrodes to sense a voltage potential between them, the change in electrolyte conductivity due to oxygen presence can be measured.

Synthesis of carbon nanotubes from waste polyethylene plastics

NASA Astrophysics Data System (ADS)

Zhuo, Chuanwei

Generation of non-biodegradable wastes, such as plastics, and resulting land as well as water pollution therefrom discarded plastics have been continuously increasing, while landfill space decreases and recycling markets dwindle. Exploration of novel uses of such materials becomes therefore imperative. Here I present an innovative and unique partial conversion of plastic waste to valuable carbon nanomaterials. It is an overall exothermic and scalable process based on feeding waste plastics to a multi-stage, pyrolysis/combustion-synthesis reactor. Plain stainless steel screens are used as substrates as well as low-cost catalyst for both carbon nanomaterials synthesis and pyrolyzates generation. Nano carbon yields of as high as 13.6% of the weight of the polymer precursor were recorded. This demonstration provides a sustainable solution to both plastic waste utilization, and carbon nanomaterials mass production.

Low-cost high purity production

NASA Technical Reports Server (NTRS)

Kapur, V. K.

1978-01-01

Economical process produces high-purity silicon crystals suitable for use in solar cells. Reaction is strongly exothermic and can be initiated at relatively low temperature, making it potentially suitable for development into low-cost commercial process. Important advantages include exothermic character and comparatively low process temperatures. These could lead to significant savings in equipment and energy costs.

Comparison of partial and full nitrification processes applied for treating high-strength nitrogen wastewaters: microbial ecology through nitrous oxide production.

PubMed

Ahn, Joon Ho; Kwan, Tiffany; Chandran, Kartik

2011-04-01

The goal of this study was to compare the microbial ecology, gene expression, biokinetics, and N2O emissions from a lab-scale bioreactor operated sequentially in full-nitrification and partial-nitrification modes. Based on sequencing of 16S rRNA and ammonia monooxygenase subunit A (amoA) genes, ammonia oxidizing bacteria (AOB) populations during full- and partial-nitrification modes were distinct from one another. The concentrations of AOB (XAOB) and their respiration rates during full- and partial-nitrification modes were statistically similar, whereas the concentrations of nitrite oxidizing bacteria (XNOB) and their respiration rates declined significantly after the switch from full- to partial-nitrification. The transition from full-nitrification to partial nitrification resulted in a protracted transient spike of nitrous oxide (N2O) and nitric oxide (NO) emissions, which later stabilized. The trends in N2O and NO emissions correlated well with trends in the expression of nirK and norB genes that code for the production of these gases in AOB. Both the transient and stabilized N2O and NO emissions during partial nitrification were statistically higher than those during steady-state full-nitrification. Based on these results, partial nitrification strategies for biological nitrogen removal, although attractive for their reduced operating costs and energy demand, may need to be optimized against the higher carbon foot-print attributed to their N2O emissions.

Oxidation of C/SiC Composites at Reduced Oxygen Partial Pressures

NASA Technical Reports Server (NTRS)

Opila, Elizabeth J.; Serra, Jessica

2009-01-01

Carbon-fiber reinforced SiC (C/SiC) composites are proposed for leading edge applications of hypersonic vehicles due to the superior strength of carbon fibers at high temperatures (greater than 1500 C). However, the vulnerability of the carbon fibers in C/SiC to oxidation over a wide range of temperatures remains a problem. Previous oxidation studies of C/SiC have mainly been conducted in air or oxygen, so that the oxidation behavior of C/SiC at reduced oxygen partial pressures of the hypersonic flight regime are less well understood. In this study, both carbon fibers and C/SiC composites were oxidized over a wide range of temperatures and oxygen partial pressures to facilitate the understanding and modeling of C/SiC oxidation kinetics for hypersonic flight conditions.

Energy conditions of high quality laser-oxygen cutting of mild steel

NASA Astrophysics Data System (ADS)

Shulyatyev, V. B.; Orishich, A. M.; Malikov, A. G.

2011-02-01

In our previous work we found experimentally the scaling laws for the oxygen-assisted laser cutting of low-carbon steel of 5 - 25 mm. No dross and minimal roughness of the cut surface were chosen as criteria of quality. Formulas were obtained to determine the optimum values of the laser power and cutting speed for the given sheet thickness. In the present paper, the energy balance of the oxygen-assisted laser cutting is studied experimentally at these optimum parameters. The absorbed laser energy and heat conduction losses and cut width were measured experimentally, and then the energy of exothermic reaction of oxidation was found from the balance equation. To define the integral coefficient of absorption, the laser power was measured on the cutting channel exit during the cutting. The heat conduction losses were measured by the calorimetric method. It has been established that the absorbed laser energy, oxidation energy, thermal losses and melting enthalpy related to a sheet thickness unit, do not depend on the sheet thickness at the cutting with the minimal roughness. The results enable to determine the fraction of the oxidized iron in the melt and thermal efficiency at the cutting with the minimal roughness. The share of the oxidation reaction energy is 50 - 60% in the total contributed energy.

Modeling and experimental performance of an intermediate temperature reversible solid oxide cell for high-efficiency, distributed-scale electrical energy storage

NASA Astrophysics Data System (ADS)

Wendel, Christopher H.; Gao, Zhan; Barnett, Scott A.; Braun, Robert J.

2015-06-01

Electrical energy storage is expected to be a critical component of the future world energy system, performing load-leveling operations to enable increased penetration of renewable and distributed generation. Reversible solid oxide cells, operating sequentially between power-producing fuel cell mode and fuel-producing electrolysis mode, have the capability to provide highly efficient, scalable electricity storage. However, challenges ranging from cell performance and durability to system integration must be addressed before widespread adoption. One central challenge of the system design is establishing effective thermal management in the two distinct operating modes. This work leverages an operating strategy to use carbonaceous reactant species and operate at intermediate stack temperature (650 °C) to promote exothermic fuel-synthesis reactions that thermally self-sustain the electrolysis process. We present performance of a doped lanthanum-gallate (LSGM) electrolyte solid oxide cell that shows high efficiency in both operating modes at 650 °C. A physically based electrochemical model is calibrated to represent the cell performance and used to simulate roundtrip operation for conditions unique to these reversible systems. Design decisions related to system operation are evaluated using the cell model including current density, fuel and oxidant reactant compositions, and flow configuration. The analysis reveals tradeoffs between electrical efficiency, thermal management, energy density, and durability.

Core-shell-structured nanothermites synthesized by atomic layer deposition

NASA Astrophysics Data System (ADS)

Qin, Lijun; Gong, Ting; Hao, Haixia; Wang, Keyong; Feng, Hao

2013-12-01

Thermite materials feature very exothermic solid-state redox reactions. However, the energy release rates of traditional thermite mixtures are limited by the reactant diffusion velocities. In this work, atomic layer deposition (ALD) is utilized to synthesize thermite materials with greatly enhanced reaction rates. By depositing certain types of metal oxides (oxidizers) onto a commercial Al nanopowder, core-shell-structured nanothermites can be produced. The average film deposition rate on the Al nanopowder is 0.17 nm/cycle for ZnO and 0.031 nm/cycle for SnO2. The thickness of the oxidizer layer can be precisely controlled by adjusting the ALD cycle number. The compositions, morphologies, and structures of the ALD nanothermites are characterized by X-ray photoelectron spectroscopy, scanning electron microscopy, and high-resolution transmission electron microscopy. The characterization results reveal nearly perfect coverage of the Al nanoparticles by uniform ALD oxidizer layers and confirm the formation of core-shell nanoparticles. Combustion properties of the nanothermites are probed by laser ignition technique. Reactions of the core-shell-structured nanothermites are several times faster than the mixture of nanopowders. The promoted reaction rate is mostly attributed to the uniform distribution of reactants on the nanometer scale. These core-shell-structured nanothermites provide a potential pathway to control and enhance thermite reactions.

Comparative studies on acid leaching of zinc waste materials

NASA Astrophysics Data System (ADS)

Rudnik, Ewa; Włoch, Grzegorz; Szatan, Leszek

2017-11-01

Three industrial waste materials were characterized in terms of their elemental and phase compositions, leaching behaviour in 10% sulfuric acid solution as well as leaching thermal effects. Slag from melting of mixed metallic scrap contained about 50% Zn and 10% Pb. It consisted mainly of various oxides and oxy-chlorides of metals. Zinc spray metallizing dust contained about 77% Zn in form of zinc and/or zinc-iron oxides, zinc metal and Zn-Fe intermetallic. Zinc ash from hot dip galvanizing was a mixture of zinc oxide, metallic zinc and zinc hydroxide chloride and contained about 80% Zn. Dissolution efficiency of zinc from the first material was 80% (independently on the solid to liquid ratio, 50-150 kg/m3), while decrease of the efficacy from 80% to 60% with increased solid to liquid ratio for the two remaining materials was observed. Both increase in the temperature (20 °C to 35 °C) and agitation rate (300 rpm to 900 rpm) did not improve seriously the leaching results. In all cases, transfer of zinc ions to the leachate was accompanied by different levels of solution contamination, depending on the type of the waste. Leaching of the materials was exothermic with the similar reaction heats for two high oxide-type products (slag, zinc ash) and higher values for the spray metallizing dust.

Atmospheric Oxidation Mechanism of Furfural Initiated by Hydroxyl Radicals.

PubMed

Zhao, Xiaocan; Wang, Liming

2017-05-04

Furfural is emitted into the atmosphere because of its potential applications as an intermediate to alkane fuels from biomass, industrial usages, and biomass burning. The kinetic and mechanistic information on the furfural chemistry is necessary to assess the fate of furfural in the atmosphere and its impact on the air quality. Here we studied the atmospheric oxidation mechanisms of furfural initiated by the OH radicals using quantum chemistry and kinetic calculations. The reaction of OH and furfural was initiated mainly by OH additions to C 2 and C 5 positions, forming R2 and R5 adducts, which could undergo rapid ring-breakage to form R2B and R5B, respectively. Our calculations showed that these intermediate radicals reacted rather slowly with O 2 under the atmospheric conditions because the additions of O 2 to these radicals are only slightly exothermic and highly reversible. Alternatively, these radicals would react directly with O 3 , NO 2 , HO 2 /RO 2 , etc. Namely, the atmospheric oxidation of furfural would unlikely result in ozone formation. Under typical atmospheric conditions, the main products in OH-initiated furfural oxidation include 2-oxo-3-pentene-1,5-dialdehyde, 5-hydroxy-2(5H)-furanone, 4-oxo-2- butenoic acid, and 2,5-furandione. These compounds will likely stay in the gas phase and are subject to further photo-oxidation.

H2S adsorption and decomposition on the gradually reduced α-Fe2O3(001) surface: A DFT study

NASA Astrophysics Data System (ADS)

Lin, Changfeng; Qin, Wu; Dong, Changqing

2016-11-01

Reduction of iron based desulfurizer occurs during hot gas desulfurization process, which will affect the interaction between H2S and the desulfurizer surface. In this work, a detailed adsorption behavior and dissociation mechanism of H2S on the perfect and reduced α-Fe2O3(001) surfaces, as well as the correlation between the interaction characteristic and reduction degree of iron oxide, have been studied by using periodic density functional theory (DFT) calculations. Results demonstrate that H2S firstly chemisorbs on surface at relatively higher oxidation state (reduction degree χ < 33%), then dissociative adsorption occurs and becomes the main adsorption type after χ > 33%. Reduction of iron oxide benefits the H2S adsorption. Further, dissociation processes of H2S via molecular and dissociative adsorption were investigated. Results show that after reduction of Fe2O3 into the oxidation state around FeO and Fe, the reduced surface exhibits very strong catalytic capacity for H2S decomposition into S species. Meanwhile, the overall dissociation process on all surfaces is exothermic. These results provide a fundamental understanding of reduction effect of iron oxide on the interaction mechanism between H2S and desulfurizer surface, and indicate that rational control of reduction degree of desulfurizer is essential for optimizing the hot gas desulfurization process.

Complex Wall Boundary Conditions for Modeling Combustion in Catalytic Channels

NASA Astrophysics Data System (ADS)

Zhu, Huayang; Jackson, Gregory

2000-11-01

Monolith catalytic reactors for exothermic oxidation are being used in automobile exhaust clean-up and ultra-low emissions combustion systems. The reactors present a unique coupling between mass, heat, and momentum transport in a channel flow configuration. The use of porous catalytic coatings along the channel wall presents a complex boundary condition when modeled with the two-dimensional channel flow. This current work presents a 2-D transient model for predicting the performance of catalytic combustion systems for methane oxidation on Pd catalysts. The model solves the 2-D compressible transport equations for momentum, species, and energy, which are solved with a porous washcoat model for the wall boundary conditions. A time-splitting algorithm is used to separate the stiff chemical reactions from the convective/diffusive equations for the channel flow. A detailed surface chemistry mechanism is incorporated for the catalytic wall model and is used to predict transient ignition and steady-state conversion of CH4-air flows in the catalytic reactor.

Thermodynamically Leveraged Tandem Catalysis for Ester RC(O)O–R' Bond Hydrogenolysis. Scope and Mechanism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lohr, Tracy L.; Li, Zhi; Assary, Rajeev S.

2015-05-18

Rapid and selective formal hydrogenolysis of aliphatic ester RC(O)O–R' linkages is achieved by a tandem homogeneous metal triflate + supported palladium catalytic system. The triflate catalyzes the mildly exothermic, turnover-limiting O–R' cleavage process, whereas the exothermic hydrogenation of the intermediate alkene further drives the overall reaction to completion.

Thermodynamically leveraged Tandem catalysis for ester RC(O)O-R' bond hydrogenolysis. scope and mechanism.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lohr, Tracy L.; Li, Zhi; Assary, Rajeev S.

2015-06-01

Rapid and selective formal hydrogenolysis of aliphatic ester RC(O)O-R' linkages is achieved by a tandem homogeneous metal triflate + supported palladium catalytic system. The triflate catalyzes the mildly exothermic, turnover-limiting O-R' cleavage process, whereas the exothermic hydrogenation of the intermediate alkene further drives the overall reaction to completion.

Molecular mechanism of NDMA formation from N,N-dimethylsulfamide during ozonation: quantum chemical insights into a bromide-catalyzed pathway.

PubMed

Trogolo, Daniela; Mishra, Brijesh Kumar; Heeb, Michèle B; von Gunten, Urs; Arey, J Samuel

2015-04-07

During ozonation of drinking water, the fungicide metabolite N,N-dimethylsulfamide (DMS) can be transformed into a highly toxic product, N-nitrosodimethylamine (NDMA). We used quantum chemical computations and stopped-flow experiments to evaluate a chemical mechanism proposed previously to describe this transformation. Stopped-flow experiments indicate a pK(a) = 10.4 for DMS. Experiments show that hypobromous acid (HOBr), generated by ozone oxidation of naturally occurring bromide, brominates the deprotonated DMS(-) anion with a near-diffusion controlled rate constant (7.1 ± 0.6 × 10(8) M(-1) s(-1)), forming Br-DMS(-) anion. According to quantum chemical calculations, Br-DMS has a pK(a) ∼ 9.0 and thus remains partially deprotonated at neutral pH. The anionic Br-DMS(-) bromamine can react with ozone with a high rate constant (10(5 ± 2.5) M(-1) s(-1)), forming the reaction intermediate (BrNO)(SO2)N(CH3)2(-). This intermediate resembles a loosely bound complex between an electrophilic nitrosyl bromide (BrNO) molecule and an electron-rich dimethylaminosulfinate ((SO2)N(CH3)2(-)) fragment, based on inspection of computed natural charges and geometric parameters. This fragile complex undergoes immediate (10(10 ± 2.5) s(-1)) reaction by two branches: an exothermic channel that produces NDMA, and an entropy-driven channel giving non-NDMA products. Computational results bring new insights into the electronic nature, chemical equilibria, and kinetics of the elementary reactions of this pathway, enabled by computed energies of structures that are not possible to access experimentally.

Magnesium Recycling of Partially Oxidized, Mixed Magnesium-Aluminum Scrap through Combined Refining and Solid Oxide Membrane Electrolysis Processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiaofei Guan; Peter A. Zink; Uday B. Pal

2012-01-01

Pure magnesium (Mg) is recycled from 19g of partially oxidized 50.5wt.% Mg-Aluminum (Al) alloy. During the refining process, potentiodynamic scans (PDS) were performed to determine the electrorefining potential for magnesium. The PDS show that the electrorefining potential increases over time as the magnesium content inside the Mg-Al scrap decreases. Up to 100% percent of magnesium is refined from the Mg-Al scrap by a novel refining process of dissolving magnesium and its oxide into a flux followed by vapor phase removal of dissolved magnesium and subsequently condensing the magnesium vapor. The solid oxide membrane (SOM) electrolysis process is employed in themore » refining system to enable additional recycling of magnesium from magnesium oxide (MgO) in the partially oxidized Mg-Al scrap. The combination of the refining and SOM processes yields 7.4g of pure magnesium.« less

Early in vivo changes in calcium ions, oxidative stress markers, and ion channel immunoreactivity following partial injury to the optic nerve.

PubMed

Wells, Jonathan; Kilburn, Matthew R; Shaw, Jeremy A; Bartlett, Carole A; Harvey, Alan R; Dunlop, Sarah A; Fitzgerald, Melinda

2012-03-01

CNS injury is often localized but can be followed by more widespread secondary degenerative events that usually result in greater functional loss. Using a partial transection model in rat optic nerve (ON). we recently demonstrated in vivo increases in the oxidative stress-associated enzyme MnSOD 5 min after injury. However, mechanisms by which early oxidative stress spreads remain unclear. In the present study, we assessed ion distributions, additional oxidative stress indicators, and ion channel immunoreactivity in ON in the first 24 hr after partial transection. Using nanoscale secondary ion mass spectroscopy (NanoSIMS), we demonstrate changes in the distribution pattern of Ca ions following partial ON transection. Regions of elevated Ca ions in normal ON in vivo rapidly decrease following partial ON transection, but there is an increasingly punctate distribution at 5 min and 24 hr after injury. We also show rapid decreases in catalase activity and later increases in immunoreactivity of the advanced glycation end product carboxymethyl lysine in astrocytes. Increased oxidative stress in astrocytes is accompanied by significantly increased immunoreactivity of the AMPA receptor subunit GluR1 and aquaporin 4 (AQP4). Taken together, the results indicate that Ca ion changes and oxidative stress are early events following partial ON injury that are associated with changes in GluR1 AMPA receptor subunits and altered ionic balance resulting from increased AQP4. Copyright © 2011 Wiley Periodicals, Inc.

The Energetics of Oxide Multilayer Systems: SOFC Cathode and Electrolyte Materials

NASA Astrophysics Data System (ADS)

Kemik, Nihan

Complex oxides are evoking a surge of scientific and technological interest due to the unexpected properties of their interfaces which have been shown to differ from the constituent materials. Layered oxide structures have found wide use in applications ranging from electronic and magnetic devices to solid oxide fuel cells (SOFCs). For devices such as SOFCs which utilize multilayers at elevated temperatures, it is critical to know the relative stabilities of these interfaces since they directly influence the device performance. In this work, we explored the energetics of two oxide multilayer systems which are relevant for SOFCs components using high temperature solution calorimetry and differential scanning calorimetry (DSC). The fundamental understanding of the interfacial and structural properties of multilayers combined with the information about phase stabilities is essential in materials selection for components for intermediate temperature SOFC's. For cathode materials, we investigated the family of perovskite oxides, La0.7Sr0.3MO3, where M=Mn and Fe, as well as their solid solution phase. Manganites have been the most investigated cathode material, while the ferrites are also being considered for future use due to their thermodynamic stability and close thermal expansion coefficient with the commonly used electrolyte materials. For the bulk La0.7Sr0.3FexMn1-xO 3 solid solution, high temperature oxide melt drop solution calorimetry was performed to determine the enthalpies of formation from binary oxides and the enthalpy of mixing. It was shown that the symmetry of the perovskite structure, the valence of transition metal, and the energetics are highly interdependent and the balance between the different valence states of the Mn and Fe ions is the main factor in determining the energetics. The energetics of interfaces in multilayered structures was investigated by high temperature oxide melt solution calorimetry for the first time. The drop solution calorimetry results of La0.7Sr0.3MnO3(LSMO)/La0.7 Sr0.3FeO3(LSFO) multilayers and LSMO film are highly exothermic and differ from the bulk material with the same composition. The magnetic and electronic properties of LSMO/LSFO superlattices are highly dependent on the thickness and the structure of the individual layers. Resonant X-Ray reflectivity (XRR) technique was utilized to characterize the structure of the LSMO/LSFO superlattices. It was shown that the XRR spectra taken at the Mn and Fe absorption edges can provide more structural information than the spectra at the X-ray energy of a conventional Cu source. With this non-destructive technique, we demonstrated the ability to compare the intermixing behavior and thickness regularity throughout the thickness of different superlattice structures. For electrolyte materials, we studied the yttria stabilized zirconia (YSZ) /Al2O3 multilayer system. Differential scanning calorimetry (DSC) was used to study the crystallization of the YSZ layers to explore the effect of the interfaces on phase stabilities. It was observed that the crystallization temperature increased and the enthalpy became more exothermic as the interfacial area increased. This work demonstrated that DSC is a promising technique to study the thin film reactions and explore the interfacial enthalpies in oxide multilayer systems.

A Model for the Oxidation of Carbon Silicon Carbide Composite Structures

NASA Technical Reports Server (NTRS)

Sullivan, Roy M.

2004-01-01

A mathematical theory and an accompanying numerical scheme have been developed for predicting the oxidation behavior of carbon silicon carbide (C/SiC) composite structures. The theory is derived from the mechanics of the flow of ideal gases through a porous solid. The result of the theoretical formulation is a set of two coupled nonlinear differential equations written in terms of the oxidant and oxide partial pressures. The differential equations are solved simultaneously to obtain the partial vapor pressures of the oxidant and oxides as a function of the spatial location and time. The local rate of carbon oxidation is determined using the map of the local oxidant partial vapor pressure along with the Arrhenius rate equation. The nonlinear differential equations are cast into matrix equations by applying the Bubnov-Galerkin weighted residual method, allowing for the solution of the differential equations numerically. The numerical method is demonstrated by utilizing the method to model the carbon oxidation and weight loss behavior of C/SiC specimens during thermogravimetric experiments. The numerical method is used to study the physics of carbon oxidation in carbon silicon carbide composites.

Synthesis of potassium ferrate using residual ferrous sulfate as iron bearing material

NASA Astrophysics Data System (ADS)

Kanari, N.; Filippov, L.; Diot, F.; Mochón, J.; Ruiz-Bustinza, I.; Allain, E.; Yvon, J.

2013-03-01

This paper summarizes the results obtained during potassium ferrate (K2FeVIO4) synthesis which is a high added value material. This compound that contains iron in the rare hexavalent state is becoming a substance of growing importance for the water and effluent treatment industries. This is due to its multi-functional nature (oxidation, flocculation, elimination of heavy metals, decomposition of organic matter, etc.). The most well known synthesis methods for potassium ferrate synthesis are those involving the chemical and/or electrochemical oxidation of iron (II) and (III) from aqueous solutions having a high alkali concentration. These methods are generally characterized by a low FeVI efficiency due to the reaction of the potassium ferrate with water, leading to the reduction of FeVI into FeIII. Concerning the work pertinent to this paper, the synthesis of K2FeVIO4 was achieved by a simultaneous reaction of two solids (iron sulfate and KOH) and one gaseous oxidant (chlorine). The synthesis process is performed in a rotary reactor at room temperature and the global synthesis reaction is exothermic. The effects of different experimental parameters on the potassium ferrate synthesis are investigated to determine the optimal conditions for the process.

Using Different Conceptual Change Methods Embedded within 5E Model: A Sample Teaching of Endothermic-Exothermic Reactions

ERIC Educational Resources Information Center

Turk, Fatma; Calik, Muammer

2008-01-01

Since Widodo, Duit and Muller (2002) addressed that there is a gap between teacher's theoretical knowledge and their practical classroom constructivist behavior, we presented a sample teaching activity about Endothermic-Exothermic Reactions for teacher usage. Therein, the aim of this study is to design a 5E model to include students' alternative…

Evaluation of amorphous magnesium phosphate (AMP) based non-exothermic orthopedic cements.

PubMed

Babaie, Elham; Lin, Boren; Goel, Vijay K; Bhaduri, Sarit B

2016-10-07

This paper reports for the first time the development of a biodegradable, non-exothermic, self-setting orthopedic cement composition based on amorphous magnesium phosphate (AMP). The occurrence of undesirable exothermic reactions was avoided through using AMP as the solid precursor. The phenomenon of self-setting with optimum rheology is achieved by incorporating a water soluble biocompatible/biodegradable polymer, polyvinyl alcohol (PVA). Additionally, PVA enables a controlled growth of the final phase via a biomimetic process. The AMP powder was synthesized using a precipitation method. The powder, when in contact with the aqueous PVA solution, forms a putty resulting in a nanocrystalline magnesium phosphate phase of cattiite. The as-prepared cement compositions were evaluated for setting times, exothermicity, compressive strength, biodegradation, and microstructural features before and after soaking in SBF, and in vitro cytocompatibility. Since cattiite is relatively unexplored in the literature, a first time evaluation reveals that it is cytocompatible, just like the other phases in the MgO-P 2 O 5 (Mg-P) system. The cement composition prepared with 15% PVA in an aqueous medium achieved clinically relevant setting times, mechanical properties, and biodegradation. Simulated body fluid (SBF) soaking resulted in coating of bobierrite onto the cement particle surfaces.

Radiolytic Gas-Driven Cryovolcanism in the Outer Solar System

NASA Technical Reports Server (NTRS)

Cooper, John F.; Cooper, Paul D.; Sittler, Edward C.; Sturner, Steven J.; Rymer, Abigail M.; Hill, Matthew E.

2007-01-01

Water ices in surface crusts of Europa, Enceladus, Saturn's main rings, and Kuiper Belt Objects can become heavily oxidized from radiolytic chemical alteration of near-surface water ice by space environment irradiation. Oxidant accumulations and gas production are manifested in part through observed H2O2 on Europa. tentatively also on Enceladus, and found elsewhere in gaseous or condensed phases at moons and rings of Jupiter and Saturn. On subsequent chemical contact in sub-surface environments with significant concentrations of primordially abundant reductants such as NH3 and CH4, oxidants of radiolytic origin can react exothermically to power gas-driven cryovolcanism. The gas-piston effect enormously amplifies the mass flow output in the case of gas formation at basal thermal margins of incompressible fluid reservoirs. Surface irradiation, H2O2 production, NH3 oxidation, and resultant heat, gas, and gas-driven mass flow rates are computed in the fluid reservoir case for selected bodies. At Enceladus the oxidant power inputs are comparable to limits on nonthermal kinetic power for the south polar plumes. Total heat output and plume gas abundance may be accounted for at Enceladus if plume activity is cyclic in high and low "Old Faithful" phases, so that oxidants can accumulate during low activity phases. Interior upwelling of primordially abundant NH3 and CH4 hydrates is assumed to resupply the reductant fuels. Much lower irradiation fluxes on Kuiper Belt Objects require correspondingly larger times for accumulation of oxidants to produce comparable resurfacing, but brightness and surface composition of some objects suggest that such activity may be ongoing.

Freeze-thawing behaviour of highly concentrated aqueous alkali chloride-glucose systems.

PubMed

Kajiwara, K; Motegi, A; Murase, N

2001-01-01

The freeze-thawing behaviour of highly concentrated aqueous alkali chloride-glucose systems was investigated by differential scanning calorimetry (DSC). In the aqueous NaCl-glucose solution system, single or double glass transitions followed by the corresponding devitrification exotherms were observed during rewarming. In the aqueous KCl-glucose solution system, on the other hand, a single glass transition followed by an exotherm was observed during rewarming. The presence of double glass transitions observed for a certain composition of the aqueous NaCl-glucose solution was taken as an evidence for the liquid-liquid immiscibility at low temperatures. Two kinds of crystallisation accompanied by exotherms during rewarming were identified by X-ray diffraction as ice and ice/NaCl x 2H(2)O, or ice/KCl eutectic component.

THE EFFECT OF SULFUR ON METHANE PARTIAL OXIDATION AND REFORMING PROCESSES FOR LEAN NOX TRAP CATALYSIS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parks, II, James E; Ponnusamy, Senthil

2006-01-01

Lean NOx trap catalysis has demonstrated the ability to reduce NOx emissions from lean natural gas reciprocating engines by >90%. The technology operates in a cyclic fashion where NOx is trapped on the catalyst during lean operation and released and reduced to N2 under rich exhaust conditions; the rich cleansing operation of the cycle is referred to as "regeneration" since the catalyst is reactivated for more NOx trapping after NOx purge. Creating the rich exhaust conditions for regeneration can be accomplished by catalytic partial oxidation of methane in the exhaust system. Furthermore, catalytic reforming of partial oxidation exhaust can enablemore » increased quantities of H2 which is an excellent reductant for lean NOx trap regeneration. It is critical to maintain clean and efficient partial oxidation and reforming processes to keep the lean NOx trap functioning properly and to reduce extra fuel consumption from the regeneration process. Although most exhaust constituents do not impede partial oxidation and reforming, some exhaust constituents may negatively affect the catalysts and result in loss of catalytic efficiency. Of particular concern are common catalyst poisons sulfur, zinc, and phosphorous. These poisons form in the exhaust through combustion of fuel and oil, and although they are present at low concentrations, they can accumulate to significant levels over the life of an engine system. In the work presented here, the effects of sulfur on the partial oxidation and reforming catalytic processes were studied to determine any durability limitations on the production of reductants for lean NOx trap catalyst regeneration.« less

Magnesium Recycling of Partially Oxidized, Mixed Magnesium-Aluminum Scrap Through Combined Refining and Solid Oxide Membrane (SOM) Electrolysis Processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guan, Xiaofei; Zink, Peter; Pal, Uday

2012-03-11

Pure magnesium (Mg) is recycled from 19g of partially oxidized 50.5wt.%Mg-Aluminum (Al) alloy. During the refining process, potentiodynamic scans (PDS) were performed to determine the electrorefining potential for magnesium. The PDS show that the electrorefining potential increases over time as the Mg content inside the Mg-Al scrap decreases. Up to 100% percent of magnesium is refined from the Mg-Al scrap by a novel refining process of dissolving magnesium and its oxide into a flux followed by vapor phase removal of dissolved magnesium and subsequently condensing the magnesium vapors in a separate condenser. The solid oxide membrane (SOM) electrolysis process ismore » employed in the refining system to enable additional recycling of magnesium from magnesium oxide (MgO) in the partially oxidized Mg-Al scrap. The combination of the refining and SOM processes yields 7.4g of pure magnesium; could not collect and weigh all of the magnesium recovered.« less

Why Combustions Are Always Exothermic, Yielding about 418 kJ per Mole of O[subscript 2

ERIC Educational Resources Information Center

Schmidt-Rohr, Klaus

2015-01-01

The strongly exothermic nature of reactions between molecular oxygen and all organic molecules as well as many other substances is explained in simple, general terms. The double bond in O[subscript 2] is much weaker than other double bonds or pairs of single bonds, and therefore the formation of the stronger bonds in CO[subscript 2] and…

Effect of structure and thermodynamic stability on the response of lanthanide stannate pyrochlores to ion beam irradiation.

PubMed

Lian, J; Helean, K B; Kennedy, B J; Wang, L M; Navrotsky, A; Ewing, R C

2006-02-09

The lanthanide stannates, Ln2Sn2O7, Ln=La-Lu and Y, have the isometric pyrochlore structure, A2B2O7, and their structural properties have been refined by Rietveld analysis of powder neutron and synchrotron X-ray diffraction data. In this study, the enthalpies of formation of selected stannate pyrochlores, Ln=La, Nd, Sm, Eu, Dy, and Yb, were measured by high-temperature oxide melt solution calorimetry. Their radiation response was determined by 1 MeV Kr2+ ion irradiation combined with in situ TEM observation over the temperature range of 25 to 1000 K. The enthalpy of formation from binary oxides of stannate pyrochlores became more endothermic (from -145 to -40 kJ/mol) as the size of the lanthanide in the A-site decreases. A more exothermic trend of the enthalpy of formation was observed in stannate pyrochlores with larger lanthanide ions, particularly La, possibly as a result of increased covalency in the Sn-O bond. In contrast to lanthanide titanate pyrochlores, Ln2Ti2O7, that are generally susceptible to radiation-induced amorphization and zirconate pyrochlores, Ln2Zr2O7, that are generally resistant to radiation-induced amorphization, the lanthanide stannate pyrochlores show a much greater variation in their response to ion irradiation. La, Nd, and Gd stannates experience the radiation-induced transformation to the aperiodic state, and the critical amorphization temperatures are approximately 960, 700, and 350 K, respectively. Y and Er stannate pyrochlores cannot be amorphized by ion beam irradiation, even at 25 K, and instead disorder to a defect fluorite structure. Comparison of the calorimetric and ion irradiation data for titanate, zirconate, and stannate pyrochlores reveals a strong correlation among subtle changes in crystal structure with changing composition, the energetics of the disordering process, and the temperature above which the material can no longer be amorphized. In summary, as the structure approaches the ideal, ordered pyrochlore structure, radiation-induced amorphization is more easily attained. This is consistent with an increasingly exothermic trend in the enthalpies of formation of pyrochlores from the oxides, that is, the greater the thermochemical stability of the pyrochlore structure, the more likely it will be amorphized upon radiation damage rather than recover to a disordered fluorite structure.

Derivatives of cysteine related to the thiosulfate metabolism of sulfur bacteria by the multi-enzyme complex "Sox"-studied by B3LYP-PCM and G3X(MP2) calculations.

PubMed

Steudel, Ralf; Steudel, Yana

2010-01-21

Certain sulfur bacteria oxidize thiosulfate enzymatically to sulfate, and derivatives of the amino acid cysteine play an important role as intermediates in this process. Since some of the proposed intermediates have so far been of hypothetical nature, we have investigated the structures and thermodynamic properties of more than 60 related derivatives of cysteine (CysH) by high-level quantum chemical calculations both in the gas phase and in a polarizable continuum using the PCM method to simulate an aqueous solution. Most of these molecules and anions were studied for the first time. Especially for the smaller species several conformational isomers of similar energy were identified; their relative stabilities are mainly determined by intramolecular hydrogen bonds. In contrast to the thiolate ion [Cys](-), the gaseous anions [CysS](-), [CysSO(2)](-), [CysSO(3)](-) and [CysSSO(3)](-) are most stable as zwitterions containing an NH(3) rather than an NH(2) group. This result also holds for the polarizable continuum. On the other hand, the related neutral molecules CysH, CysSH and CysSO(2)H are predicted to exist as NH(2) derivatives rather than zwitterions in the gas phase and this connectivity is predicted for CysH and CysSH also in the polarizable continuum. A model molecule of composition C(4)H(7)N(2)O(2)SH (abbreviated as RSH) simulating the structural environment of a cysteine residue within the peptide chain near the corresponding reaction center of the thiosulfate oxidizing enzyme complex "Sox" was used to elucidate the geometry of the proposed reaction intermediates as well as their thermodynamic properties. In the polarizable phase, the S-sulfonate ions [CysSO(3)](-) and [RSSO(3)](-) are predicted to react exothermically with water to the corresponding thiol and hydrogensulfate ions. These results support the proposed mechanism for enzymatic thiosulfate metabolism. Sulfur dioxide and hydrogensulfite anions are predicted to react exothermically and exergonically with thiolate and persulfide anions to give the corresponding S-sulfinate species [RSSO(2)](-) and [RSSSO(2)](-), respectively. The latter ions help to explain the inhibition of certain thiolate based enzymes by aqueous sulfite, disulfite and dithionite anions in sulfur oxidizing microorganisms.

Effect of temperature modulations on TEMPO-mediated regioselective oxidation of unprotected carbohydrates and nucleosides.

PubMed

Yadav, Mahipal; Liotta, Charles L; Krishnamurthy, Ramanarayanan

2018-02-02

Regioselective oxidation of unprotected and partially protected oligosaccharides is a much sought-after goal. Herein, we report a notable improvement in the efficiency of TEMPO-catalyzed oxidation by modulating the temperature of the reaction. Mono-, di-, and tri-saccharides are oxidized regioselectively in yields of 75 to 92%. The present method is simple to implement and is also applicable for selective oxidations of other mono- and poly-hydroxy compounds including unprotected and partially protected nucleosides. Copyright © 2018 Elsevier Ltd. All rights reserved.

Emission characteristics of a premix combustor fueled with a simulated partial-oxidation product gas

NASA Technical Reports Server (NTRS)

Clayton, R. M.

1979-01-01

A two-stage gas turbine combustor concept employing a very fuel-rich partial oxidation stage is being explored for broadening the combustion margin between ultralow emissions and the lean stability limit. Combustion and emission results are presented for a series of experiments where a simulated partial oxidation product gas was used in a premix combustor operated with inlet air state conditions typical of cruise power for high-performance aviation engines (12 atm and 850 F). Ultralow NOx, CO, and HC emissions and an extended lean burning limit were achieved simultaneously.

Direct synthesis of hydrophobic graphene-based nanosheets via chemical modification of exfoliated graphene oxide.

PubMed

Wang, Jigang; Wang, Yongsheng; He, Dawei; Liu, Zhiyong; Wu, Hongpeng; Wang, Haiteng; Zhao, Yu; Zhang, Hui; Yang, Bingyang; Xu, Haiteng; Fu, Ming

2012-08-01

Hydrophobic graphene-based material at the nanoscale was prepared by treatment of exfoliated graphene oxide with organic isocyanates. The lipophilic modified graphene oxide (LMGO) can then be exfoliated into the functionalized graphene nanoplatelets that can form a stable dispersion in polar aprotic solvents. AFM image shows the thickness of LMGO is approximately 1 nm. Characterization of LMGO by elemental analysis suggested that the chemical treatment results in the functionalization of the carboxyl and hydroxyl groups in GO via formation of amides and carbamate esters, respectively. The degree of GO functionalization can be controlled via either the reactivity of the isocyanate or the reaction time. Then we investigated the thermal properties of the SPFGraphene by using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), the TGA curve shows a greater weight loss of approximately 20% occurred indicating removal of functional groups from the LMGO sheets and an obvious exothermic peak at 176 degrees can be observed from 150 to 250 degrees. We also compared the structure of graphene oxide with the structure of chemical treated graphene oxide by FT-IR spectroscopy. The morphology and microstructure of the LMGO nanosheets were also characterized by SEM and XRD. Graphene can be used to fabricate a wide range of simple electronic devices such as field-effect transistors, resonators, quantum dots and some other extensive industrial manufacture such as super capacitor, li ion battery, solar cells and even transparent electrodes in device applications.

Self-Assembled Nano-energetic Gas Generators based on Bi2O3

NASA Astrophysics Data System (ADS)

Hobosyan, Mkhitar; Trevino, Tyler; Martirosyan, Karen

2012-10-01

Nanoenergetic Gas-Generators are formulations that rapidly release a large amount of gaseous products and generate a fast moving thermal wave. They are mainly based on thermite systems, which are pyrotechnic mixtures of metal powders (fuel- Al, Mg, etc.) and metal oxides (oxidizer, Bi2O3, Fe2O3, WO3, MoO3 etc.) that can generate an exothermic oxidation-reduction reaction referred to as a thermite reaction. A thermite reaction releases a large amount of energy and can generate rapidly extremely high temperatures. The intimate contact between the fuel and oxidizer can be enhanced by use of nano instead of micro particles. The contact area between oxidizer and metal particles depends from method of mixture preparation. In this work we utilize the self-assembly processes, which use the electrostatic forces to produce ordered and self-organized binary systems. In this process the intimate contact significantly enhances and gives the ability to build an energetic material in molecular level, which is crucial for thepressure discharge efficiency of nano-thermites. The DTA-TGA, Zeta-size analysis and FTIR technique were performed to characterize the Bi2O3 particles. The self-assembly of Aluminum and Bi2O3 was conducted in sonic bath with appropriate solvents and linkers. The resultant thermite pressure discharge values were tested in modified Parr reactor. In general, the self-assembled thermites give much higher-pressure discharge values than the thermites prepared with conventional roll-mixing technique.

Reactions of Free Radicals with Nitro-Compounds and Nitrates

DTIC Science & Technology

1981-03-31

PAGE(I/hmm a•Ia ntatemd the fragment derived from the nitrates but not from the nitro-compounds could undergo exothermic rearrangement. Product analyses...compounds could undergo exothermic rearrangement. Product analyses and computer modelling were undertaken, these provided a clear explanation of why the...Nitrate 14 Reaction of Oxygen Atoms with Nitromethane 16 Reaction of Oxygen Atoms with Nitroethane 17 Products from Nitrocompounds 18 Effect of Carbon

Synthetic process for preparation of high surface area electroactive compounds for battery applications

DOEpatents

Evenson, Carl; Mackay, Richard

2013-07-23

A process is disclosed for the preparation of electroactive cathode compounds useful in lithium-ion batteries, comprising exothermic mixing of low-cost precursors and calcination under appropriate conditions. The exothermic step may be a spontaneous flameless combustion reaction. The disclosed process can be used to prepare any lithium metal phosphate or lithium mixed metal phosphate as a high surface area single phase compound.

Reforming of fuel inside fuel cell generator

DOEpatents

Grimble, Ralph E.

1988-01-01

Disclosed is an improved method of reforming a gaseous reformable fuel within a solid oxide fuel cell generator, wherein the solid oxide fuel cell generator has a plurality of individual fuel cells in a refractory container, the fuel cells generating a partially spent fuel stream and a partially spent oxidant stream. The partially spent fuel stream is divided into two streams, spent fuel stream I and spent fuel stream II. Spent fuel stream I is burned with the partially spent oxidant stream inside the refractory container to produce an exhaust stream. The exhaust stream is divided into two streams, exhaust stream I and exhaust stream II, and exhaust stream I is vented. Exhaust stream II is mixed with spent fuel stream II to form a recycle stream. The recycle stream is mixed with the gaseous reformable fuel within the refractory container to form a fuel stream which is supplied to the fuel cells. Also disclosed is an improved apparatus which permits the reforming of a reformable gaseous fuel within such a solid oxide fuel cell generator. The apparatus comprises a mixing chamber within the refractory container, means for diverting a portion of the partially spent fuel stream to the mixing chamber, means for diverting a portion of exhaust gas to the mixing chamber where it is mixed with the portion of the partially spent fuel stream to form a recycle stream, means for injecting the reformable gaseous fuel into the recycle stream, and means for circulating the recycle stream back to the fuel cells.

Reforming of fuel inside fuel cell generator

DOEpatents

Grimble, R.E.

1988-03-08

Disclosed is an improved method of reforming a gaseous reformable fuel within a solid oxide fuel cell generator, wherein the solid oxide fuel cell generator has a plurality of individual fuel cells in a refractory container, the fuel cells generating a partially spent fuel stream and a partially spent oxidant stream. The partially spent fuel stream is divided into two streams, spent fuel stream 1 and spent fuel stream 2. Spent fuel stream 1 is burned with the partially spent oxidant stream inside the refractory container to produce an exhaust stream. The exhaust stream is divided into two streams, exhaust stream 1 and exhaust stream 2, and exhaust stream 1 is vented. Exhaust stream 2 is mixed with spent fuel stream 2 to form a recycle stream. The recycle stream is mixed with the gaseous reformable fuel within the refractory container to form a fuel stream which is supplied to the fuel cells. Also disclosed is an improved apparatus which permits the reforming of a reformable gaseous fuel within such a solid oxide fuel cell generator. The apparatus comprises a mixing chamber within the refractory container, means for diverting a portion of the partially spent fuel stream to the mixing chamber, means for diverting a portion of exhaust gas to the mixing chamber where it is mixed with the portion of the partially spent fuel stream to form a recycle stream, means for injecting the reformable gaseous fuel into the recycle stream, and means for circulating the recycle stream back to the fuel cells. 1 fig.

Electrochemical treatment of evaporated residue of soak liquor generated from leather industry.

PubMed

Boopathy, R; Sekaran, G

2013-09-15

The organic and suspended solids present in soak liquor, generated from leather industry, demands treatment. The soak liquor is being segregated and evaporated in solar evaporation pans/multiple effect evaporator due to non availability of viable technology for its treatment. The residue left behind in the pans/evaporator does not carry any reuse value and also faces disposal threat due to the presence of high concentration of sodium chloride, organic and bacterial impurities. In the present investigation, the aqueous evaporated residue of soak liquor (ERSL) was treated by electrochemical oxidation. Graphite/graphite and SS304/graphite systems were used in electrochemical oxidation of organics in ERSL. Among these, graphite/graphite system was found to be effective over SS304/graphite system. Hence, the optimised conditions for the electrochemical oxidation of organics in ERSL using graphite/graphite system was evaluated by response surface methodology (RSM). The mass transport coefficient (km) was calculated based on pseudo-first order rate kinetics for both the electrode systems (graphite/graphite and SS304/graphite). The thermodynamic properties illustrated the electrochemical oxidation was exothermic and non-spontaneous in nature. The calculated specific energy consumption at the optimum current density of 50 mA cm(-2) was 0.41 kWh m(-3) for the removal of COD and 2.57 kWh m(-3) for the removal of TKN. Copyright © 2013 Elsevier B.V. All rights reserved.

Multiple sample characterization of coals and other substances by controlled-atmosphere programmed temperature oxidation

DOEpatents

LaCount, Robert B.

1993-01-01

A furnace with two hot zones holds multiple analysis tubes. Each tube has a separable sample-packing section positioned in the first hot zone and a catalyst-packing section positioned in the second hot zone. A mass flow controller is connected to an inlet of each sample tube, and gas is supplied to the mass flow controller. Oxygen is supplied through a mass flow controller to each tube to either or both of an inlet of the first tube and an intermediate portion between the tube sections to intermingle with and oxidize the entrained gases evolved from the sample. Oxidation of those gases is completed in the catalyst in each second tube section. A thermocouple within a sample reduces furnace temperature when an exothermic condition is sensed within the sample. Oxidized gases flow from outlets of the tubes to individual gas cells. The cells are sequentially aligned with an infrared detector, which senses the composition and quantities of the gas components. Each elongated cell is tapered inward toward the center from cell windows at the ends. Volume is reduced from a conventional cell, while permitting maximum interaction of gas with the light beam. Reduced volume and angulation of the cell inlets provide rapid purgings of the cell, providing shorter cycles between detections. For coal and other high molecular weight samples, from 50% to 100% oxygen is introduced to the tubes.

Integrated Modeling and Experimental Studies at the Meso Scale for Advanced Reactive Materials

DTIC Science & Technology

2016-07-01

T E C H N IC A L R E P O R T DTRA-TR-16-76 Integrated Modeling and Experimental Studies at the Meso- Scale for Advanced Reactive Materials ...study the energy release processes that thermitic and/or exothermic intermetallic reactive materials experience when they are subjected to...thermitic and/or exothermic intermetallic materials experience when they are subjected to sustained shock loading. Data from highly spatially and

NaF-assisted combustion synthesis of MoSi2 nanoparticles and their densification behavior

NASA Astrophysics Data System (ADS)

Nersisyan, Hayk H.; Lee, Tae Hyuk; Ri, Vladislav; Lee, Jong Hyeon; Suh, Hoyoung; Kim, Jin-Gyu; Son, Hyeon Taek; Kim, Yong-Ho

2017-03-01

The exothermic reduction of oxides mixture (MoO3+2SiO2) by magnesium in NaF melt enables the synthesis of nanocrystalline MoSi2 powders in near-quantitative yields. The combustion wave with temperature of about 1000-1200 °C was recorded in highly diluted by NaF starting mixtures. The by-products of combustion reaction (NaF and MgO) were subsequently removed by leaching with acid and washing with water. The as-prepared MoSi2 nanopowder composed of spherical and dendritic shape particles was consolidated using the spark plasma sintering method at 1200-1500 °C and 50 MPa for 10 min. The result was dense compacts (98.6% theoretical density) possessing submicron grains and exhibiting hardness of 8.74-12.92 GPa.

Thermal analysis of the exothermic reaction between galvanic porous silicon and sodium perchlorate.

PubMed

Becker, Collin R; Currano, Luke J; Churaman, Wayne A; Stoldt, Conrad R

2010-11-01

Porous silicon (PS) films up to ∼150 μm thick with specific surface area similar to 700 m(2)/g and pore diameters similar to 3 nm are fabricated using a galvanic corrosion etching mechanism that does not require a power supply. After fabrication, the pores are impregnated with the strong oxidizer sodium perchlorate (NaClO(4)) to create a composite that constitutes a highly energetic system capable of explosion. Using bomb calorimetry, the heat of reaction is determined to be 9.9 ± 1.8 and 27.3 ± 3.2 kJ/g of PS when ignited under N(2) and O(2), respectively. Differential scanning calorimetry (DSC) reveals that the energy output is dependent on the hydrogen termination of the PS.

Study of recrystallization and devitrification of lunar glass

NASA Technical Reports Server (NTRS)

Ulrich, D. R.

1974-01-01

The technique of differential thermal analysis (DTA) was applied to the study of the Apollo 17 orange soil (74220,63) and the Apollo 16 glass coated anorthite (64455,21). These glasses show accentuated exotherms of strain relief in the annealing range which is indicative of rapid cooling. These are amenable to interpretation by comparison to the known history of synthetic glasses. Synthetic glasses were prepared whose similarity in behavior between the lunar glasses and their synthetic analogs is striking. Approximate rates of cooling of the lunar glasses were determined from comparative DTA of lunar and synthetic glasses and from the determination of the relation of strain relief in the annealing range to quench rate. At higher temperatures the glasses show exotherms of crystallization. The crystallization products associated with the exothermic reactions have been identified by X-ray diffraction and the surface morphologies developed by strain relief and crystallization have been characterized with scanning electron microscopy.

Chlorination of zirconium (0001) surface: A first-principles study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, E.; Weck, Philippe F; Poineau, F.

The mechanisms and energetics of Zr(0001) surface chlorination by dissociative adsorption of gaseous Cl 2, and associated speciation and surface degradation processes, have been investigated within the framework of density functional theory. Chlorination of Zr(0001) is predicted to be exothermic by 3 eV/Cl for dissociative adsorption of a single Cl 2 molecule, followed by exothermic chlorination to 1ML and 2 ML under Cl-rich conditions, with respective energy gains of 1.93 and 2.79 eV/Cl. Calculations also show that exfoliation of the top Cl-Zr-Cl sandwich layers is exothermic and most energetically favorable, and can thus be considered as a leading mechanism formore » Zr(0001) surface dissolution. Finally, consistent with experimental findings, formation of ZrCl 4 molecular products is also found to be dominant during Zr(0001) chlorination.« less

Chlorination of zirconium (0001) surface: A first-principles study.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Eunja; Weck, Philippe F; Borjas, Rosendo

Here, the mechanisms and energetics of Zr(0001) surface chlorination by dissociative adsorption of gaseous Cl 2, and associated speciation and surface degradation processes, have been investigated within the framework of density functional theory. Chlorination of Zr(0001) is predicted to be exothermic by ~3 eV/Cl for dissociative adsorption of a single Cl 2 molecule, followed by exothermic chlorination to 1ML and 2 ML under Cl-rich conditions, with respective energy gains of 1.93 and 2.79 eV/Cl. Calculations also show that exfoliation of the top Cl-Zr-Cl sandwich layers is exothermic and most energetically favorable, and can thus be considered as a leading mechanismmore » for Zr(0001) surface dissolution. Consistent with experimental findings, formation of ZrCl 4 molecular products is also found to be dominant during Zr(0001) chlorination.« less

Development of exothermically cast single-crystal Mar-M 247 and derivative alloys

NASA Technical Reports Server (NTRS)

Strangman, T. E.; Hoppin, G. S., III; Phipps, C. M.; Harris, K.; Schwer, R. E.

1980-01-01

A low-cost, exothermic directional-solidification (DS) process was developed to produce single-crystal (SC) Mar-M 247 high-pressure turbine blades. Stress-rupture data indicated that SC Mar-M 247 provides only marginal improvements in longitudinal strength relative to the columnar grained DS material. Removal of grain boundary strengthening elements (B, C, Zr, Hf) from the Mar-M 247 composition (which are also melting point depressants) permitted the alloy to be solutioned at significantly higher temperatures. An order of magnitude improvement in rupture life relative to SC Mar-M 247 was observed for several derivative alloys at 103.5 MPa (15 KSI) and 1093 C. Rupture lives of the modified SC alloys were significantly affected by both alloy purity and heat treatment. Critical aspects of vacuum induction refining, exothermic casting technology, alloy development and heat treatment, which contributed to this new class of turbine blades, are reviewed

Direct detection of light ''Ge-phobic'' exothermic dark matter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gelmini, Graciela B.; Georgescu, Andreea; Huh, Ji-Haeng, E-mail: gelmini@physics.ucla.edu, E-mail: a.georgescu@physics.ucla.edu, E-mail: jhhuh@physics.ucla.edu

2014-07-01

We present comparisons of direct dark matter (DM) detection data for light WIMPs with exothermic scattering with nuclei (exoDM), both assuming the Standard Halo Model (SHM) and in a halo model–independent manner. Exothermic interactions favor light targets, thus reducing the importance of upper limits derived from xenon targets, the most restrictive of which is at present the LUX limit. In our SHM analysis the CDMS-II-Si and CoGeNT regions become allowed by these bounds, however the recent SuperCDMS limit rejects both regions for exoDM with isospin-conserving couplings. An isospin-violating coupling of the exoDM, in particular one with a neutron to protonmore » coupling ratio of -0.8 (which we call ''Ge-phobic''), maximally reduces the DM coupling to germanium and allows the CDMS-II-Si region to become compatible with all bounds. This is also clearly shown in our halo-independent analysis.« less

Model free simulations of a high speed reacting mixing layer

NASA Technical Reports Server (NTRS)

Steinberger, Craig J.

1992-01-01

The effects of compressibility, chemical reaction exothermicity and non-equilibrium chemical modeling in a combusting plane mixing layer were investigated by means of two-dimensional model free numerical simulations. It was shown that increased compressibility generally had a stabilizing effect, resulting in reduced mixing and chemical reaction conversion rate. The appearance of 'eddy shocklets' in the flow was observed at high convective Mach numbers. Reaction exothermicity was found to enhance mixing at the initial stages of the layer's growth, but had a stabilizing effect at later times. Calculations were performed for a constant rate chemical rate kinetics model and an Arrhenius type kinetics prototype. The Arrhenius model was found to cause a greater temperature increase due to reaction than the constant kinetics model. This had the same stabilizing effect as increasing the exothermicity of the reaction. Localized flame quenching was also observed when the Zeldovich number was relatively large.

Effect of oxygen partial pressure on oxidation of Mo-metal

NASA Astrophysics Data System (ADS)

Sharma, Rabindar Kumar; Kumar, Prabhat; Singh, Megha; Gopal, Pawar; Reddy, G. B.

2018-05-01

This report explains the effect of oxygen partial pressure (PO2 ) on oxidation of Mo-metal in oxygen plasma. XRD results indulge that oxide layers formed on Mo-surfaces at different oxygen partial pressures have two different oxide phases (i.e. orthorhombic MoO3 and monoclinic Mo8O23). Intense XRD peaks at high pressure (i.e. 2.0×10-1 Torr) points out the formation of thick oxide layer on Mo-surface due to presence of large oxygen species in chamber and less oxide volatilization. Whereas, at low PO2 (6.5×10-2 and 7.5×10-2 Torr.) the reduced peak strength is owing to high oxide volatilization rate. SEM micrographs and thickness measurements also support XRD results and confirm that the optimum -2value of PO2 to deposited thicker and uniform oxide film on glass substrate is 7.5×10-2 Torr through plasma assistedoxidation process. Further to study the compositional properties, EDX of the sample M2 (the best sample) is carried out, which confirms that the stoichiometric ratio is less than 3 (i.e. 2.88). Less stoichiometric ratio again confirms the presence of sub oxides in oxide layers on Mo metal as evidenced by XRD results. All the observed results are well in consonance with each other.

Twice as smart behavior of tert-butylthiacalix[4]arene derivative in glassy and crystalline form.

PubMed

Gataullina, K V; Ziganshin, M A; Stoikov, I I; Gubaidullin, A T; Gorbatchuk, V V

2015-06-28

A studied tert-butylthiacalix[4]arene derivative with four N-(2-acetoxyethyl)carbamoylmethoxy substituents on its lower rim in partial-cone configuration (calixarene 1) can remember its previous treatment in three essentially different ways by the formation either of a molecular glass or two metastable polymorphs after heating or the removal of an included guest molecule. Guest-induced memory is very selective with a polymorph created only after the release of a few included guests among a large series of those studied and is detected via an exothermic transition. Along with ordinary properties, like glass transition, curing and cold crystallization, the molecular glass from 1 is selective due to its ability to crystallize in solvent vapors and vapor mixtures over a well-defined concentration range. Being cooperative, this property may be used for the visual detection of ethanol content in water solution when it reaches a threshold value.

Stable, Ultra-Low Residence Time Partial Oxidation

DOEpatents

Schmidt, Lanny D.; Hickman, Daniel A.

1997-07-15

A process for the catalytic partial oxidation of methane in gas phase at very short residence time (800,000 to 12,000,000 hr.sup.-1) by contacting a gas stream containing methane and oxygen with a metal supported catalyst, such as platinum deposited on a ceramic monolith.

Adsorption mechanism of magnetically separable Fe3O4/graphene oxide hybrids

NASA Astrophysics Data System (ADS)

Ouyang, Ke; Zhu, Chuanhe; Zhao, Ya; Wang, Leichao; Xie, Shan; Wang, Qun

2015-11-01

A reclaimable Fe3O4/graphene oxide (GO) magnetic hybrid was successfully synthesized via a facile one-pot polyol approach and employed as a recyclable adsorbent for Bisphenol A (BPA) in aqueous solutions. The maximum adsorption capacity (qm) of the Fe3O4/GO hybrid for BPA was 72.80 mg/g at 273 K. The kinetics of the adsorption process and the adsorption isotherm data were fitted using the Freundlich equation and a pseudo-second-order kinetic model. The results of the thermodynamic parameters ΔH°, ΔS° and ΔG° showed that the adsorption process was exothermic and spontaneous. Furthermore, the reusability of the samples was investigated, and the results indicated that the samples exhibited high stability. The magnetic characterization demonstrated that hybrids were superparamagnetic and could be recovered conveniently by magnetic separation. The strong π-π interaction was determined to be the predominant driving force behind the adsorption of BPA onto the Fe3O4/GO hybrid. Therefore, the Fe3O4/GO hybrid could be regarded as a potential adsorbent for wastewater treatment and purification processes.

Energetics of magnesium, strontium, and barium doped lanthanum gallate perovskites

NASA Astrophysics Data System (ADS)

Cheng, Jihong; Navrotsky, Alexandra

2004-01-01

LaGaO 3 perovskites doped with Sr or Ba at the La site and Mg at the Ga site were prepared by solid-state reaction or sol-gel method and characterized. Enthalpies of formation from constituent oxides at 298 K were determined by high-temperature oxide melt solution calorimetry. Energetic trends are discussed in terms of defect chemistry. As oxygen deficiency increases, formation enthalpies define three trends, LaGa 1- yMg yO 3- δ (LGM), La 1- xSr xGa 1- yMg yO 3- δ (LSGM), and La 1- xBa xGa 1- yMg yO 3- δ (LBGM). They become less exothermic with increasing doping, suggesting a dominant destabilization effect from oxygen vacancies. The endothermic enthalpy of vacancy formation is 275±37, 166±18 and 138±12 kJ/mol of VO·· for LGM, LBGM and LSGM, respectively. Tolerance factor and ion size mismatch also affect enthalpies. In terms of energetics, Sr is the best dopant for the La site and Mg for the Ga site, supporting earlier studies, including oxygen ion conductivity and computer modeling.

Partial oxidation of alkanes by dioxiranes formed in situ at low temperature.

PubMed

Yacob, Sara; Caulfield, Michael J; Barckholtz, Timothy A

2018-01-13

Partial oxidation catalysts capable of efficiently operating at low temperatures may limit the over-oxidation of alkane substrates and thereby improve selectivity. This work focuses on examining alkane oxidation using completely metal-free organocatalysts, dioxiranes. The dioxiranes employed here are synthesized by oxidation of a ketone using a terminal oxidant, such as hydrogen peroxide. Our work generates the dioxirane in situ , so that the process can be catalytic with respect to the ketone. To date, we have demonstrated selective partial oxidation of adamantane using ketone catalysts resulting in yields upwards of 60% towards 1-adamantanol with greater than 99% selectivity. Furthermore, we have demonstrated that changing the electrophilic character of the ketone R groups to contain more electron-donating ligands facilitates the dioxirane ring formation and improves overall oxidation yields. Isotopic labelling studies using H 2 18 O 2 show the preferential incorporation of an 18 O label into the parent ketone, providing evidence for a dioxirane intermediate formed in situ The isotopic labelling studies, along with solvent effect studies, suggest the formation of peracetic acid as a reactive intermediate.This article is part of a discussion meeting issue 'Providing sustainable catalytic solutions for a rapidly changing world'. © 2017 The Author(s).

Combined fuel and air staged power generation system

DOEpatents

Rabovitser, Iosif K; Pratapas, John M; Boulanov, Dmitri

2014-05-27

A method and apparatus for generation of electric power employing fuel and air staging in which a first stage gas turbine and a second stage partial oxidation gas turbine power operated in parallel. A first portion of fuel and oxidant are provided to the first stage gas turbine which generates a first portion of electric power and a hot oxidant. A second portion of fuel and oxidant are provided to the second stage partial oxidation gas turbine which generates a second portion of electric power and a hot syngas. The hot oxidant and the hot syngas are provided to a bottoming cycle employing a fuel-fired boiler by which a third portion of electric power is generated.

Proceedings of the International Pyrotechnics Seminar (6th) Held at Estes Park, Colorado, 17-21 July 1978

DTIC Science & Technology

1978-06-01

in metal form, and not as an oxide , as with conventional HC compositions. "That verified the fact that the aluminum did not take part in the chemical...the melting of the protective oxide layer on the aluminum particle with an attendant increase in surface reaction rate leading to ignition. Oxide ...detonation 5 aluminum BrF5 partial detonation 6 propylene oxide ClF3 partial detonation 621 041 IR! Each teat used about 5 kg of fuel, about 400 g

Ferromagnetic phase in partially oxidized FeMn films

NASA Astrophysics Data System (ADS)

Svalov, A. V.; Savin, P. A.; Lepalovskij, V. N.; Vas'kovskiy, V. O.; Larrañaga, A.; Kurlyandskaya, G. V.

2018-04-01

The structure, magnetic and magnetoresistive properties of ferromagnetic phase in partially oxidized FeMn films was studied. The oxidation was performed by annealing of the samples under atmospheric pressure in a gas mixture (nitrogen with 0.5% oxygen) at the temperature of 300 °C. The resulting ferromagnetic phase was isotropic in the film plane. The value of the anisotropic magnetoresistance was similar to the value of the anisotropic magnetoresistance usually observed in films of pure iron. The oxidation of antiferromagnetic FeMn films resulted in the appearance of an exchange bias.

Facile Preparation of Magnetic Graphene Oxide and Attapulgite Composite Adsorbent for the Adsorption of Ni (II)

NASA Astrophysics Data System (ADS)

Bigui, Wei; Xiaofei, Zhu; Xiabing, Cheng

2017-12-01

Graphene oxide (GO) is an excellent absorbent for heavy ion from wastewater, but it is hard to separate from water. To improve the adsorption capacity and separation performance of GO to nickel-containing wastewater, a composite magnetic GO-ATP adsorbent (MGA) was prepared by magnetizing GO and attapulgite (ATP) using ferroferric oxide and then carrying out hydrothermal reaction. The adsorption capacity and mechanism of MGA were investigated based on Ni2+ as targeted pollutant. Experimental results showed that the pH value significantly affects the removal rate of Ni2+, which is mainly due to that OH- in wastewater reacts with Ni2+, resulting in sediment that leads to the increase of removal rate. MGA can achieve max adsorption capacity of Ni2+ to 190.8 mg/g at pH = 5, and the adsorption process was mainly determined by chemical adsorption, which was in line with pseudo-secondary dynamics model. The adsorption was basically homogeneous monolayer adsorption with heat release, which was more agree with Langmuir adsorption isotherm equation. the adsorption process of Ni2+ by MGA. The adsorption process was a spontaneous process and an exothermic reaction. It can be confirmed that the prepared MGA adsorbent can realize slurry separation using magnetic separation principle and has high adsorption capacity to Ni2+.

Energetics of sodium-calcium exchanged zeolite A.

PubMed

Sun, H; Wu, D; Guo, X; Shen, B; Navrotsky, A

2015-05-07

A series of calcium-exchanged zeolite A samples with different degrees of exchange were prepared. They were characterized by powder X-ray diffraction (XRD) and differential scanning calorimetry (DSC). High temperature oxide melt drop solution calorimetry measured the formation enthalpies of hydrated zeolites CaNa-A from constituent oxides. The water content is a linear function of the degree of exchange, ranging from 20.54% for Na-A to 23.77% for 97.9% CaNa-A. The enthalpies of formation (from oxides) at 25 °C are -74.50 ± 1.21 kJ mol(-1) TO2 for hydrated zeolite Na-A and -30.79 ± 1.64 kJ mol(-1) TO2 for hydrated zeolite 97.9% CaNa-A. Dehydration enthalpies obtained from differential scanning calorimetry are 32.0 kJ mol(-1) H2O for hydrated zeolite Na-A and 20.5 kJ mol(-1) H2O for hydrated zeolite 97.9% CaNa-A. Enthalpies of formation of Ca-exchanged zeolites A are less exothermic than for zeolite Na-A. A linear relationship between the formation enthalpy and the extent of calcium substitution was observed. The energetic effect of Ca-exchange on zeolite A is discussed with an emphasis on the complex interactions between the zeolite framework, cations, and water.

SYNTHESIZING ALCOHOLS AND KETONES BY PHOTOINDUCED CATALYTIC PARTIAL-OXIDATION OF HYDROCARBONS IN TI02 FILM REACTORS PREPARED BY THREE DIFFERENT METHODS

EPA Science Inventory

The partial oxidation of cyclohexane to cyclohexanol and cyclohexanone on UV irradiated titanium dioxide films in the presence of molecular oxygen at ambient temperatures and pressures was studied. Three different coating methodologies (dip coating using titanium isopropoxide an...

Method of fabricating a monolithic solid oxide fuel cell

DOEpatents

Minh, N.Q.; Horne, C.R.

1994-03-01

In a two-step densifying process of making a monolithic solid oxide fuel cell, a limited number of anode-electrolyte-cathode cells separated by an interconnect layer are formed and partially densified. Subsequently, the partially densified cells are stacked and further densified to form a monolithic array. 10 figures.

Method of fabricating a monolithic solid oxide fuel cell

DOEpatents

Minh, Nguyen Q.; Horne, Craig R.

1994-01-01

In a two-step densifying process of making a monolithic solid oxide fuel cell, a limited number of anode-electrolyte-cathode cells separated by an interconnect layer are formed and partially densified. Subsequently, the partially densified cells are stacked and further densified to form a monolithic array.

Scientific Transactions No. 11 of the Institute of Mechanics, Moscow State University. [supersonic and hypersonic gas flow and the movement of gas with exothermic reactions

NASA Technical Reports Server (NTRS)

Gonor, A. L. (Editor)

1982-01-01

The results of flow around wings, the determination of the optimal form, and the interaction of the wake with the accompanying flow at supersonic and hypersonic speeds of the free-stream flow are given. Methods of numerical and analytical calculation of one dimensional unsteady and two dimensional steady motions of fuel-gas mixtures with exothermic reactions are also considered.

System Acquires Data On Reactivities Of Foams

NASA Technical Reports Server (NTRS)

Walls, Joe T.

1994-01-01

Data-acquisition and -plotting system, called DAPS(TM), developed enabling accurate and objective determination of physical properties related to reactivities of polyurethane and polyisocyanurate foams. Automated, computer-controlled test apparatus that acquires data on rates of rise, rise profiles, exothermic temperatures, and internal pressures of foams prepared from both manual and machine-mixed batches. Data used to determine minute differences between reaction kinetics and exothermic profiles of foam formulations, properties of end products which are statistically undifferentiated.

Nanocrystalline films for gas-reactive applications

DOEpatents

Eastman, Jeffrey A.; Thompson, Loren J.

2004-02-17

A gas sensor for detection of oxidizing and reducing gases, including O.sub.2, CO.sub.2, CO, and H.sub.2, monitors the partial pressure of a gas to be detected by measuring the temperature rise of an oxide-thin-film-coated metallic line in response to an applied electrical current. For a fixed input power, the temperature rise of the metallic line is inversely proportional to the thermal conductivity of the oxide coating. The oxide coating contains multi-valent cation species that change their valence, and hence the oxygen stoichiometry of the coating, in response to changes in the partial pressure of the detected gas. Since the thermal conductivity of the coating is dependent on its oxygen stoichiometry, the temperature rise of the metallic line depends on the partial pressure of the detected gas. Nanocrystalline (<100 nm grain size) oxide coatings yield faster sensor response times than conventional larger-grained coatings due to faster oxygen diffusion along grain boundaries rather than through grain interiors.

Method and apparatus for converting hydrocarbon fuel into hydrogen gas and carbon dioxide

DOEpatents

Clawson, Lawrence G.; Mitchell, William L.; Bentley, Jeffrey M.; Thijssen, Johannes H.J.

2000-01-01

An apparatus and a method are disclosed for converting hydrocarbon fuel or an alcohol into hydrogen gas and carbon dioxide. The apparatus includes a first vessel having a partial oxidation reaction zone and a separate steam reforming reaction zone that is distinct from the partial oxidation reaction zone. The first vessel has a first vessel inlet at the partial oxidation reaction zone and a first vessel outlet at the steam reforming zone. The reformer also includes a helical tube extending about the first vessel. The helical tube has a first end connected to an oxygen-containing source and a second end connected to the first vessel at the partial oxidation reaction zone. Oxygen gas from an oxygen-containing source can be directed through the helical tube to the first vessel. A second vessel having a second vessel inlet and second vessel outlet is annularly disposed about the first vessel. The helical tube is disposed between the first vessel and the second vessel and gases from the first vessel can be directed through second vessel.

Method for generating hydrogen for fuel cells

DOEpatents

Ahmed, Shabbir; Lee, Sheldon H. D.; Carter, John David; Krumpelt, Michael

2004-03-30

A method of producing a H.sub.2 rich gas stream includes supplying an O.sub.2 rich gas, steam, and fuel to an inner reforming zone of a fuel processor that includes a partial oxidation catalyst and a steam reforming catalyst or a combined partial oxidation and stream reforming catalyst. The method also includes contacting the O.sub.2 rich gas, steam, and fuel with the partial oxidation catalyst and the steam reforming catalyst or the combined partial oxidation and stream reforming catalyst in the inner reforming zone to generate a hot reformate stream. The method still further includes cooling the hot reformate stream in a cooling zone to produce a cooled reformate stream. Additionally, the method includes removing sulfur-containing compounds from the cooled reformate stream by contacting the cooled reformate stream with a sulfur removal agent. The method still further includes contacting the cooled reformate stream with a catalyst that converts water and carbon monoxide to carbon dioxide and H.sub.2 in a water-gas-shift zone to produce a final reformate stream in the fuel processor.

Fuel processor and method for generating hydrogen for fuel cells

DOEpatents

Ahmed, Shabbir [Naperville, IL; Lee, Sheldon H. D. [Willowbrook, IL; Carter, John David [Bolingbrook, IL; Krumpelt, Michael [Naperville, IL; Myers, Deborah J [Lisle, IL

2009-07-21

A method of producing a H.sub.2 rich gas stream includes supplying an O.sub.2 rich gas, steam, and fuel to an inner reforming zone of a fuel processor that includes a partial oxidation catalyst and a steam reforming catalyst or a combined partial oxidation and stream reforming catalyst. The method also includes contacting the O.sub.2 rich gas, steam, and fuel with the partial oxidation catalyst and the steam reforming catalyst or the combined partial oxidation and stream reforming catalyst in the inner reforming zone to generate a hot reformate stream. The method still further includes cooling the hot reformate stream in a cooling zone to produce a cooled reformate stream. Additionally, the method includes removing sulfur-containing compounds from the cooled reformate stream by contacting the cooled reformate stream with a sulfur removal agent. The method still further includes contacting the cooled reformate stream with a catalyst that converts water and carbon monoxide to carbon dioxide and H.sub.2 in a water-gas-shift zone to produce a final reformate stream in the fuel processor.

Alcohol-free alkoxide process for containing nuclear waste

DOEpatents

Pope, James M.; Lahoda, Edward J.

1984-01-01

Disclosed is a method of containing nuclear waste. A composition is first prepared of about 25 to about 80%, calculated as SiO.sub.2, of a partially hydrolyzed silicon compound, up to about 30%, calculated as metal oxide, of a partially hydrolyzed aluminum or calcium compound, about 5 to about 20%, calculated as metal oxide, of a partially hydrolyzed boron or calcium compound, about 3 to about 25%, calculated as metal oxide, of a partially hydrolyzed sodium, potassium or lithium compound, an alcohol in a weight ratio to hydrolyzed alkoxide of about 1.5 to about 3% and sufficient water to remove at least 99% of the alcohol as an azeotrope. The azeotrope is boiled off and up to about 40%, based on solids in the product, of the nuclear waste, is mixed into the composition. The mixture is evaporated to about 25 to about 45% solids and is melted and cooled.

Thin film oxygen partial pressure sensor

NASA Technical Reports Server (NTRS)

Wortman, J. J.; Harrison, J. W.; Honbarrier, H. L.; Yen, J.

1972-01-01

The development is described of a laboratory model oxygen partial pressure sensor using a sputtered zinc oxide thin film. The film is operated at about 400 C through the use of a miniature silicon bar. Because of the unique resistance versus temperature relation of the silicon bar, control of the operational temperature is achieved by controlling the resistance. A circuit for accomplishing this is described. The response of sputtered zinc oxide films of various thicknesses to oxygen, nitrogen, argon, carbon dioxide, and water vapor caused a change in the film resistance. Over a large range, film conductance varied approximately as the square root of the oxygen partial pressure. The presence of water vapor in the gas stream caused a shift in the film conductance at a given oxygen partial pressure. A theoretical model is presented to explain the characteristic features of the zinc oxide response to oxygen.

Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles

NASA Technical Reports Server (NTRS)

Liechty, Derek S.; Lewis, Mark J.

2010-01-01

Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.

Energy distribution among reaction products. VI - F + H2, D2.

NASA Technical Reports Server (NTRS)

Polanyi, J. C.; Woodall, K. B.

1972-01-01

Study of the F + H2 reaction, which is of special theoretical interest since it is one of the simplest examples of an exothermic chemical reaction. The FH2 system involves only 11 electrons, and the computation of a potential-energy hypersurface to chemical accuracy may now be within the reach of ab initio calculations. The 'arrested relaxation' variant of the infrared chemiluminescence method is used to obtain the initial vibrational, rotational and translational energy distributions in the products of exothermic reactions.

A Comparison of Photocatalytic Oxidation Reactor Performance for Spacecraft Cabin Trace Contaminant Control Applications

NASA Technical Reports Server (NTRS)

Perry, Jay L.; Frederick, Kenneth R.; Scott, Joseph P.; Reinermann, Dana N.

2011-01-01

Photocatalytic oxidation (PCO) is a maturing process technology that shows potential for spacecraft life support system application. Incorporating PCO into a spacecraft cabin atmosphere revitalization system requires an understanding of basic performance, particularly with regard to partial oxidation product production. Four PCO reactor design concepts have been evaluated for their effectiveness for mineralizing key trace volatile organic com-pounds (VOC) typically observed in crewed spacecraft cabin atmospheres. Mineralization efficiency and selectivity for partial oxidation products are compared for the reactor design concepts. The role of PCO in a spacecraft s life support system architecture is discussed.

A solar receiver-storage modular cascade based on porous ceramic structures for hybrid sensible/thermochemical solar energy storage

NASA Astrophysics Data System (ADS)

Agrafiotis, Christos; de Oliveira, Lamark; Roeb, Martin; Sattler, Christian

2016-05-01

The current state-of-the-art solar heat storage concept in air-operated Solar Tower Power Plants is to store the solar energy provided during on-sun operation as sensible heat in porous solid materials that operate as recuperators during off-sun operation. The technology is operationally simple; however its storage capacity is limited to 1.5 hours. An idea for extending this capacity is to render this storage concept from "purely" sensible to "hybrid" sensible/ thermochemical one, via coating the porous heat exchange modules with oxides of multivalent metals for which their reduction/oxidation reactions are accompanied by significant heat effects, or by manufacturing them entirely of such oxides. In this way solar heat produced during on-sun operation can be used (in addition to sensibly heating the porous solid) to power the endothermic reduction of the oxide from its state with the higher metal valence to that of the lower; the thermal energy can be entirely recovered by the reverse exothermic oxidation reaction (in addition to sensible heat) during off-sun operation. Such sensible and thermochemical storage concepts were tested on a solar-irradiated receiver- heat storage module cascade for the first time. Parametric studies performed so far involved the comparison of three different SiC-based receivers with respect to their capability of supplying solar-heated air at temperatures sufficient for the reduction of the oxides, the effect of air flow rate on the temperatures achieved within the storage module, as well as the comparison of different porous storage media made of cordierite with respect to their sensible storage capacity.

Modeling of a CeO2 thermochemistry reduction process for hydrogen production by solar concentrated energy

NASA Astrophysics Data System (ADS)

Valle-Hernández, Julio; Romero-Paredes, Hernando; Arancibia-Bulnes, Camilo A.; Villafan-Vidales, Heidi I.; Espinosa-Paredes, Gilberto

2016-05-01

In this paper the simulation of the thermal reduction for hydrogen production through the decomposition of cerium oxide is presented. The thermochemical cycle for hydrogen production consists of the endothermic reduction of CeO2 at high temperature, where concentrated solar energy is used as a source of heat; and of the subsequent steam hydrolysis of the resulting cerium oxide to produce hydrogen. For the thermochemical process, a solar reactor prototype is proposed; consisting of a cubic receptacle made of graphite fiber thermally insulated. Inside the reactor a pyramidal arrangement with nine tungsten pipes is housed. The pyramidal arrangement is made respect to the focal point where the reflected energy is concentrated. The solar energy is concentrated through the solar furnace of high radiative flux. The endothermic step is the reduction of the cerium oxide to lower-valence cerium oxide, at very high temperature. The exothermic step is the hydrolysis of the cerium oxide (III) to form H2 and the corresponding initial cerium oxide made at lower temperature inside the solar reactor. For the modeling, three sections of the pipe where the reaction occurs were considered; the carrier gas inlet, the porous medium and the reaction products outlet. The mathematical model describes the fluid mechanics; mass and energy transfer occurring therein inside the tungsten pipe. Thermochemical process model was simulated in CFD. The results show a temperature distribution in the solar reaction pipe and allow obtaining the fluid dynamics and the heat transfer within the pipe. This work is part of the project "Solar Fuels and Industrial Processes" from the Mexican Center for Innovation in Solar Energy (CEMIE-Sol).

Enthalpy of mixing of liquid Co–Sn alloys

PubMed Central

Yakymovych, A.; Fürtauer, S.; Elmahfoudi, A.; Ipser, H.; Flandorfer, H.

2014-01-01

A literature overview of enthalpy of mixing data for liquid Co–Sn alloys shows large scattering but no clear temperature dependence. Therefore drop calorimetry was performed in the Co–Sn system at twelve different temperatures in 100 K steps in the temperature range (673 to 1773) K. The integral enthalpy of mixing was determined starting from 1173 K and fitted to a standard Redlich–Kister polynomial. In addition, the limiting partial molar enthalpy of Co in Sn was investigated by small additions of Co to liquid Sn at temperatures (673 to 1773) K. The integral and partial molar enthalpies of the Co–Sn system generally show an exothermic mixing behavior. Significant temperature dependence was detected for the enthalpies of mixing. The minimum integral enthalpy values vary with rising temperature from approx. −7820 J/mol at T = 1173 K to −1350 J/mol at T = 1773 K; the position of the minimum is between (59 and 61) at.% Co. The results are discussed and compared with literature data available for this system. X-ray studies and scanning electron microscopy of selected alloys obtained from the calorimetric measurements were carried out in order to check the completeness of the solution process. PMID:24994940

Fuel cell system for transportation applications

DOEpatents

Kumar, Romesh; Ahmed, Shabbir; Krumpelt, Michael; Myles, Kevin M.

1993-01-01

A propulsion system for a vehicle having pairs of front and rear wheels and a fuel tank. An electrically driven motor having an output shaft operatively connected to at least one of said pair of wheels is connected to a fuel cell having a positive electrode and a negative electrode separated by an electrolyte for producing dc power to operate the motor. A partial oxidation reformer is connected both to the fuel tank and to the fuel cell receives hydrogen-containing fuel from the fuel tank and water and air and for partially oxidizing and reforming the fuel with water and air in the presence of an oxidizing catalyst and a reforming catalyst to produce a hydrogen-containing gas. The hydrogen-containing gas is sent from the partial oxidation reformer to the fuel cell negative electrode while air is transported to the fuel cell positive electrode to produce dc power for operating the electric motor.

Fuel cell system for transportation applications

DOEpatents

Kumar, R.; Ahmed, S.; Krumpelt, M.; Myles, K.M.

1993-09-28

A propulsion system is described for a vehicle having pairs of front and rear wheels and a fuel tank. An electrically driven motor having an output shaft operatively connected to at least one of said pair of wheels is connected to a fuel cell having a positive electrode and a negative electrode separated by an electrolyte for producing dc power to operate the motor. A partial oxidation reformer is connected both to the fuel tank and to the fuel cell and receives hydrogen-containing fuel from the fuel tank and uses water and air for partially oxidizing and reforming the fuel in the presence of an oxidizing catalyst and a reforming catalyst to produce a hydrogen-containing gas. The hydrogen-containing gas is sent from the partial oxidation reformer to the fuel cell negative electrode while air is transported to the fuel cell positive electrode to produce dc power for operating the electric motor. 3 figures.

Energy characteristics of the CO2 laser cutting of thick steel sheets

NASA Astrophysics Data System (ADS)

Orishich, A. M.

2012-01-01

In the present paper the scaling laws for the oxygen-assisted laser cutting of low-carbon steel of 5-25 mm is studied experimentally. No dross and minimal roughness of the cut surface were chosen as criteria of quality. The paper also studies the possibility to describe the cutting process by the similarity method and as ratios between dimensionless variables. Normalized power W/ktT, normalized velocity Vcb/a (Peclet number) and kerf width have special optimum numb. Formulas were obtained to determine the optimum values of the laser power and cutting speed for the given sheet thickness. The energy balance of the oxygen-assisted laser cutting is studied experimentally at these optimum parameters. The absorbed laser energy, heat conduction losses and cut width were measured experimentally, and then the energy of exothermic reaction of oxidation was found from the balance equation. To define the integral coefficient of absorption, the laser power was measured on the cutting channel exit during the cutting. The heat conduction losses were measured by the calorimetric method. It has been established that the absorbed laser energy, oxidation energy, thermal losses and melting enthalpy related to a sheet thickness unit, do not depend on the sheet thickness at the cutting with the minimal roughness. The results enable to determine the fraction of the oxidized iron in the melt and thermal efficiency at the cutting with the minimal roughness. The share of the oxidation reaction energy is 50-60% in the total contributed energy.

Application of as-synthesised MCM-41 and MCM-41 wrapped with reduced graphene oxide/graphene oxide in the remediation of acetaminophen and aspirin from aqueous system.

PubMed

Akpotu, Samson O; Moodley, Brenda

2018-03-01

In this study, ASM41 (as-synthesised MCM-41), MCM-41, MCM-41 encapsulated with graphene oxide (MCM-41-GO) and reduced graphene oxide (MCM-41-G) were fabricated and utilized in the remediation of acetaminophen and aspirin from water. A surfactant template (cetyltrimethylammonium bromide) was added to ASM41 to make it more hydrophobic and its effects on the remediation of acetaminophen and aspirin from wastewater was studied. To further improve the adsorption capacity of the adsorbent, MCM-41 was encapsulated with GO and G which also aided in easy separation of the adsorbent from the aqueous solution. Comparative studies of the adsorption of acetaminophen and aspirin on all four adsorbents were investigated. Batch adsorption studies of acetaminophen and aspirin were carried out to determine the effects of pH, initial concentration, time and adsorbent dose. Adsorption mechanism was through EDA, π-π interactions, and hydrophobic effects. Data from sorption kinetics showed ASM41 had the highest q m value for aspirin (909.1 mg/g) and MCM-41-G had the highest q m value for acetaminophen (555.6 mg/g). The significant adsorption by ASM41 can be attributed to increased hydrophobicity due to the retention of the surfactant template. Thermodynamic studies revealed the adsorption process as spontaneous and exothermic. Desorption studies revealed that adsorbents could be regenerated and reused for adsorption. Copyright © 2017 Elsevier Ltd. All rights reserved.

Heat up and potential failure of BWR upper internals during a severe accident

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robb, Kevin R

2015-01-01

In boiling water reactors, the steam dome, steam separators, and dryers above the core are comprised of approximately 100 tons of stainless steel. During a severe accident in which the coolant boils away and exothermic oxidation of zirconium occurs, gases (steam and hydrogen) are superheated in the core region and pass through the upper internals. Historically, the upper internals have been modeled using severe accident codes with relatively simple approximations. The upper internals are typically modeled in MELCOR as two lumped volumes with simplified heat transfer characteristics, with no structural integrity considerations, and with limited ability to oxidize, melt, andmore » relocate. The potential for and the subsequent impact of the upper internals to heat up, oxidize, fail, and relocate during a severe accident was investigated. A higher fidelity representation of the shroud dome, steam separators, and steam driers was developed in MELCOR v1.8.6 by extending the core region upwards. This modeling effort entailed adding 45 additional core cells and control volumes, 98 flow paths, and numerous control functions. The model accounts for the mechanical loading and structural integrity, oxidation, melting, flow area blockage, and relocation of the various components. The results indicate that the upper internals can reach high temperatures during a severe accident; they are predicted to reach a high enough temperature such that they lose their structural integrity and relocate. The additional 100 tons of stainless steel debris influences the subsequent in-vessel and ex-vessel accident progression.« less

Pinning down inelastic dark matter in the Sun and in direct detection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blennow, Mattias; Clementz, Stefan; Herrero-Garcia, Juan, E-mail: emb@kth.se, E-mail: scl@kth.se, E-mail: juhg@kth.se

2016-04-01

We study the solar capture rate of inelastic dark matter with endothermic and/or exothermic interactions. By assuming that an inelastic dark matter signal will be observed in next generation direct detection experiments we can set a lower bound on the capture rate that is independent of the local dark matter density, the velocity distribution, the galactic escape velocity as well as the scattering cross section. In combination with upper limits from neutrino observatories we can place upper bounds on the annihilation channels leading to neutrinos. We find that, while endothermic scattering limits are weak in the isospin-conserving case, strong boundsmore » may be set for exothermic interactions, in particular in the spin-dependent case. Furthermore, we study the implications of observing two direct detection signals, in which case one can halo-independently obtain the dark matter mass and the mass splitting, and disentangle the endothermic/exothermic nature of the scattering. Finally we discuss isospin violation.« less

Direct detection of light “Ge-phobic” exothermic dark matter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gelmini, Graciela B.; Georgescu, Andreea; Huh, Ji-Haeng

2014-07-15

We present comparisons of direct dark matter (DM) detection data for light WIMPs with exothermic scattering with nuclei (exoDM), both assuming the Standard Halo Model (SHM) and in a halo model — independent manner. Exothermic interactions favor light targets, thus reducing the importance of upper limits derived from xenon targets, the most restrictive of which is at present the LUX limit. In our SHM analysis the CDMS-II-Si and CoGeNT regions become allowed by these bounds, however the recent SuperCDMS limit rejects both regions for exoDM with isospin-conserving couplings. An isospin-violating coupling of the exoDM, in particular one with a neutronmore » to proton coupling ratio of −0.8 (which we call “Ge-phobic”), maximally reduces the DM coupling to germanium and allows the CDMS-II-Si region to become compatible with all bounds. This is also clearly shown in our halo-independent analysis.« less

Encapsulated nano-heat-sinks for thermal management of heterogeneous chemical reactions.

PubMed

Zhang, Minghui; Hong, Yan; Ding, Shujiang; Hu, Jianjun; Fan, Yunxiao; Voevodin, Andrey A; Su, Ming

2010-12-01

This paper describes a new way to control temperatures of heterogeneous exothermic reactions such as heterogeneous catalytic reaction and polymerization by using encapsulated nanoparticles of phase change materials as thermally functional additives. Silica-encapsulated indium nanoparticles and silica encapsulated paraffin nanoparticles are used to absorb heat released in catalytic reaction and to mitigate gel effect of polymerization, respectively. The local hot spots that are induced by non-homogenous catalyst packing, reactant concentration fluctuation, and abrupt change of polymerization rate lead to solid to liquid phase change of nanoparticle cores so as to avoid thermal runaway by converting energies from exothermic reactions to latent heat of fusion. By quenching local hot spots at initial stage, reaction rates do not rise significantly because the thermal energy produced in reaction is isothermally removed. Nanoparticles of phase change materials will open a new dimension for thermal management of exothermic reactions to quench local hot spots, prevent thermal runaway of reaction, and change product distribution.

A Model for the Oxidation of C/SiC Composite Structures

NASA Technical Reports Server (NTRS)

Sullivan, Roy M.

2003-01-01

A mathematical theory and an accompanying numerical scheme have been developed for predicting the oxidation behavior of C/SiC composite structures. The theory is derived from the mechanics of the flow of ideal gases through a porous solid. Within the mathematical formulation, two diffusion mechanisms are possible: (1) the relative diffusion of one species with respect to the mixture, which is concentration gradient driven and (2) the diffusion associated with the average velocity of the gas mixture, which is total gas pressure gradient driven. The result of the theoretical formulation is a set of two coupled nonlinear differential equations written in terms of the oxidant and oxide partial pressures. The differential equations must be solved simultaneously to obtain the partial vapor pressures of the oxidant and oxides as a function of space and time. The local rate of carbon oxidation is determined as a function of space and time using the map of the local oxidant partial vapor pressure along with the Arrhenius rate equation. The nonlinear differential equations are cast into matrix equations by applying the Bubnov-Galerkin weighted residual method, allowing for the solution of the differential equations numerically. The end result is a numerical scheme capable of determining the variation of the local carbon oxidation rates as a function of space and time for any arbitrary C/SiC composite structures.

Float processing of high-temperature complex silicate glasses and float baths used for same

NASA Technical Reports Server (NTRS)

Cooper, Reid Franklin (Inventor); Cook, Glen Bennett (Inventor)

2000-01-01

A float glass process for production of high melting temperature glasses utilizes a binary metal alloy bath having the combined properties of a low melting point, low reactivity with oxygen, low vapor pressure, and minimal reactivity with the silicate glasses being formed. The metal alloy of the float medium is exothermic with a solvent metal that does not readily form an oxide. The vapor pressure of both components in the alloy is low enough to prevent deleterious vapor deposition, and there is minimal chemical and interdiffusive interaction of either component with silicate glasses under the float processing conditions. Alloys having the desired combination of properties include compositions in which gold, silver or copper is the solvent metal and silicon, germanium or tin is the solute, preferably in eutectic or near-eutectic compositions.

Evaluation of the SSRCT engine with a hydrazine as a fuel, phase 1

NASA Technical Reports Server (NTRS)

Minton, S. J.

1978-01-01

The performance parameters for the space shuttle reaction control thruster (SSRCT) when the fuel is changed from monomethylhydrazine to hydrazine were predicted. Potential problems are higher chamber wall temperature during steady state operation and explosive events during pulse mode operation. Solutions to the problems are suggested. To conduct the analysis, a more realistic film cooling model was devised which considers that hydrazine based fuels are reactive when used as a film coolant on the walls of the combustion chamber. Hydrazine based fuels can decompose exothermally as a monopropellant and also enter into bipropellant reactions with any excess oxidizer in the combustion chamber. It is concluded that the conversion of the thruster from MMH to hydrazine fuel is feasible but that a number of changes would be required to achieve the same safety margins as the monomethylhydrazine-fueled thruster.

Supercritical water gasification of biomass: Thermodynamic constraints.

PubMed

Castello, Daniele; Fiori, Luca

2011-08-01

In the present work, the supercritical water gasification (SCWG) of biomass is analyzed with a view to outlining the possible thermodynamic constraints that must be taken into account to develop this new process. In particular, issues concerning the formation of solid carbon and the process heat duty are discussed. The analysis is conducted by means of a two-phase non-stoichiometric thermodynamic model, based on Gibbs free energy minimization. Results show that char formation at equilibrium only occurs at high biomass concentrations, with a strong dependence on biomass composition. As regards the process heat duty, SCWG is mostly endothermic when biomass concentration is low, although a very small amount of oxidizing agent is able to make the process exothermic, with only a small loss in the heating value of the syngas produced. Copyright © 2011 Elsevier Ltd. All rights reserved.

Sol-gel synthesis and densification of aluminoborosilicate powders. Part 1: Synthesis

NASA Technical Reports Server (NTRS)

Bull, Jeffrey; Selvaduray, Guna; Leiser, Daniel

1992-01-01

Aluminoborosilicate powders high in alumina content were synthesized by the sol-gel process utilizing various methods of preparation. Properties and microstructural effects related to these syntheses were examined. After heating to 600 C for 2 h in flowing air, the powders were amorphous with the metal oxides comprising 87 percent of the weight and uncombusted organics the remainder. DTA of dried powders revealed a T(sub g) at approximately 835 C and an exotherm near 900 C due to crystallization. Powders derived from aluminum secbutoxide consisted of particles with a mean diameter 5 microns less than those from aluminum isopropoxide. Powders synthesized with aluminum isopropoxide produced agglomerates comprised of rod shaped particulates while powders made with the secbutoxide precursor produced irregular glassy shards. Compacts formed from these powders required different loadings for equivalent densities according to the method of synthesis.

Energetics of the multi-phase fluid flow in a narrow kerf in laser cutting conditions

NASA Astrophysics Data System (ADS)

Golyshev, A. A.; Orishich, A. M.; Shulyatyev, V. B.

2016-10-01

The energy balance of the multi-phase medium flow is studied experimentally under the laser cutting. Experimental data are generalized due to the condition of minimal roughness of the created surface used as a quality criterion of the melt flow, and also due to the application of dimensionless parameters: Peclet number and dimensionless absorbed laser power. For the first time ever it is found that, regardless the assistant gas (oxygen or nitrogen), laser type (the fiber one with the wavelength of 1.07 µm or CO2-laser with the wavelength of 10.6 µm), the minimal roughness is provided at a certain energy input in a melt unit, about 26 J/mm3. With oxygen, 50% of this input is provided by the radiation, the other 50% - by the exothermic reaction of iron oxidation.

Partial oxidation catalyst

DOEpatents

Krumpelt, Michael; Ahmed, Shabbir; Kumar, Romesh; Doshi, Rajiv

2000-01-01

A two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion. The dehydrogenation portion is a group VIII metal and the oxide-ion conducting portion is selected from a ceramic oxide crystallizing in the fluorite or perovskite structure. There is also disclosed a method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400.degree. C. for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also disclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide.

Influence of exothermic chemical reactions on laser-induced shock waves.

PubMed

Gottfried, Jennifer L

2014-10-21

Differences in the excitation of non-energetic and energetic residues with a 900 mJ, 6 ns laser pulse (1064 nm) have been investigated. Emission from the laser-induced plasma of energetic materials (e.g. triaminotrinitrobenzene [TATB], cyclotrimethylene trinitramine [RDX], and hexanitrohexaazaisowurtzitane [CL-20]) is significantly reduced compared to non-energetic materials (e.g. sugar, melamine, and l-glutamine). Expansion of the resulting laser-induced shock wave into the air above the sample surface was imaged on a microsecond timescale with a high-speed camera recording multiple frames from each laser shot; the excitation of energetic materials produces larger heat-affected zones in the surrounding atmosphere (facilitating deflagration of particles ejected from the sample surface), results in the formation of additional shock fronts, and generates faster external shock front velocities (>750 m s(-1)) compared to non-energetic materials (550-600 m s(-1)). Non-explosive materials that undergo exothermic chemical reactions in air at high temperatures such as ammonium nitrate and magnesium sulfate produce shock velocities which exceed those of the inert materials but are less than those generated by the exothermic reactions of explosive materials (650-700 m s(-1)). The most powerful explosives produced the highest shock velocities. A comparison to several existing shock models demonstrated that no single model describes the shock propagation for both non-energetic and energetic materials. The influence of the exothermic chemical reactions initiated by the pulsed laser on the velocity of the laser-induced shock waves has thus been demonstrated for the first time.

Thermal and electrochemical properties of nonflammable electrolyte solutions containing fluorinated alkylphosphates for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Todorov, Yanko Marinov; Aoki, Masahiro; Mimura, Hideyuki; Fujii, Kenta; Yoshimoto, Nobuko; Morita, Masayuki

2016-11-01

Nonflammable organic electrolyte solutions containing fluorinated alkylphosphates (FAP) have been examined as safer electrolytes for lithium-ion batteries (LIB). Although the ionic conductivity of LiPF6 in neat tris(2,2,2-trifluoroethyl)phosphate (TFEP) solvent is very low, it increases upon the addition of alkyl carbonates such as ethylene carbonate (EC) and fluoroethylene carbonate (4-fluoro-2-oxo-1,3-dioxolane, FEC). A specific conductivity of 1 mS cm-1 or higher was obtained at room temperature for the system containing proper amounts of the carbonates and 0.5 M (mol dm-3) LiPF6. A conventional mixed alkylcarbonate-based solution containing LiPF6 showed a sign of considerable exothermic reactions on the differential scanning calorimetry (DSC) response below 300 °C. However, the LiPF6/TFEP solution showed no significant exothermic response up to 400 °C, even in the presence of charged LiCoO2 (LCO) positive electrode. The addition of an alkylcarbonate to the LiPF6/TFEP solution produced an exothermic response as a result of the thermal decomposition of the carbonate over the charged LCO. However, the temperature at which the exothermic reaction starts was significantly higher in the system containing FEC than that containing EC. The thermal analysis results suggested that the LiPF6/FEC + TFEP combination could work as a safer electrolyte system in LIB under severe conditions.

Thin film devices used as oxygen partial pressure sensors

NASA Technical Reports Server (NTRS)

Canady, K. S.; Wortman, J. J.

1970-01-01

Electrical conductivity of zinc oxide films to be used in an oxygen partial pressure sensor is measured as a function of temperature, oxygen partial pressure, and other atmospheric constituents. Time response following partial pressure changes is studied as a function of temperature and environmental changes.

Nitrous oxide emissions from one-step partial nitritation/anammox processes.

PubMed

Yang, Jingjing; Trela, Jozef; Plaza, Elzbieta

2016-12-01

Measurements of nitrous oxide were made at pilot- and full-scale plants to evaluate greenhouse gas emissions from one-step partial nitritation/anammox processes applied in moving bed biofilm reactors treating reject water. It was found that 0.51-1.29% and 0.35-1.33% of the total nitrogen loads in the pilot- and full-scale reactor, respectively, were emitted as nitrous oxide. Between 80 and 90% of nitrous oxide emissions were in gaseous form and the rest amount was found in the reactor effluent; over 90% of nitrous oxide emissions occurred in the aerated period and less than 8% in the non-aerated period in the full-scale study. Nitrous oxide productions/consumptions were closely related to aeration and the nitrogen loads applied in the system.

Two stage catalytic combustor

NASA Technical Reports Server (NTRS)

Alvin, Mary Anne (Inventor); Bachovchin, Dennis (Inventor); Smeltzer, Eugene E. (Inventor); Lippert, Thomas E. (Inventor); Bruck, Gerald J. (Inventor)

2010-01-01

A catalytic combustor (14) includes a first catalytic stage (30), a second catalytic stage (40), and an oxidation completion stage (49). The first catalytic stage receives an oxidizer (e.g., 20) and a fuel (26) and discharges a partially oxidized fuel/oxidizer mixture (36). The second catalytic stage receives the partially oxidized fuel/oxidizer mixture and further oxidizes the mixture. The second catalytic stage may include a passageway (47) for conducting a bypass portion (46) of the mixture past a catalyst (e.g., 41) disposed therein. The second catalytic stage may have an outlet temperature elevated sufficiently to complete oxidation of the mixture without using a separate ignition source. The oxidation completion stage is disposed downstream of the second catalytic stage and may recombine the bypass portion with a catalyst exposed portion (48) of the mixture and complete oxidation of the mixture. The second catalytic stage may also include a reticulated foam support (50), a honeycomb support, a tube support or a plate support.

Analysis of effect of flameholder characteristics on lean, premixed, partially vaporized fuel-air mixtures quality and nitrogen oxides emissions

NASA Technical Reports Server (NTRS)

Cooper, L. P.

1981-01-01

An analysis was conducted of the effect of flameholding devices on the precombustion fuel-air characteristics and on oxides of nitrogen (NOx) emissions for combustion of premixed partially vaporized mixtures. The analysis includes the interrelationships of flameholder droplet collection efficiency, reatomization efficiency and blockage, and the initial droplet size distribution and accounts for the contribution of droplet combustion in partially vaporized mixtures to NOx emissions. Application of the analytical procedures is illustrated and parametric predictions of NOx emissions are presented.

Enhanced Electro-Kinetics of C-C Bond-Splitting during Ethanol Oxidation Reaction using Pt/Rh/Sn Catalyst with a Partially Oxidized Pt and Rh Core and a SnO2 Shell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, G.; Su, D.; Frenkel, A. I.

Direct ethanol fuel cell (DEFC) is a promising technology for generating electricity via the electro-oxidation of liquid ethanol. Its implementation requires the development of anode catalysts capable of producing CO 2 and yielding 12-electron transfer through breaking C-C bond of ethanol. Here we presented comprehensive studies of electro-kinetics of the CO 2 generation on Pt/Rh/Sn ternary catalysts. Our studies showed that, for the first time, the tri–phase PtRhOx- SnO 2 catalysts with a partially oxidized Pt and Rh core and a SnO 2 shell, validated by X-ray absorption analyses and scanning transmission electron microscope-electron energy loss spectroscopy line scan, coincidedmore » with a 2.5-fold increase in the CO 2 generation rate towards ethanol oxidation reaction, compared with the bi-phase PtRh-SnO 2 catalysts with a metallic PtRh alloy core and commercial Pt. These studies provided insight on the design of a new genre of electro-catalysts with a partially oxidized noble metal.« less

Oxidation of SiC Fiber-Reinforced SiC Matrix Composites with a BN Interphase

NASA Technical Reports Server (NTRS)

Opila, Elizabeth; Boyd, Meredith K.

2010-01-01

SiC-fiber reinforced SiC matrix composites with a BN interphase were oxidized in reduced oxygen partial pressures of oxygen to simulate the environment for hypersonic vehicle leading edge applications. The constituent fibers as well as composite coupons were oxidized in oxygen partial pressures ranging from 1000 ppm O2 to 5% O2 balance argon. Exposure temperatures ranged from 816 C to 1353 C (1500 F to 2450 F). The oxidation kinetics of the coated fibers were monitored by thermogravimetric analysis (TGA). An initial rapid transient weight gain was observed followed by parabolic kinetics. Possible mechanisms for the transient oxidation are discussed. One edge of the composite coupon seal coat was ground off to simulate damage to the composite which allowed oxygen ingress to the interior of the composite. Oxidation kinetics of the coupons were characterized by scanning electron microscopy since the weight changes were minimal. It was found that sealing of the coupon edge by silica formation occurred. Differences in the amount and morphology of the sealing silica as a function of time, temperature and oxygen partial pressure are discussed. Implications for use of these materials for hypersonic vehicle leading edge materials are summarized.

Enhanced Electro-Kinetics of C-C Bond-Splitting during Ethanol Oxidation Reaction using Pt/Rh/Sn Catalyst with a Partially Oxidized Pt and Rh Core and a SnO2 Shell

DOE PAGES

Yang, G.; Su, D.; Frenkel, A. I.; ...

2016-09-04

Direct ethanol fuel cell (DEFC) is a promising technology for generating electricity via the electro-oxidation of liquid ethanol. Its implementation requires the development of anode catalysts capable of producing CO 2 and yielding 12-electron transfer through breaking C-C bond of ethanol. Here we presented comprehensive studies of electro-kinetics of the CO 2 generation on Pt/Rh/Sn ternary catalysts. Our studies showed that, for the first time, the tri–phase PtRhOx- SnO 2 catalysts with a partially oxidized Pt and Rh core and a SnO 2 shell, validated by X-ray absorption analyses and scanning transmission electron microscope-electron energy loss spectroscopy line scan, coincidedmore » with a 2.5-fold increase in the CO 2 generation rate towards ethanol oxidation reaction, compared with the bi-phase PtRh-SnO 2 catalysts with a metallic PtRh alloy core and commercial Pt. These studies provided insight on the design of a new genre of electro-catalysts with a partially oxidized noble metal.« less

Transformations of C2-C4 alcohols on the surface of a copper catalyst

NASA Astrophysics Data System (ADS)

Magaeva, A. A.; Lyamina, G. V.; Sudakova, N. N.; Shilyaeva, L. P.; Vodyankina, O. V.

2007-10-01

The interaction of monoatomic alcohols C2-C4 with the surface of a copper catalyst preliminarily oxidized under various conditions was studied by the temperature-programmed reaction method to determine the detailed mechanism of partial oxidation. The conditions of oxygen preadsorption on the surface of copper for the preparation of the desired products were determined. The selective formation of carbonyl compounds was shown to occur at the boundary between reduced and oxidized copper surface regions. The role played by Cu2O was the deep oxidation of alcohols to CO2. Alcohols with branched hydrocarbon structures experienced parallel partial oxidation and dehydrogenation, which was related to the high stability of intermediate keto-type compounds.

Electrochemical components employing polysiloxane-derived binders

DOEpatents

Delnick, Frank M.

2013-06-11

A processed polysiloxane resin binder for use in electrochemical components and the method for fabricating components with the binder. The binder comprises processed polysiloxane resin that is partially oxidized and retains some of its methyl groups following partial oxidation. The binder is suitable for use in electrodes of various types, separators in electrochemical devices, primary lithium batteries, electrolytic capacitors, electrochemical capacitors, fuel cells and sensors.

Catalytic performance of V2O5-MoO3/γ-Al2O3 catalysts for partial oxidation of n-hexane1

NASA Astrophysics Data System (ADS)

Mahmoudian, R.; Khodadadi, Z.; Mahdavi, Vahid; Salehi, Mohammed

2016-01-01

In the current study, a series of V2O5-MoO3 catalyst supported on γ-Al2O3 with various V2O5 and MoO3 loadings was prepared by wet impregnation technique. The characterization of prepared catalysts includes BET surface area, powder X-ray diffraction (XRD), and oxygen chemisorptions. The partial oxidation of n-hexane by air over V2O5-MoO3/γ-Al2O3 catalysts was carried out under flow condition in a fixed bed glass reactor. The effect of V2O5 loading, temperature, MoO3 loading, and n-hexane LHSV on the n-hexane conversion and the product selectivity were investigated. The partial oxygenated products of n-hexane oxidation were ethanol, acetic anhydride, acetic acid, and acetaldehyde. The 10% V2O5-1%MoO3/γ-Al2O3 was found in most active and selective catalyst during partial oxidation of n-hexane. The results indicated that by increasing the temperature, the n-hexane conversion increases as well, although the selectivity of the products passes through a maximum by increasing the temperature.

Early diagenetic partial oxidation of organic matter and sulfides in the Middle Pennsylvanian (Desmoinesian) Excello Shale Member of the Fort Scott Limestone and equivalents, northern Midcontinent region, USA

USGS Publications Warehouse

Hatch, J.R.; Leventhal, M.S.

1997-01-01

A process of early diagenetic partial oxidation of organic matter and sulfides has altered the chemical composition of the Middle Pennsylvanian Excello Shale Member of the Fort Scott Limestone and equivalents in the northern Midcontinent region. This process was identified by comparison of organic carbon contents, Rock-Eval hydrogen indices, organic carbon ??13C and element compositions of core and surface mine samples of the Excello Shale Member with analyses of three other underlying and overlying organic-matter-rich marine shales (offshore shale lithofacies) from southern Iowa, northern Missouri, eastern Kansas and northeastern Oklahoma. The end product of the partial oxidation process is shale with relatively low contents of hydrogen-poor, C13-enriched organic matter, lower contents of sulfur and sulfide-forming elements, and relatively unchanged contents of phosphorus and many trace elements (e.g. Cr, Ni, and V). However, because of lower organic carbon contents, element/organic carbon ratios are greatly increased. The partial oxidation process apparently took place during subaerial exposure of the overlying marine carbonate member (Blackjack Creek Member of the Fort Scott Limestone) following a marine regression when meteoric waters percolated down to the level of the Excello muds allowing oxidation of organic matter and sulfides. This hypothesis is supported by earlier workers, who have identified meteoric carbonate cements within, and soil horizons at the top of the Blackjack Creek Member. The period of oxidation is constrained in that organic matter and sulfides in the Little Osage Shale Member of the Fort Scott Limestone and equivalents (immediately overlying the Blackjack Creek Member) appear unaltered. Similar alteration of other shales in the Middle and Upper Pennsylvanian sections may be local to regional in extent and would depend on the extent and duration of the marine regression and be influenced by local variations in permeability and topography. The partial oxidation process has likely led to a redistribution of sulfur and sulfide-forming elements into other organic-rich lithologies in the section. The altered/oxidized shales are nongenerative with respect to hydrocarbon generation.

Partially Premixed Flame (PPF) Research for Fire Safety

NASA Technical Reports Server (NTRS)

Puri, Ishwar K.; Aggarwal, Suresh K.; Lock, Andrew J.; Hegde, Uday

2004-01-01

Incipient fires typically occur after the partial premixing of fuel and oxidizer. The mixing of product species into the fuel/oxidizer mixture influences flame stabilization and fire spread. Therefore, it is important to characterize the impact of different levels of fuel/oxidizer/product mixing on flame stabilization, liftoff and extinguishment under different gravity conditions. With regard to fire protection, the agent concentration required to achieve flame suppression is an important consideration. The initial stage of an unwanted fire in a microgravity environment will depend on the level of partial premixing and the local conditions such as air currents generated by the fire itself and any forced ventilation (that influence agent and product mixing into the fire). The motivation of our investigation is to characterize these impacts in a systematic and fundamental manner.

Oxygen-induced defects at the lead halide perovskite/graphene oxide interfaces

DOE PAGES

Acik, Muge; Park, In Kee; Koritala, Rachel E.; ...

2017-12-21

Here, graphene oxide or its reduced derivative (GO/RGO) replace metal oxides in perovskite photovoltaics to achieve energy band alignment for minimization of the energy barriers at the film interfaces allowing efficient charge transport, and eliminate stability issues. However, the power conversion efficiencies fall in a wide range (~0.6–18%). Therefore, the perovskite growth and nucleation on GO/RGO require fundamental understanding to improve device function for controlled fabrication, which remain a major challenge. We analyze the surface morphology and crystallization of the lead halide perovskites (MAPbX 3) at 20–300 °C on GO using X-ray diffraction and photoelectron spectroscopy. To determine defect mechanismsmore » and their composition, we perform in situ transmission infrared and micro Raman spectroscopy, and the cross-sectional scanning microscopy that captures interfacial imperfections with the oxygen defects. We demonstrate the oxygen-induced defects at the MAPbX 3/GO interfaces that initiate at room temperature, and occur through the nucleophilic substitution reactions. Unexpectedly, structural defects nucleate in GO forming chemically reduced GO, and modify the surface morphology that yield a poor perovskite growth. Our theoretical studies also reveal that energetically favorable, exothermic reactions between the halides of the perovskite precursors and the oxygen groups of GO generate acidic reaction by-products ( i.e. HX), that confirm the formation of oxygen-induced defects.« less

Insight into the interactions of proteinase inhibitor-alpha-2-macroglobulin with hypochlorite-thermal analysis and biophysical approach.

PubMed

Siddiqui, Tooba; Zia, Mohammad Khalid; Ali, Syed Saqib; Ahsan, Haseeb; Khan, Fahim Halim

2018-05-17

Hypochlorous acid, an active bleaching agent is one of the major oxidants produced by neutrophils under physiological conditions. It is a potent reactive oxygen species (ROS) which causes oxidation of biomolecules. Treatment of proteins with hypochlorite results in direct oxidative damage to proteins. Alpha-2-macroglobulin is a major proteinase inhibitor and it can inhibit proteinase of any kind regardless of specificity and catalytic mechanism. The proteinase-antiproteinase balance plays an important role in mediating inflammation associated tissue destruction. In this paper, we have studied hypochlorite induced modifications in proteinase inhibitor-alpha-2-macroglobulin via biophysical techniques such as absorption spectroscopy, fluorescence spectroscopy, circular dichroism (CD), fourier transform infrared spectrometery (FTIR) and isothermal titration calorimetry (ITC). It was found that hypochlorite decreases the anti-proteolytic potential and causes inactivation of sheep alpha-2-macroglobulin. It also causes structural and functional change in alpha-2-macroglobulin as evident by absorption spectroscopy and fluorescence spectroscopy. Change in secondary structure of alpha-2-macroglobulin was confirmed by CD and FTIR. Thermodynamics parameters such as entropy (ΔS), enthalpy (ΔH) and Gibb's free energy changes (ΔG). The number of binding sites (N) of alpha-2-macroglobulin-HOCl binding in solution was determined by isothermal titration calorimetry and it was found that binding of hypochlorite with alpha-2-macroglobulin was exothermic in nature. Copyright © 2017. Published by Elsevier B.V.

Oxygen-induced defects at the lead halide perovskite/graphene oxide interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Acik, Muge; Park, In Kee; Koritala, Rachel E.

Here, graphene oxide or its reduced derivative (GO/RGO) replace metal oxides in perovskite photovoltaics to achieve energy band alignment for minimization of the energy barriers at the film interfaces allowing efficient charge transport, and eliminate stability issues. However, the power conversion efficiencies fall in a wide range (~0.6–18%). Therefore, the perovskite growth and nucleation on GO/RGO require fundamental understanding to improve device function for controlled fabrication, which remain a major challenge. We analyze the surface morphology and crystallization of the lead halide perovskites (MAPbX 3) at 20–300 °C on GO using X-ray diffraction and photoelectron spectroscopy. To determine defect mechanismsmore » and their composition, we perform in situ transmission infrared and micro Raman spectroscopy, and the cross-sectional scanning microscopy that captures interfacial imperfections with the oxygen defects. We demonstrate the oxygen-induced defects at the MAPbX 3/GO interfaces that initiate at room temperature, and occur through the nucleophilic substitution reactions. Unexpectedly, structural defects nucleate in GO forming chemically reduced GO, and modify the surface morphology that yield a poor perovskite growth. Our theoretical studies also reveal that energetically favorable, exothermic reactions between the halides of the perovskite precursors and the oxygen groups of GO generate acidic reaction by-products ( i.e. HX), that confirm the formation of oxygen-induced defects.« less

Chemistry of fast electrons

PubMed Central

Maximoff, Sergey N.; Head-Gordon, Martin P.

2009-01-01

A chemicurrent is a flux of fast (kinetic energy ≳ 0.5−1.3 eV) metal electrons caused by moderately exothermic (1−3 eV) chemical reactions over high work function (4−6 eV) metal surfaces. In this report, the relation between chemicurrent and surface chemistry is elucidated with a combination of top-down phenomenology and bottom-up atomic-scale modeling. Examination of catalytic CO oxidation, an example which exhibits a chemicurrent, reveals 3 constituents of this relation: The localization of some conduction electrons to the surface via a reduction reaction, 0.5 O2 + δe− → Oδ− (Red); the delocalization of some surface electrons into a conduction band in an oxidation reaction, Oδ− + CO → CO2δ− → CO2 + δe− (Ox); and relaxation without charge transfer (Rel). Juxtaposition of Red, Ox, and Rel produces a daunting variety of metal electronic excitations, but only those that originate from CO2 reactive desorption are long-range and fast enough to dominate the chemicurrent. The chemicurrent yield depends on the universality class of the desorption process and the distribution of the desorption thresholds. This analysis implies a power-law relation with exponent 2.66 between the chemicurrent and the heat of adsorption, which is consistent with experimental findings for a range of systems. This picture also applies to other oxidation-reduction reactions over high work function metal surfaces. PMID:19561296

Physicochemical and thermal characteristics of the sludge produced after thermochemical treatment of petrochemical wastewater.

PubMed

Verma, Shilpi; Prasad, Basheshwar; Mishra, I M

2012-01-01

The present work describes the physicochemical and thermal characteristics of the sludge generated after thermochemical treatment of wastewater from a petrochemical plant manufacturing purified terephthalic acid (PTA). Although FeCl3 was found to be more effective than CuSO4 in removing COD from wastewater, the settling and filtration characteristics of FeCl3 sludge were poorer. Addition of cationic polyacrylamide (CPAA; 0.050kg/m3) to the FeCl3 wastewater system greatly improved the values of the filter characteristics of specific cake resistance (1.2 x 10(8) m/kg) and resistance of filter medium (9.9 x 10(8) m(-1)) from the earlier values of 1.9 x 10(9) m/kg and 1.7 x 10(8) m(-1), respectively. SEM-EDAX and FTIR studies were undertaken, to understand the sludge structure and composition, respectively. The moisture distribution in the CuSO4 sludge, FeCl3 sludge and FeCl3 + CPAA sludge showed that the amount of bound water content in the CuSO4 and FeCl3 + CPAA sludges is less than that of the FeCl3 sludge and there was a significant reduction in the solid-water bond strength of FeCl3 + CPAA sludge, which was responsible for better settling and filtration characteristics. Due to the hazardous nature of the sludge, land application is not a possible route of disposal. The thermal degradation behaviour of the sludge was studied for its possible use as a co-fuel. The studies showed that degradation behaviour of the sludge was exothermic in nature. Because of the exothermic nature of the sludge, it can be used in making fuel briquettes or it can be disposed of via wet air oxidation.

First-principles study of the interaction of H2O with the GaSb (001) surface

NASA Astrophysics Data System (ADS)

Bermudez, V. M.

2013-05-01

The adsorption of H2O on the GaSb (001) surface, both clean and with pre-adsorbed H atoms, has been studied computationally using dispersion-corrected density functional theory. The model employed is the α-(4×3) reconstruction consisting of Ga-Sb dimers adsorbed on the Sb-terminated surface, a disordered version of which is believed to constitute the frequently observed Sb-rich (1×3) surface. On the clean surface, molecular adsorption of H2O at a coordinatively unsaturated Ga site is exothermic (ΔE = -0.57 eV), but dissociation of this adsorbed H2O is significantly endothermic (ΔE = +0.45 eV or more). Dissociation can form either a (HO)Ga-Sb(H) site involving a Ga-Sb dimer or a (H)Ga-O(H)-Sb bridge. Other reactions are also energetically feasible, depending on the bond strength of different inequivalent Ga-Sb dimers. The two structures have essentially the same energy, and both can undergo an exothermic reaction with a second H2O. For the (HO)Ga-Sb(H) site, this reaction leads to the breaking of the dimer bond and the adsorption of molecular water, while the (H)Ga-O(H)-Sb bridge transforms to (HO)Ga-O(H)-Sb with the release of H2. On the H-terminated surface, molecular adsorption of H2O can be suppressed and dissociative adsorption enhanced, which means that formation of an OH-terminated surface may be easier when starting with an H-terminated vs. a clean surface. The implications of these results for the growth of oxide/GaSb heterostructures via atomic layer deposition are discussed.

Surface-Mediated Solvent Decomposition in Li–Air Batteries: Impact of Peroxide and Superoxide Surface Terminations

DOE PAGES

Kumar, Nitin; Radin, Maxwell D.; Wood, Brandon C.; ...

2015-04-13

A viable Li/O 2 battery will require the development of stable electrolytes that do not continuously decompose during cell operation. In some recent experiments it is suggested that reactions occurring at the interface between the liquid electrolyte and the solid lithium peroxide (Li 2O 2) discharge phase are a major contributor to these instabilities. To clarify the mechanisms associated with these reactions, a variety of atomistic simulation techniques, classical Monte Carlo, van der Waals-augmented density functional theory, ab initio molecular dynamics, and various solvation models, are used to study the initial decomposition of the common electrolyte solvent, dimethoxyethane (DME), onmore » surfaces of Li 2O 2. Comparisons are made between the two predominant Li 2O 2 surface charge states by calculating decomposition pathways on peroxide-terminated (O 2 2–) and superoxide-terminated (O 2 1–) facets. For both terminations, DME decomposition proceeds exothermically via a two-step process comprised of hydrogen abstraction (H-abstraction) followed by nucleophilic attack. In the first step, abstracted H dissociates a surface O 2 dimer, and combines with a dissociated oxygen to form a hydroxide ion (OH –). In the remaining surface oxygen then attacks the DME, resulting in a DME fragment that is strongly bound to the Li 2O 2 surface. DME decomposition is predicted to be more exothermic on the peroxide facet; nevertheless, the rate of DME decomposition is faster on the superoxide termination. The impact of solvation (explicit vs implicit) and an applied electric field on the reaction energetics are investigated. Finally, our calculations suggest that surface-mediated electrolyte decomposition should out-pace liquid-phase processes such as solvent auto-oxidation by dissolved O 2.« less

Thermodynamic data of lawsonite and zoisite in the system CaO-Al2O3-SiO2-H2O based on experimental phase equilibria and calorimetric work

NASA Astrophysics Data System (ADS)

Grevel, Klaus-Dieter; Schoenitz, Mirko; Skrok, Volker; Navrotsky, Alexandra; Schreyer, Werner

2001-08-01

The enthalpy of drop-solution in molten 2PbO.B2O3 of synthetic and natural lawsonite, CaAl2(Si2O7)(OH)2.H2O, was measured by high-temperature oxide melt calorimetry. The enthalpy of formation determined for the synthetic material is ΔfHOxides=-168.7+/-3.4 kJ mol-1, or ΔfH0298=-4,872.5+/-4.0 kJ mol-1. These values are in reasonable agreement with previously published data, although previous calorimetric work yielded slightly more exothermic data and optimisation methods resulted in slightly less exothermic values. The equilibrium conditions for the dehydration of lawsonite to zoisite, kyanite and quartz/coesite at pressures and temperatures up to 5 GPa and 850 °C were determined by piston cylinder experiments. These results, other recent phase equilibrium data, and new calorimetric and thermophysical data for lawsonite and zoisite, Ca2Al3(SiO4)(Si2O7)O(OH), were used to constrain a mathematical programming analysis of the thermodynamic data for these two minerals in the chemical system CaO-Al2O3-SiO2-H2O (CASH). The following data for lawsonite and zoisite were obtained: ΔfH0298 (lawsonite)=-4,865.68 kJ mol-1 , S0298 (lawsonite)=229.27 J K-1 mol-1 , ΔfH0298 (zoisite)=-6,888.99 kJ mol-1 , S0298 (zoisite)=297.71 J K-1 mol-1 . Additionally, a recalculation of the bulk modulus of lawsonite yielded K=120.7 GPa, which is in good agreement with recent experimental work.

A thermally self-sustained micro-power plant with integrated micro-solid oxide fuel cells, micro-reformer and functional micro-fluidic carrier

NASA Astrophysics Data System (ADS)

Scherrer, Barbara; Evans, Anna; Santis-Alvarez, Alejandro J.; Jiang, Bo; Martynczuk, Julia; Galinski, Henning; Nabavi, Majid; Prestat, Michel; Tölke, René; Bieberle-Hütter, Anja; Poulikakos, Dimos; Muralt, Paul; Niedermann, Philippe; Dommann, Alex; Maeder, Thomas; Heeb, Peter; Straessle, Valentin; Muller, Claude; Gauckler, Ludwig J.

2014-07-01

Low temperature micro-solid oxide fuel cell (micro-SOFC) systems are an attractive alternative power source for small-size portable electronic devices due to their high energy efficiency and density. Here, we report on a thermally self-sustainable reformer-micro-SOFC assembly. The device consists of a micro-reformer bonded to a silicon chip containing 30 micro-SOFC membranes and a functional glass carrier with gas channels and screen-printed heaters for start-up. Thermal independence of the device from the externally powered heater is achieved by exothermic reforming reactions above 470 °C. The reforming reaction and the fuel gas flow rate of the n-butane/air gas mixture controls the operation temperature and gas composition on the micro-SOFC membrane. In the temperature range between 505 °C and 570 °C, the gas composition after the micro-reformer consists of 12 vol.% to 28 vol.% H2. An open-circuit voltage of 1.0 V and maximum power density of 47 mW cm-2 at 565 °C is achieved with the on-chip produced hydrogen at the micro-SOFC membranes.

Hydrogen production from carbonaceous material

DOEpatents

Lackner, Klaus S.; Ziock, Hans J.; Harrison, Douglas P.

2004-09-14

Hydrogen is produced from solid or liquid carbon-containing fuels in a two-step process. The fuel is gasified with hydrogen in a hydrogenation reaction to produce a methane-rich gaseous reaction product, which is then reacted with water and calcium oxide in a hydrogen production and carbonation reaction to produce hydrogen and calcium carbonate. The calcium carbonate may be continuously removed from the hydrogen production and carbonation reaction zone and calcined to regenerate calcium oxide, which may be reintroduced into the hydrogen production and carbonation reaction zone. Hydrogen produced in the hydrogen production and carbonation reaction is more than sufficient both to provide the energy necessary for the calcination reaction and also to sustain the hydrogenation of the coal in the gasification reaction. The excess hydrogen is available for energy production or other purposes. Substantially all of the carbon introduced as fuel ultimately emerges from the invention process in a stream of substantially pure carbon dioxide. The water necessary for the hydrogen production and carbonation reaction may be introduced into both the gasification and hydrogen production and carbonation reactions, and allocated so as transfer the exothermic heat of reaction of the gasification reaction to the endothermic hydrogen production and carbonation reaction.

Fabrication of magnetic water-soluble hyperbranched polyol functionalized graphene oxide for high-efficiency water remediation

PubMed Central

Hu, Lihua; Li, Yan; Zhang, Xuefei; Wang, Yaoguang; Cui, Limei; Wei, Qin; Ma, Hongmin; Yan, Liangguo; Du, Bin

2016-01-01

Magnetic water-soluble hyperbranched polyol functionalized graphene oxide nanocomposite (MWHPO-GO) was successfully prepared and applied to water remediation in this paper. MWHPO-GO was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), magnetization curve, zeta potential, scanning electron microscope (SEM) and transmission electron microscope (TEM) analyses. MWHPO-GO exhibited excellent adsorption performance for the removal of synthetic dyes (methylene blue (MB) and methyl violet (MV)) and heavy metal (Pb(II)). Moreover, MWHPO-GO could be simply recovered from water with magnetic separation. The pseudo-second order equation and the Langmuir model exhibited good correlation with the adsorption kinetic and isotherm data, respectively, for these three pollutants. The thermodynamic results (ΔG < 0, ΔH < 0, ΔS < 0) implied that the adsorption process of MB, MV and Pb(II) was feasible, exothermic and spontaneous in nature. A possible adsorption mechanism has been proposed where π-π stacking interactions, H-bonding interaction and electrostatic attraction dominated the adsorption of MB/MV and chelation and electrostatic attraction dominated the adsorption of Pb(II). In addition, the excellent reproducibility endowed MWHPO-GO with the potential for application in water remediation. PMID:27354318

Methane to methanol conversion induced by thorium oxide through the CH3Th(O)H intermediate in solid argon.

PubMed

Gong, Yu; Andrews, Lester; Jackson, Virgil E; Dixon, David A

2012-10-15

Reactions of ThO molecules and CH(4) have been investigated in solid argon near 4 K. The CH(3)Th(O)H molecule is produced when the sample is exposed to UV irradiation. Identification of this new intermediate is substantiated by observation of the Th═O and Th-H stretching vibrational modes with isotopic substitution via matrix infrared spectroscopy, and the assignments are supported by electronic structure frequency calculations. Methanol absorptions increase together with formation of the CH(3)Th(O)H molecule, suggesting a methane to methanol conversion induced by thorium oxide proceeding through the CH(3)Th(O)H intermediate. The formation of CH(3)Th(O)H from ThO + CH(4) is exothermic (ΔH(rxn) = -11 kcal/mol) with an energy barrier of 30 kcal/mol at the CCSD(T)//B3LYP level. Decomposition of this intermediate to form methanol involves spin crossing, and the overall reaction from the intermediate is endothermic by 127 kcal/mol. There is no activation energy for the reaction of thorium atoms with methanol to give CH(3)Th(O)H, as observed in separate experiments with Th and CH(3)OH.

Radiation damage and annealing in plutonium tetrafluoride

NASA Astrophysics Data System (ADS)

McCoy, Kaylyn; Casella, Amanda; Sinkov, Sergey; Sweet, Lucas; McNamara, Bruce; Delegard, Calvin; Jevremovic, Tatjana

2017-12-01

A sample of plutonium tetrafluoride that was separated prior to 1966 at the Hanford Site in Washington State was analyzed at the Pacific Northwest National Laboratory (PNNL) in 2015 and 2016. The plutonium tetrafluoride, as received, was an unusual color and considering the age of the plutonium, there were questions about the condition of the material. These questions had to be answered in order to determine the suitability of the material for future use or long-term storage. Therefore, thermogravimetric/differential thermal analysis and X-ray diffraction evaluations were conducted to determine the plutonium's crystal structure, oxide content, and moisture content; these analyses reported that the plutonium was predominately amorphous and tetrafluoride, with an oxide content near ten percent. Freshly fluorinated plutonium tetrafluoride is known to be monoclinic. During the initial thermogravimetric/differential thermal analyses, it was discovered that an exothermic event occurred within the material near 414 °C. X-ray diffraction analyses were conducted on the annealed tetrafluoride. The X-ray diffraction analyses indicated that some degree of recrystallization occurred in conjunction with the 414 °C event. The following commentary describes the series of thermogravimetric/differential thermal and X-ray diffraction analyses that were conducted as part of this investigation at PNNL.

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

NASA Astrophysics Data System (ADS)

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

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

Sunlight Controls Water Column Processing of Carbon in Arctic Freshwaters

NASA Astrophysics Data System (ADS)

Cory, R. M.; Ward, C. P.; Crump, B. C.; Kling, G. W.

2014-12-01

Carbon (C) in thawing permafrost soils may have global impacts on climate change, yet controls on its processing and fate are poorly understood. The dominant fate of dissolved organic C (DOC) released from soils to inland waters is either complete oxidation to CO2 or partial oxidation and river export to oceans. Both processes are most often attributed to bacterial respiration, but we recently showed that photochemical oxidation exceeds rates of respiration and accounts for 70-95% of total DOC processed in the water column of arctic lakes and rivers. While the overall dominance of photochemical processing in streams and lakes remained, the fate of DOC varied consistently by water type. In small streams DOC was mainly mineralized by sunlight to CO2, while in lakes the main fate of DOC was partial photo-oxidation. Large rivers were intermediate between these end members, and photo-mineralization to CO2 was about equal to or less than partial photo-oxidation. We suggest this pattern is a result of light-exposure history, where DOC leached from soils into headwater streams has little prior light exposure and is labile to complete photo-oxidation, but as light exposure increases moving downstream and into lakes with longer residence times the DOC photo-lability declines. Thus as easily photo-mineralized moieties are removed, DOC fate shifts toward partial photo-oxidation and downstream export in rivers and lakes. At the basin scale, photochemical processing of DOC is about one third of the total CO2 released from surface waters, and is thus an important, newly measured component of the Arctic C budget. We also suggest that these photochemical transformations of DOC will occur in any shallow surface water, and could be important for better understanding inland water carbon cycling.

Thermal Decomposition Study on CuInSe2 Single Crystals

NASA Astrophysics Data System (ADS)

Chauhan, Sanjaysinh M.; Chaki, Sunil H.; Deshpande, M. P.; Malek, Tasmira J.; Tailor, J. P.

2018-01-01

The thermal analysis of the chemical vapor transport (CVT)-grown CuInSe2 single crystals was carried out by recording the thermogravimetric, differential thermogravimetric and differential thermal analysis curves. All the three thermo-curves were recorded simultaneously by thermal analyzer in the temperature range of ambient to 1080 K in inert nitrogen atmosphere. The thermo-curves were recorded for four heating rates of 5 K \\cdot min^{-1}, 10 K \\cdot min^{-1}, 15 K \\cdot min^{-1} and 20 K \\cdot min^{-1}. The TG curve analysis showed negligible mass loss in the temperature range of ambient to 600 K, stating the sample material to be thermally stable in this temperature range. Above 601 K to the temperature of 1080 K, the sample showed continuous mass loss. The DTG curves showed two peaks in the temperature range of 601 K to 1080 K. The corresponding DTA showed initial minor exothermic nature followed by endothermic nature up to nearly 750 K and above it showed exothermic nature. The initial exothermic nature is due to absorbed water converting to water vapor, whereas the endothermic nature states the absorption of heat by the sample up to nearly 950 K. Above nearly 950 K the exothermic nature is due to the decomposition of sample material. The absorption of heat in the endothermic region is substantiated by corresponding weight loss in TG. The thermal kinetic parameters of the CVT-grown CuInSe2 single crystals were determined employing the non-mechanistic Kissinger relation. The determined kinetic parameters support the observations of the thermo-curves.

Uranium and minor-element partitioning in Fe-Ti oxides and zircon from partially melted granodiorite, Crater Lake, Oregon

USGS Publications Warehouse

Tourrette, T.Z.L.; Burnett, D.S.; Bacon, C.R.

1991-01-01

Crystal-liquid partitioning in Fe-Ti oxides and zircon was studied in partially melted granodiorite blocks ejected during the climactic eruption of Mt. Mazama (Crater Lake), Oregon. The blocks, which contain up to 33% rhyolite glass (75 wt% SiO2), are interpreted to be portions of the magma chamber walls that were torn off during eruption. The glass is clear and well homogenized for all measured elements except Zr. Results for Fe-Ti oxides give DUoxide/liq ??? 0.1. Partitioning of Mg, Mn, Al, Si, V, and Cr in Fe-Ti oxides indicates that grains surrounded by glass are moderately well equilibrated with the melt for many of the minor elements, while those that are inclusions in relict plagioclase are not. Uranium and ytterbium inhomogeneities in zircons indicate that the zircons have only partially equilibrated with the melt and that uranium appears to have been diffusing out of the zircons faster than the zircons were dissolving. Minimum U, Y, and P concentrations in zircons give maximum DUzrc/liq = 13,DYzrc/liq = 23, and DPzrc/liq = 1, but these are considerably lower than reported by other workers for U and Y. Based on our measurements and given their low abundances in most rocks, Fe-Ti oxides probably do not play a major role in U-Th fractionation during partial melting. The partial melts were undersaturated with zircon and apatite, but both phases are present in our samples. This demonstrates an actual case of non-equilibrium source retention of accessory phases, which in general could be an important trace-element fractionation mechanism. Our results do not support the hypothesis that liquid structure is the dominant factor controlling trace-element partitioning in high-silica rhyolites. Rough calculations based on Zr gradients in the glass indicate that the samples could have been partially molten for 800 to 8000 years. ?? 1991.

A Theoretical Study of Methanol Oxidation on RuO 2(110): Bridging the Pressure Gap

DOE Office of Scientific and Technical Information (OSTI.GOV)

Latimer, Allegra A.; Abild-Pedersen, Frank; Norskov, Jens K.

Partial oxidation catalysis is often fraught with selectivity problems, largely because there is a tendency of oxidation products to be more reactive than the starting material. One industrial process that has successfully overcome this problem is partial oxidation of methanol to formaldehyde. This process has become a global success, with an annual production of 30 million tons. Although ruthenium catalysts have not shown activity as high as the current molybdena or silver-based industrial standards, the study of ruthenium systems has the potential to elucidate which catalyst properties facilitate the desired partial oxidation reaction as opposed to deep combustion due tomore » a pressure-dependent selectivity “switch” that has been observed in ruthenium-based catalysts. In this work, we find that we are able to successfully rationalize this “pressure gap” using near-ab initio steady-state microkinetic modeling on RuO 2(110). We obtain molecular desorption prefactors from experiment and determine all other energetics using density functional theory. We show that, under ambient pressure conditions, formaldehyde production is favored on RuO 2(110), whereas under ultrahigh vacuum pressure conditions, full combustion to CO 2 takes place. We glean from our model several insights regarding how coverage effects, oxygen activity, and rate-determining steps influence selectivity and activity. As a result, we believe the understanding gained in this work might advise and inspire the greater partial oxidation community and be applied to other catalytic processes which have not yet found industrial success.« less

A Theoretical Study of Methanol Oxidation on RuO 2(110): Bridging the Pressure Gap

DOE PAGES

Latimer, Allegra A.; Abild-Pedersen, Frank; Norskov, Jens K.

2017-05-26

Partial oxidation catalysis is often fraught with selectivity problems, largely because there is a tendency of oxidation products to be more reactive than the starting material. One industrial process that has successfully overcome this problem is partial oxidation of methanol to formaldehyde. This process has become a global success, with an annual production of 30 million tons. Although ruthenium catalysts have not shown activity as high as the current molybdena or silver-based industrial standards, the study of ruthenium systems has the potential to elucidate which catalyst properties facilitate the desired partial oxidation reaction as opposed to deep combustion due tomore » a pressure-dependent selectivity “switch” that has been observed in ruthenium-based catalysts. In this work, we find that we are able to successfully rationalize this “pressure gap” using near-ab initio steady-state microkinetic modeling on RuO 2(110). We obtain molecular desorption prefactors from experiment and determine all other energetics using density functional theory. We show that, under ambient pressure conditions, formaldehyde production is favored on RuO 2(110), whereas under ultrahigh vacuum pressure conditions, full combustion to CO 2 takes place. We glean from our model several insights regarding how coverage effects, oxygen activity, and rate-determining steps influence selectivity and activity. As a result, we believe the understanding gained in this work might advise and inspire the greater partial oxidation community and be applied to other catalytic processes which have not yet found industrial success.« less

Catalytic oxidation of light alkanes in presence of a base

DOEpatents

Bhinde, Manoj V.; Bierl, Thomas W.

1998-01-01

The presence of a base in the reaction mixture in a metal-ligand catalyzed partial oxidation of alkanes results in sustained catalyst activity, and in greater percent conversion as compared with oxidation in the absence of base, while maintaining satisfactory selectivity for the desired oxidation, for example the oxidation of isobutane to isobutanol.

Sulfur control in ion-conducting membrane systems

DOEpatents

Stein, VanEric Edward; Richards, Robin Edward; Brengel, David Douglas; Carolan, Michael Francis

2003-08-05

A method for controlling the sulfur dioxide partial pressure in a pressurized, heated, oxygen-containing gas mixture which is contacted with an ion-conducting metallic oxide membrane which permeates oxygen ions. The sulfur dioxide partial pressure in the oxygen-depleted non-permeate gas from the membrane module is maintained below a critical sulfur dioxide partial pressure, p.sub.SO2 *, to protect the membrane material from reacting with sulfur dioxide and reducing the oxygen flux of the membrane. Each ion-conducting metallic oxide material has a characteristic critical sulfur dioxide partial pressure which is useful in determining the required level of sulfur removal from the feed gas and/or from the fuel gas used in a direct-fired feed gas heater.

The reactivity of 1,3-butadiene with butadiene-derived popcorn polymer.

PubMed

Levin, M E; Hill, A D; Zimmerman, L W; Paxson, T E

2004-11-11

Adiabatic calorimetry performed on butadiene-derived popcorn polymer samples from industrial facilities has revealed exothermic behavior accompanied by non-condensible gas production, indicative of possible decomposition, at elevated temperatures. In the presence of low concentrations of 1,3-butadiene, reactivity is observed at temperatures of 60-70 degrees C; that is, 20-30 degrees C below those usually seen for butadiene alone. Once the butadiene is consumed, the reaction behavior reverts to that of the popcorn polymer alone. At higher butadiene concentrations, the low temperature reaction persists, eventually merging with typical butadiene behavior. The butadiene reactivity with popcorn polymer is attributed to polymerization reaction at free radical sites in the popcorn polymer. Different popcorn polymer samples exhibit distinct extents of reactivity, presumably depending on the nature and concentration of the free radical sites and the structure of the material. Uninhibited butadiene exposed to 100 psia air, which may act to generate peroxide species, shows a small, additional exotherm around 50-80 degrees C. Contact of butadiene with lauroyl peroxide, providing free radicals upon decomposition, generates an exotherm at temperatures as low as 60 degrees C.

Exothermic dark matter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Graham, Peter W.; Saraswat, Prashant; Harnik, Roni

2010-09-15

We propose a novel mechanism for dark matter to explain the observed annual modulation signal at DAMA/LIBRA which avoids existing constraints from every other dark matter direct detection experiment including CRESST, CDMS, and XENON10. The dark matter consists of at least two light states with mass {approx}few GeV and splittings {approx}5 keV. It is natural for the heavier states to be cosmologically long-lived and to make up an O(1) fraction of the dark matter. Direct detection rates are dominated by the exothermic reactions in which an excited dark matter state downscatters off of a nucleus, becoming a lower energy state.more » In contrast to (endothermic) inelastic dark matter, the most sensitive experiments for exothermic dark matter are those with light nuclei and low threshold energies. Interestingly, this model can also naturally account for the observed low-energy events at CoGeNT. The only significant constraint on the model arises from the DAMA/LIBRA unmodulated spectrum but it can be tested in the near future by a low-threshold analysis of CDMS-Si and possibly other experiments including CRESST, COUPP, and XENON100.« less

Biomass pyrolysis and combustion integral and differential reaction heats with temperatures using thermogravimetric analysis/differential scanning calorimetry.

PubMed

Shen, Jiacheng; Igathinathane, C; Yu, Manlu; Pothula, Anand Kumar

2015-06-01

Integral reaction heats of switchgrass, big bluestem, and corn stalks were determined using thermogravimetric analysis/differential scanning calorimetry (TGA/DSC). Iso-conversion differential reaction heats using TGA/DSC pyrolysis and combustion of biomass were not available, despite reports available on heats required and released. A concept of iso-conversion differential reaction heats was used to determine the differential reaction heats of each thermal characteristics segment of these materials. Results showed that the integral reaction heats were endothermic from 30 to 700°C for pyrolysis of switchgrass and big bluestem, but they were exothermic for corn stalks prior to 587°C. However, the integral reaction heats for combustion of the materials followed an endothermic to exothermic transition. The differential reaction heats of switchgrass pyrolysis were predominantly endothermic in the fraction of mass loss (0.0536-0.975), and were exothermic for corn stalks (0.0885-0.850) and big bluestem (0.736-0.919). Study results provided better insight into biomass thermal mechanism. Published by Elsevier Ltd.

Evaluation of natural organic matter adsorption on Fe-Al binary oxide: Comparison with single metal oxides.

PubMed

Kim, Kyung-Jo; Jang, Am

2017-10-01

The adsorption characteristics of three types of standard natural organic matter (NOM) on iron-aluminum (Fe-Al) binary oxide (FAO) and heated aluminum oxide (HAO) under natural surface water condition were investigated using various adsorption isotherms and kinetic models. FAO was synthesized by Fe oxide and Al oxide, mixed using the sol-gel hydrothermal method, and aluminum sulfate was used to make HAO. The amount of adsorbed NOM was increased to 79.6 mg g -1 for humic acid (HA), 101.1 mg g -1 for sodium alginate (SA) in the FAO, but the maximum adsorption capacity of bovine serum albumin (BSA) (461.3 mg g -1 ) was identified on the HAO. The adsorption of HA, BSA, and SA dramatically increased (>70%) on FAO in 5 min and HA was significantly removed (90%) among the three NOM. Mutual interaction among the adsorbed NOM (BSA) occurred on the HAO surface during adsorption due to formation of monolayer by protein molecules at neutral pH. The pseudo second order clearly represented the adsorption kinetics for both adsorbents. The equilibrium isotherm data of FAO was better exhibited by the Langmuir isotherm model than by the Freundlich isotherm, but HAO was a slightly non-linear Langmuir type. Also, the free energy, enthalpy, and entropy of adsorption were determined from the thermodynamic experiments. Adsorption on FAO was spontaneous and an exothermic process. Fluorescence excitation-emission matrix (FEEM) spectra were used to elucidate the variation in organic components. The results obtained suggests that the significant changes in the surface property of the adsorbent (large surface area, increased crystalline intensity, and fine particle size) were effectively determined by the Fe-synthesized Al oxide mixed using the sol-gel hydrothermal method. The results also suggest that the changes enhanced the adsorption capacity, whereby three NOM were notably removed on FAO regardless of NOM characteristics (hydrophobic and hydrophilic). Copyright © 2017 Elsevier Ltd. All rights reserved.

Acid-catalyzed hydrogenation during kerosene hydrodewaxing over H/ZSM-5

DOE Office of Scientific and Technical Information (OSTI.GOV)

Longstaff, D.C.; Hanson, F.V.

1996-11-01

Hydrogen addition to the products derived from cracking kerosene over H/ZSM-5 was observed at hydrogen pressures between 4.1-8.7 MPa and at 373-390{degrees}C. At low pressures, kerosene cracking over H/ZSM-5 yielded typical cracked products: aromatics, as well as low molecular weight saturates and olefins. Endothermic reactor temperature profiles were also observed, indicative of cracking reactions. At high hydrogen partial pressures product selectivity was altered in that kerosene cracking gave high yields of low molecular weight paraffins and low yields of olefins and aromatics. Reactor temperature profiles were exothermic, indicative of hydrocracking reactions. A mechanism for acid catalyzed hydrogenation is suggested. Althoughmore » hydrogenation was not observed at lower hydrogen pressures, hydrogen proved beneficial in maintaining catalyst activity at a stable level. Lost catalyst activity was restored by maintaining the catalyst under static hydrogen at 1.4 MPa and 370{degrees}C for 16h. 36 refs., 14 figs., 3 tabs.« less

Thermal control system. [removing waste heat from industrial process spacecraft

NASA Technical Reports Server (NTRS)

Hewitt, D. R. (Inventor)

1983-01-01

The temperature of an exothermic process plant carried aboard an Earth orbiting spacecraft is regulated using a number of curved radiator panels accurately positioned in a circular arrangement to form an open receptacle. A module containing the process is insertable into the receptacle. Heat exchangers having broad exterior surfaces extending axially above the circumference of the module fit within arcuate spacings between adjacent radiator panels. Banks of variable conductance heat pipes partially embedded within and thermally coupled to the radiator panels extend across the spacings and are thermally coupled to broad exterior surfaces of the heat exchangers by flanges. Temperature sensors monitor the temperature of process fluid flowing from the module through the heat exchanges. Thermal conduction between the heat exchangers and the radiator panels is regulated by heating a control fluid within the heat pipes to vary the effective thermal length of the heat pipes in inverse proportion to changes in the temperature of the process fluid.

Surface interaction of H2S, SO2, and SO3 on fullerene-like gallium nitride (GaN) nanostructure semiconductor

NASA Astrophysics Data System (ADS)

Salimifard, M.; Rad, A. Shokuhi; Mahanpoor, K.

2017-10-01

Density functional theory (DFT) using MPW1PW91 and B3LYP hybrid functionals was utilized for quantum-based investigations of three major sulfur compounds (H2S, SO2, and SO3) adsorption onto fullerene-like Ga12N12 nanocluster. All chemicals showed high chemisorption with the order of SO3>SO2>>H2S. Results of charge analysis showed that during adsorption, transfer of charge is from H2S to nanocluster while reverse direction of charge transfer is found for SO2 and SO3 molecules. Partial dissociation is found for adsorbates especially for SO2 and SO3 molecules. Results of thermochemistry analysis show negative values for enthalpy and Gibbs free energy of adsorption, confirming exothermic spontaneous process. Analysis of frontier molecular orbital (FMO) showed important role of orbital hybridizing towards formation of new bonds upon adsorption. As a result, we introduce Ga12N12 nanocluster as a strong adsorbent for sulfur compounds.

Carbon-free H2 production from ammonia triggered at room temperature with an acidic RuO2/γ-Al2O3 catalyst.

PubMed

Nagaoka, Katsutoshi; Eboshi, Takaaki; Takeishi, Yuma; Tasaki, Ryo; Honda, Kyoko; Imamura, Kazuya; Sato, Katsutoshi

2017-04-01

Ammonia has been suggested as a carbon-free hydrogen source, but a convenient method for producing hydrogen from ammonia with rapid initiation has not been developed. Ideally, this method would require no external energy input. We demonstrate hydrogen production by exposing ammonia and O 2 at room temperature to an acidic RuO 2 /γ-Al 2 O 3 catalyst. Because adsorption of ammonia onto the catalyst is exothermic, the catalyst bed is rapidly heated to the catalytic ammonia autoignition temperature, and subsequent oxidative decomposition of ammonia produces hydrogen. A differential calorimeter combined with a volumetric gas adsorption analyzer revealed a large quantity of heat evolved both with chemisorption of ammonia onto RuO 2 and acidic sites on the γ-Al 2 O 3 and with physisorption of multiple ammonia molecules.

NO ICE HYDROGENATION: A SOLID PATHWAY TO NH{sub 2}OH FORMATION IN SPACE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Congiu, Emanuele; Dulieu, Francois; Chaabouni, Henda

2012-05-01

Icy dust grains in space act as catalytic surfaces onto which complex molecules form. These molecules are synthesized through exothermic reactions from precursor radicals and, mostly, hydrogen atom additions. Among the resulting products are species of biological relevance, such as hydroxylamine-NH{sub 2}OH-a precursor molecule in the formation of amino acids. In this Letter, laboratory experiments are described that demonstrate NH{sub 2}OH formation in interstellar ice analogs for astronomically relevant temperatures via successive hydrogenation reactions of solid nitric oxide (NO). Inclusion of the experimental results in an astrochemical gas-grain model proves the importance of a solid-state NO+H reaction channel as amore » starting point for prebiotic species in dark interstellar clouds and adds a new perspective to the way molecules of biological importance may form in space.« less

Exploding Nitromethane in Silico, in Real Time.

PubMed

Fileti, Eudes Eterno; Chaban, Vitaly V; Prezhdo, Oleg V

2014-10-02

Nitromethane (NM) is widely applied in chemical technology as a solvent for extraction, cleaning, and chemical synthesis. NM was considered safe for a long time, until a railroad tanker car exploded in 1958. We investigate the detonation kinetics and explosion reaction mechanisms in a variety of systems consisting of NM, molecular oxygen, and water vapor. Reactive molecular dynamics allows us to simulate reactions in time-domain, as they occur in real life. High polarity of the NM molecule is shown to play a key role, driving the first exothermic step of the reaction. Rapid temperature and pressure growth stimulate the subsequent reaction steps. Oxygen is important for faster oxidation, whereas its optimal concentration is in agreement with the proposed reaction mechanism. Addition of water (50 mol %) inhibits detonation; however, water does not prevent detonation entirely. The reported results provide important insights for improving applications of NM and preserving the safety of industrial processes.

Review of the Two-Step H2O/CO2-Splitting Solar Thermochemical Cycle Based on Zn/ZnO Redox Reactions

PubMed Central

Loutzenhiser, Peter G.; Meier, Anton; Steinfeld, Aldo

2010-01-01

This article provides a comprehensive overview of the work to date on the two‑step solar H2O and/or CO2 splitting thermochemical cycles with Zn/ZnO redox reactions to produce H2 and/or CO, i.e., synthesis gas—the precursor to renewable liquid hydrocarbon fuels. The two-step cycle encompasses: (1) The endothermic dissociation of ZnO to Zn and O2 using concentrated solar energy as the source for high-temperature process heat; and (2) the non-solar exothermic oxidation of Zn with H2O/CO2 to generate H2/CO, respectively; the resulting ZnO is then recycled to the first step. An outline of the underlying science and the technological advances in solar reactor engineering is provided along with life cycle and economic analyses. PMID:28883361

Volcano plots in hydrogen electrocatalysis - uses and abuses.

PubMed

Quaino, Paola; Juarez, Fernanda; Santos, Elizabeth; Schmickler, Wolfgang

2014-01-01

Sabatier's principle suggests, that for hydrogen evolution a plot of the rate constant versus the hydrogen adsorption energy should result in a volcano, and several such plots have been presented in the literature. A thorough examination of the data shows, that there is no volcano once the oxide-covered metals are left out. We examine the factors that govern the reaction rate in the light of our own theory and conclude, that Sabatier's principle is only one of several factors that determine the rate. With the exception of nickel and cobalt, the reaction rate does not decrease for highly exothermic hydrogen adsorption as predicted, because the reaction passes through more suitable intermediate states. The case of nickel is given special attention; since it is a 3d metal, its orbitals are compact and the overlap with hydrogen is too low to make it a good catalyst.

Volcano plots in hydrogen electrocatalysis – uses and abuses

PubMed Central

Quaino, Paola; Juarez, Fernanda; Santos, Elizabeth

2014-01-01

Summary Sabatier’s principle suggests, that for hydrogen evolution a plot of the rate constant versus the hydrogen adsorption energy should result in a volcano, and several such plots have been presented in the literature. A thorough examination of the data shows, that there is no volcano once the oxide-covered metals are left out. We examine the factors that govern the reaction rate in the light of our own theory and conclude, that Sabatier’s principle is only one of several factors that determine the rate. With the exception of nickel and cobalt, the reaction rate does not decrease for highly exothermic hydrogen adsorption as predicted, because the reaction passes through more suitable intermediate states. The case of nickel is given special attention; since it is a 3d metal, its orbitals are compact and the overlap with hydrogen is too low to make it a good catalyst. PMID:24991521

Carbon-free H2 production from ammonia triggered at room temperature with an acidic RuO2/γ-Al2O3 catalyst

PubMed Central

Nagaoka, Katsutoshi; Eboshi, Takaaki; Takeishi, Yuma; Tasaki, Ryo; Honda, Kyoko; Imamura, Kazuya; Sato, Katsutoshi

2017-01-01

Ammonia has been suggested as a carbon-free hydrogen source, but a convenient method for producing hydrogen from ammonia with rapid initiation has not been developed. Ideally, this method would require no external energy input. We demonstrate hydrogen production by exposing ammonia and O2 at room temperature to an acidic RuO2/γ-Al2O3 catalyst. Because adsorption of ammonia onto the catalyst is exothermic, the catalyst bed is rapidly heated to the catalytic ammonia autoignition temperature, and subsequent oxidative decomposition of ammonia produces hydrogen. A differential calorimeter combined with a volumetric gas adsorption analyzer revealed a large quantity of heat evolved both with chemisorption of ammonia onto RuO2 and acidic sites on the γ-Al2O3 and with physisorption of multiple ammonia molecules. PMID:28508046

Fast start-up reactor for partial oxidation of methane with electrically-heated metallic monolith catalyst

NASA Astrophysics Data System (ADS)

Jung, Heon; Yoon, Wang Lai; Lee, Hotae; Park, Jong Soo; Shin, Jang Sik; La, Howon; Lee, Jong Dae

A palladium-washcoated metallic monolith catalyst is applied to the partial oxidation of methane to syngas. This catalyst is highly active at a gas hourly space velocity (GHSV) of 100,000 h -1. The compact partial oxidation (POX) reactor equipped with both 96 cc of the metallic monolith catalyst and an electrically-heated catalyst (EHC) has a start-up time of less than 1.5 min and a syngas generation capacity of 9.5 Nm 3 h -1. The POX reaction is sustained without the need for an external heater. With the stand-alone POX reactor, the methane conversion can be increased either by preheating the reactant mixture heat-exchanged with the product gas, or by supplying a larger amount of oxygen than is necessary for the reaction stoichiometry.

Selective Oxidation and Reactive Wetting during Galvanizing of a CMnAl TRIP-Assisted Steel

NASA Astrophysics Data System (ADS)

Bellhouse, E. M.; McDermid, J. R.

2011-09-01

A transformation induced plasticity (TRIP)-assisted steel with 0.2 pct C, 1.5 pct Mn, and 1.5 pct Al was successfully galvanized using a thermal cycle previously shown to produce an excellent combination of strength and ductility. The steel surface chemistry and oxide morphology were determined as a function of process atmosphere oxygen partial pressure. For the 220 K (-53 °C) dew point (dp) + 20 pct H2 atmosphere, the oxide morphology was a mixture of films and nodules. For the 243 K (-30 °C) dp + 5 pct H2 atmosphere, nodules of MnO were found primarily at grain boundaries. For the 278 K (+5 °C) dp + 5 pct H2 atmosphere, nodules of metallic Fe were found on the surface as a result of alloy element internal oxidation. The steel surface chemistry and oxide morphology were then related to the reactive wetting behavior during continuous hot dip galvanizing. Good wetting was obtained using the two lower oxygen partial pressure process atmospheres [220 K dp and 243 K dp (-53 °C dp and -30 °C dp)]. An increase in the number of bare spots was observed when using the higher oxygen partial pressure process atmosphere (+5 °C dp) due to the increased thickness of localized oxide films.

Heat up and failure of BWR upper internals during a severe accident

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robb, Kevin R.

In boiling water reactors, the shroud dome, separators, and dryers above the core are made of approximately 100,000 kg of stainless steel. During a severe accident in which the coolant boils away and exothermic oxidation of zirconium occurs, gases (steam and hydrogen) are superheated in the core region and pass through the upper internals. In this scenario, the upper internals can also be heated by thermal radiation from the hot degrading core. Historically, models of the upper internals have been relatively simple in severe accident codes. The upper internals are typically modeled in MELCOR as two lumped volumes with simplifiedmore » heat transfer characteristics and no structural integrity considerations, and with limited ability to oxidize, melt, and relocate. The potential for and the subsequent impact of the upper internals to heat up, oxidize, fail, and relocate during a severe accident was investigated. A higher fidelity representation of the shroud dome, steam separators, and steam driers was developed in MELCOR v1.8.6 by extending the core region upwards. The MELCOR modeling effort entailed adding 45 additional core cells and control volumes, 98 flow paths, and numerous control functions. The model accounts for the mechanical loading and structural integrity, oxidation, melting, flow area blockage, and relocation of the various components. Consistent with a previous study, the results indicate that the upper internals can reach high temperatures during a severe accident sufficient to lose their structural integrity and relocate. Finally, the additional 100 metric tons of stainless steel debris influences the subsequent in-vessel and ex-vessel accident progression.« less

Development of Self-Healing Zirconium-Silicide Coatings for Improved Performance Zirconium-Alloy Fuel Cladding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sridharan, Kumar; Mariani, Robert; Bai, Xianming

Zirconium-alloy fuel claddings have been used successfully in Light Water Reactors (LWR) for over four decades. However, under high temperature accident conditions, zirconium-alloys fuel claddings exhibit profuse exothermic oxidation accompanied by release of hydrogen gas due to the reaction with water/steam. Additionally, the ZrO 2 layer can undergo monoclinic to tetragonal to cubic phase transformations at high temperatures which can induce stresses and cracking. These events were unfortunately borne out in the Fukushima-Daiichi accident in in Japan in 2011. In reaction to such accident, protective oxidation-resistant coatings for zirconium-alloy fuel claddings has been extensively investigated to enhance safety margins inmore » accidents as well as fuel performance under normal operation conditions. Such surface modification could also beneficially affect fuel rod heat transfer characteristics. Zirconium-silicide, a candidate coating material, is particularly attractive because zirconium-silicide coating is expected to bond strongly to zirconium-alloy substrate. Intermetallic compound phases of zirconium-silicide have high melting points and oxidation of zirconium silicide produces highly corrosion resistant glassy zircon (ZrSiO 4) and silica (SiO 2) which possessing self-healing qualities. Given the long-term goal of developing such coatings for use with nuclear reactor fuel cladding, this work describes results of oxidation and corrosion behavior of bulk zirconium-silicide and fabrication of zirconium-silicide coatings on zirconium-alloy test flats, tube configurations, and SiC test flats. In addition, boiling heat transfer of these modified surfaces (including ZrSi 2 coating) during clad quenching experiments is discussed in detail.« less

Heat up and failure of BWR upper internals during a severe accident

DOE PAGES

Robb, Kevin R.

2017-02-21

In boiling water reactors, the shroud dome, separators, and dryers above the core are made of approximately 100,000 kg of stainless steel. During a severe accident in which the coolant boils away and exothermic oxidation of zirconium occurs, gases (steam and hydrogen) are superheated in the core region and pass through the upper internals. In this scenario, the upper internals can also be heated by thermal radiation from the hot degrading core. Historically, models of the upper internals have been relatively simple in severe accident codes. The upper internals are typically modeled in MELCOR as two lumped volumes with simplifiedmore » heat transfer characteristics and no structural integrity considerations, and with limited ability to oxidize, melt, and relocate. The potential for and the subsequent impact of the upper internals to heat up, oxidize, fail, and relocate during a severe accident was investigated. A higher fidelity representation of the shroud dome, steam separators, and steam driers was developed in MELCOR v1.8.6 by extending the core region upwards. The MELCOR modeling effort entailed adding 45 additional core cells and control volumes, 98 flow paths, and numerous control functions. The model accounts for the mechanical loading and structural integrity, oxidation, melting, flow area blockage, and relocation of the various components. Consistent with a previous study, the results indicate that the upper internals can reach high temperatures during a severe accident sufficient to lose their structural integrity and relocate. Finally, the additional 100 metric tons of stainless steel debris influences the subsequent in-vessel and ex-vessel accident progression.« less

New pathways for formation of acids and carbonyl products in low-temperature oxidation: the Korcek decomposition of γ-ketohydroperoxides.

PubMed

Jalan, Amrit; Alecu, Ionut M; Meana-Pañeda, Rubén; Aguilera-Iparraguirre, Jorge; Yang, Ke R; Merchant, Shamel S; Truhlar, Donald G; Green, William H

2013-07-31

We present new reaction pathways relevant to low-temperature oxidation in gaseous and condensed phases. The new pathways originate from γ-ketohydroperoxides (KHP), which are well-known products in low-temperature oxidation and are assumed to react only via homolytic O-O dissociation in existing kinetic models. Our ab initio calculations identify new exothermic reactions of KHP forming a cyclic peroxide isomer, which decomposes via novel concerted reactions into carbonyl and carboxylic acid products. Geometries and frequencies of all stationary points are obtained using the M06-2X/MG3S DFT model chemistry, and energies are refined using RCCSD(T)-F12a/cc-pVTZ-F12 single-point calculations. Thermal rate coefficients are computed using variational transition-state theory (VTST) calculations with multidimensional tunneling contributions based on small-curvature tunneling (SCT). These are combined with multistructural partition functions (Q(MS-T)) to obtain direct dynamics multipath (MP-VTST/SCT) gas-phase rate coefficients. For comparison with liquid-phase measurements, solvent effects are included using continuum dielectric solvation models. The predicted rate coefficients are found to be in excellent agreement with experiment when due consideration is made for acid-catalyzed isomerization. This work provides theoretical confirmation of the 30-year-old hypothesis of Korcek and co-workers that KHPs are precursors to carboxylic acid formation, resolving an open problem in the kinetics of liquid-phase autoxidation. The significance of the new pathways in atmospheric chemistry, low-temperature combustion, and oxidation of biological lipids are discussed.

New Pathways for Formation of Acids and Carbonyl Products in Low-Temperature Oxidation: The Korcek Decomposition of γ-Ketohydroperoxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jalan, Amrit; Alecu, Ionut M.; Meana-Pañeda, Rubén

2013-07-31

We present new reaction pathways relevant to low-temperature oxidation in gaseous and condensed phases. The new pathways originate from γ-ketohydroperoxides (KHP), which are well-known products in low-temperature oxidation and are assumed to react only via homolytic O-O dissociation in existing kinetic models. Our ab initio calculations identify new exothermic reactions of KHP forming a cyclic peroxide isomer, which decomposes via novel concerted reactions into carbonyl and carboxylic acid products. Geometries and frequencies of all stationary points are obtained using the M06-2X/MG3S DFT model chemistry, and energies are refined using RCCSD(T)-F12a/cc-pVTZ-F12 single-point calculations. Thermal rate coefficients are computed using variational transition-statemore » theory (VTST) calculations with multidimensional tunneling contributions based on small-curvature tunneling (SCT). These are combined with multistructural partition functions (QMS-T) to obtain direct dynamics multipath (MP-VTST/ SCT) gas-phase rate coefficients. For comparison with liquid-phase measurements, solvent effects are included using continuum dielectric solvation models. The predicted rate coefficients are found to be in excellent agreement with experiment when due consideration is made for acid-catalyzed isomerization. This work provides theoretical confirmation of the 30-year-old hypothesis of Korcek and co-workers that KHPs are precursors to carboxylic acid formation, resolving an open problem in the kinetics of liquid-phase autoxidation. The significance of the new pathways in atmospheric chemistry, low-temperature combustion, and oxidation of biological lipids are discussed.« less

Facile Preparation of Highly Conductive Metal Oxides by Self-Combustion for Solution-Processed Thermoelectric Generators.

PubMed

Kang, Young Hun; Jang, Kwang-Suk; Lee, Changjin; Cho, Song Yun

2016-03-02

Highly conductive indium zinc oxide (IZO) thin films were successfully fabricated via a self-combustion reaction for application in solution-processed thermoelectric devices. Self-combustion efficiently facilitates the conversion of soluble precursors into metal oxides by lowering the required annealing temperature of oxide films, which leads to considerable enhancement of the electrical conductivity of IZO thin films. Such enhanced electrical conductivity induced by exothermic heat from a combustion reaction consequently yields high performance IZO thermoelectric films. In addition, the effect of the composition ratio of In to Zn precursors on the electrical and thermoelectric properties of the IZO thin films was investigated. IZO thin films with a composition ratio of In:Zn = 6:2 at the low annealing temperature of 350 °C showed an enhanced electrical conductivity, Seebeck coefficient, and power factor of 327 S cm(-1), 50.6 μV K(-1), and 83.8 μW m(-1) K(-2), respectively. Moreover, the IZO thin film prepared at an even lower temperature of 300 °C retained a large power factor of 78.7 μW m(-1) K(-2) with an electrical conductivity of 168 S cm(-1). Using the combustive IZO precursor, a thermoelectric generator consisting of 15 legs was fabricated by a printing process. The thermoelectric array generated a thermoelectric voltage of 4.95 mV at a low temperature difference (5 °C). We suggest that the highly conductive IZO thin films by self-combustion may be utilized for fabricating n-type flexible printed thermoelectric devices.

Modeling the detailed kinetics of mitochondrial cytochrome c oxidase: Catalytic mechanism and nitric oxide inhibition

PubMed Central

Pannala, Venkat R.; Camara, Amadou K. S.

2016-01-01

Cytochrome c oxidase (CcO) catalyzes the exothermic reduction of O2 to H2O by using electrons from cytochrome c, and hence plays a crucial role in ATP production. Although details on the enzyme structure and redox centers involved in O2 reduction have been known, there still remains a considerable ambiguity on its mechanism of action, e.g., the number of sequential electrons donated to O2 in each catalytic step, the sites of protonation and proton pumping, and nitric oxide (NO) inhibition mechanism. In this work, we developed a thermodynamically constrained mechanistic mathematical model for the catalytic action of CcO based on available kinetic data. The model considers a minimal number of redox centers on CcO and couples electron transfer and proton pumping driven by proton motive force (PMF), and accounts for the inhibitory effects of NO on the reaction kinetics. The model is able to fit well all the available kinetic data under diverse experimental conditions with a physiologically realistic unique parameter set. The model predictions show that: 1) the apparent Km of O2 varies considerably and increases from fully reduced to fully oxidized cytochrome c depending on pH and the energy state of mitochondria, and 2) the intermediate enzyme states depend on pH and cytochrome c redox fraction and play a central role in coupling mitochondrial respiration to PMF. The developed CcO model can easily be integrated into existing mitochondrial bioenergetics models to understand the role of the enzyme in controlling oxidative phosphorylation in normal and disease conditions. PMID:27633738

Complete and Partial Photo-oxidation of Dissolved Organic Matter Draining Permafrost Soils.

PubMed

Ward, Collin P; Cory, Rose M

2016-04-05

Photochemical degradation of dissolved organic matter (DOM) to carbon dioxide (CO2) and partially oxidized compounds is an important component of the carbon cycle in the Arctic. Thawing permafrost soils will change the chemical composition of DOM exported to arctic surface waters, but the molecular controls on DOM photodegradation remain poorly understood, making it difficult to predict how inputs of thawing permafrost DOM may alter its photodegradation. To address this knowledge gap, we quantified the susceptibility of DOM draining the shallow organic mat and the deeper permafrost layer of arctic soils to complete and partial photo-oxidation and investigated changes in the chemical composition of each DOM source following sunlight exposure. Permafrost and organic mat DOM had similar lability to photomineralization despite substantial differences in initial chemical composition. Concurrent losses of carboxyl moieties and shifts in chemical composition during photodegradation indicated that photodecarboxylation could account for 40-90% of DOM photomineralized to CO2. Permafrost DOM had a higher susceptibility to partial photo-oxidation compared to organic mat DOM, potentially due to a lower abundance of phenolic moieties with antioxidant properties. These results suggest that photodegradation will likely continue to be an important control on DOM fate in arctic freshwaters as the climate warms and permafrost soils thaw.

Exothermic furnace module development. [space processing

NASA Technical Reports Server (NTRS)

Darnell, R. R.; Poorman, R. M.

1982-01-01

An exothermic furnace module was developed to rapidly heat and cool a 0.820-in. (2.1 cm) diameter by 2.75-in. (7.0 cm) long TZM molybdenum alloy crucible. The crucible contains copper, oxygen, and carbon for processing in a low-g environment. Peak temperatures of 1270 C were obtainable 3.5 min after start of ignition, and cooling below 950 C some 4.5 min later. These time-temperature relationships were conditioned for a foam-copper experiment, Space Processing Applications Rocket experiment 77-9, in a sounding rocket having a low-g period of 5 min.

Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

DOEpatents

Cortright, Randy D [Madison, WI; Dumesic, James A [Verona, WI

2012-04-10

A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

DOEpatents

Cortright, Randy D.; Dumesic, James A.

2013-04-02

A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

DOEpatents

Cortright, Randy D [Madison, WI; Dumesic, James A [Verona, WI

2011-01-18

A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

Boundary conditions for developing a safety concept for an exothermal reaction.

PubMed

Hauptmanns, Ulrich

2007-09-05

Kinetic calculations for an example exothermal chemical process, the production of TCB, are carried out. They address both parameter uncertainties and random failures of the cooling system. In this way, they enable one to establish comprehensive boundary conditions for a safety system in terms of unavailability, the quantities of the undesired by-product (TCDD) produced and the times available before a required intervention, if a pre-determined quantity of TCDD is tolerated. It is shown that accounting for stochastic effects and uncertainties derived from insufficient knowledge provides a broader and more realistic knowledge base for devising a viable safety concept.

Effects of inoculum type and bulk dissolved oxygen concentration on achieving partial nitrification by entrapped-cell-based reactors.

PubMed

Rongsayamanont, Chaiwat; Limpiyakorn, Tawan; Khan, Eakalak

2014-07-01

An entrapment of nitrifiers into gel matrix is employed as a tool to fulfill partial nitrification under non-limiting dissolved oxygen (DO) concentrations in bulk solutions. This study aims to clarify which of these two attributes, inoculum type and DO concentration in bulk solutions, is the decisive factor for partial nitrification in an entrapped-cell based system. Four polyvinyl alcohol entrapped inocula were prepared to have different proportions of nitrite-oxidizing bacteria (NOB) and nitrite-oxidizing activity. At a DO concentration of 3 mg l(-1), the number of active NOB cells in an inoculum was the decisive factor for partial nitrification enhancement. However, when the DO concentration was reduced to 2 mg l(-1), all entrapped cell inocula showed similar degrees of partial nitrification. The results suggested that with the lower bulk DO concentration, the preparation of entrapped cell inocula is not useful as the DO level becomes the decisive factor for achieving partial nitrification. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effect of PEEP and inhaled nitric oxide on pulmonary gas exchange during gaseous and partial liquid ventilation with small volumes of perfluorocarbon.

PubMed

Max, M; Kuhlen, R; Falter, F; Reyle-Hahn, M; Dembinski, R; Rossaint, R

2000-04-01

Partial liquid ventilation, positive end-expiratory pressure (PEEP) and inhaled nitric oxide (NO) can improve ventilation/perfusion mismatch in acute lung injury (ALI). The aim of the present study was to compare gas exchange and hemodynamics in experimental ALI during gaseous and partial liquid ventilation at two different levels of PEEP, with and without the inhalation of nitric oxide. Seven pigs (24+/-2 kg BW) were surfactant-depleted by repeated lung lavage with saline. Gas exchange and hemodynamic parameters were assessed in all animals during gaseous and subsequent partial liquid ventilation at two levels of PEEP (5 and 15 cmH2O) and intermittent inhalation of 10 ppm NO. Arterial oxygenation increased significantly with a simultaneous decrease in cardiac output when PEEP 15 cmH2O was applied during gaseous and partial liquid ventilation. All other hemodynamic parameters revealed no relevant changes. Inhalation of NO and instillation of perfluorocarbon had no additive effects on pulmonary gas exchange when compared to PEEP 15 cmH2O alone. In experimental lung injury, improvements in gas exchange are most distinct during mechanical ventilation with PEEP 15 cmH2O without significantly impairing hemodynamics. Partial liquid ventilation and inhaled NO did not cause an additive increase of PaO2.

Catalytic oxidation of light alkanes in presence of a base

DOEpatents

Bhinde, M.V.; Bierl, T.W.

1998-03-03

The presence of a base in the reaction mixture in a metal-ligand catalyzed partial oxidation of alkanes results in sustained catalyst activity, and in greater percent conversion as compared with oxidation in the absence of base, while maintaining satisfactory selectivity for the desired oxidation, for example the oxidation of isobutane to isobutanol. 1 fig.

Bismuth Oxide Nanoparticles Partially Substituted with EuIII, MnIV, and SiIV: Structural, Spectroscopic, and Optical Findings.

PubMed

Ortiz-Quiñonez, José-Luis; Zumeta-Dubé, Inti; Díaz, David; Nava-Etzana, Noel; Cruz-Zaragoza, Epifanio; Santiago-Jacinto, Patricia

2017-03-20

Interest in nanostructured partially substituted bismuth oxides has been increasing over the last years. Research on new synthesis methods, properties, and possible uses for these oxides is needed. The objective of this paper is to synthesize β-Bi 2 O 3 , β-Bi 2 O 3 :Eu 3+ , β-Bi 2 O 3 :Mn 4+ , Bi 12 Bi 0.8 O 19.2 , Bi 12 Bi 0.8 O 19.2 /Li + , Bi 12 MnO 20 , and Bi 12 SiO 20 nanoparticles and to investigate their structural, spectroscopic, and optical changes. Some of the causes that generated their properties are also discussed. These materials are important because the doping or partial substitution of bismuth oxide with these cations (Eu 3+ , Mn 4+ , and Si 4+ ) modifies some properties such as optical absorption, reactivity toward CO 2 , among others. X-ray diffraction (in powders), high-resolution transmission electron microscopy, Fourier transform infrared (FTIR), resonance Raman scattering, diffuse reflectance, and solid-state magic-angle-spinning 29 Si NMR were used for the characterization of the synthesized materials. We found that partial substitution of yellow Bi 12 Bi 0.8 O 19.2 with Mn 4+ and Si 4+ changed the color to green and whitish, respectively. New bands in the Raman scattering and FTIR spectra of these oxides are deeply discussed. Raman scattering spectroscopy was a valuable and reliable technique to detect the Eu 3+ and Mn 4+ cations as dopants in the bismuth oxides. The 29 Si chemical shift (δ) in Bi 12 SiO 20 was -78.16 ppm, whereas in SiO 2 , it was around -110 ppm. This considerable shift in Bi 12 SiO 20 occurred because of an increased shielding of the Si nucleus in the Si(O) 4 tetrahedron. This shielding was provided by the low-electronegativity and highly polarizable Bi cations. The isovalent doping of β-Bi 2 O 3 nanoparticles with Eu 3+ enhanced their thermal stability over 400 °C. Variation in the optical absorption and reactivity toward the acidic CO 2 molecule of the partially substituted bismuth oxides was explained on the basis of the optical basicity and ionic-covalent parameter concepts. Some possible uses for the synthesized oxides are suggested.

Autothermal hydrogen storage and delivery systems

DOEpatents

Pez, Guido Peter [Allentown, PA; Cooper, Alan Charles [Macungie, PA; Scott, Aaron Raymond [Allentown, PA

2011-08-23

Processes are provided for the storage and release of hydrogen by means of dehydrogenation of hydrogen carrier compositions where at least part of the heat of dehydrogenation is provided by a hydrogen-reversible selective oxidation of the carrier. Autothermal generation of hydrogen is achieved wherein sufficient heat is provided to sustain the at least partial endothermic dehydrogenation of the carrier at reaction temperature. The at least partially dehydrogenated and at least partially selectively oxidized liquid carrier is regenerated in a catalytic hydrogenation process where apart from an incidental employment of process heat, gaseous hydrogen is the primary source of reversibly contained hydrogen and the necessary reaction energy.

Morphology and phase evolution in microwave synthesized Al/FeO4 system.

PubMed

Chuan, Lee Chang; Yoshikawaa, Noboru; Taniguchia, Shoji

2011-01-01

Thermite reaction between Al/Fe3O4 raised by microwave (MW) heating under N2 atmosphere has been investigated, and compared with that by the electric furnace. In addition to the stoichiometric ratio for the production of metallic iron and alumina, mixture with slightly Lower in Al content is also studied. As thermite reaction is highly exothermic, melting of reaction product and destruction of microstructure may occur, which corresponds to the enthalpy and adiabatic temperature of the reaction. Hence, to avoid this problem, reaction coupled with a smaller driving force by controlling the MW ignition condition at low temperature exotherm has been investigated. The phase and microstructure evolution during the reaction were analyzed by differential thermal analysis (DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Thermogram of the DTA analysis, irrespective of their mole ratio, recorded two exothermic peaks, one at - 1310 degrees C and another one at - 1370 degrees C. When heated by microwave at 955 degrees C, the main products were identified as Al, FeO and Fe, minor amount of Fe3O4 and some Fe and alumina were detected. When heating to 1155 degrees C, Al and Fe3O4 peaks disappeared, formation of Fe-Al alloy was observed. For sample heated at 1265 degrees C, a porous body was obtained. Micron sized metal particles with complex morphology, irregular in size and shapes were formed, uniformly distributed within the spinel hercynite and/or alumina matrix. In contrast, conventional heating produced no porous products. Formation of alumina is also observed around the metal particles. Controlling of the reaction progress was possible while heating the sample by MW around the low temperature exotherm region, whereas the combustion wave could not be self-propagated.

Hydrogen rich gas generator

NASA Technical Reports Server (NTRS)

Houseman, J. (Inventor)

1976-01-01

A process and apparatus is described for producing a hydrogen rich gas by introducing a liquid hydrocarbon fuel in the form of a spray into a partial oxidation region and mixing with a mixture of steam and air that is preheated by indirect heat exchange with the formed hydrogen rich gas, igniting the hydrocarbon fuel spray mixed with the preheated mixture of steam and air within the partial oxidation region to form a hydrogen rich gas.

Methanol partial oxidation on Ag(111) from first principles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aljama, Hassan; Yoo, Jong Suk; Nørskov, Jens K.

In this work, we examine the thermochemistry and kinetics of the partial oxidation of methanol to formaldehyde on silver surfaces. Periodic density functional theory calculations employing the BEEF-vdW functional are used to identify the most stable phases of the silver surface under relevant reaction conditions and the reaction energetics are obtained on these surfaces. The calculated binding energies and transition state energies are used as input in a mean-field microkinetic model providing the reaction kinetics on silver surfaces under different reaction conditions. Our results show that, under conditions pertaining to methanol partial oxidation, oxygen is present at low concentrations andmore » it plays a critical role in the catalytic reaction. Surface oxygen promotes the reaction by activating the OH bond in methanol, thus forming a methoxy intermediate, which can react further to form formaldehyde. Finally, the dissociation of molecular oxygen is identified as the most critical step.« less

Methanol partial oxidation on Ag(111) from first principles

DOE PAGES

Aljama, Hassan; Yoo, Jong Suk; Nørskov, Jens K.; ...

2016-10-26

In this work, we examine the thermochemistry and kinetics of the partial oxidation of methanol to formaldehyde on silver surfaces. Periodic density functional theory calculations employing the BEEF-vdW functional are used to identify the most stable phases of the silver surface under relevant reaction conditions and the reaction energetics are obtained on these surfaces. The calculated binding energies and transition state energies are used as input in a mean-field microkinetic model providing the reaction kinetics on silver surfaces under different reaction conditions. Our results show that, under conditions pertaining to methanol partial oxidation, oxygen is present at low concentrations andmore » it plays a critical role in the catalytic reaction. Surface oxygen promotes the reaction by activating the OH bond in methanol, thus forming a methoxy intermediate, which can react further to form formaldehyde. Finally, the dissociation of molecular oxygen is identified as the most critical step.« less

Magnetic properties of partially oxidized Fe films

NASA Astrophysics Data System (ADS)

Garcia, Miguel Angel; Lopez-Dominguez, Victor; Hernando, Antonio

Hybrid magnetic nanostructures exhibit appealing properties due to interface and proximity effects. A simple and interesting system of hybrid magnetic nanomaterials are partially oxidized ferromagnetic films. We have fabricated Fe films by thermal evaporation and performed a partial oxidation to magnetite (Fe3O4) by annealing in air at different times and temperatures. The magnetic properties of the films evolve from those of pure metallic iron to pure magnetite, showing intermediate states where the proximity effects control the magnetic behavior. At some stages, the magnetization curves obtained by SQUID and MOKE magnetometry exhibit important differences due to the dissimilar contribution of both phases to the magneto-optical response of the system This work has been supported by the Ministerio Español de Economia y Competitividad (MINECO) MAT2013-48009-C4-1. V.L.D and M.A.G. acknowledges financial support from BBVA foundation.

The change of steel surface chemistry regarding oxygen partial pressure and dew point

NASA Astrophysics Data System (ADS)

Norden, Martin; Blumenau, Marc; Wuttke, Thiemo; Peters, Klaus-Josef

2013-04-01

By investigating the surface state of a Ti-IF, TiNb-IF and a MnCr-DP after several series of intercritical annealing, the impact of the annealing gas composition on the selective oxidation process is discussed. On behalf of the presented results, it can be concluded that not the general oxygen partial pressure in the annealing furnace, which is a result of the equilibrium reaction of water and hydrogen, is the main driving force for the selective oxidation process. It is shown that the amounts of adsorbed gases at the strip surface and the effective oxygen partial pressure resulting from the adsorbed gases, which is mainly dependent on the water content of the annealing furnace, is driving the selective oxidation processes occurring during intercritical annealing. Thus it is concluded, that for industrial applications the dew point must be the key parameter value for process control.

Bactericidal activity of partially oxidized nanodiamonds.

PubMed

Wehling, Julia; Dringen, Ralf; Zare, Richard N; Maas, Michael; Rezwan, Kurosch

2014-06-24

Nanodiamonds are a class of carbon-based nanoparticles that are rapidly gaining attention, particularly for biomedical applications, i.e., as drug carriers, for bioimaging, or as implant coatings. Nanodiamonds have generally been considered biocompatible with a broad variety of eukaryotic cells. We show that, depending on their surface composition, nanodiamonds kill Gram-positive and -negative bacteria rapidly and efficiently. We investigated six different types of nanodiamonds exhibiting diverse oxygen-containing surface groups that were created using standard pretreatment methods for forming nanodiamond dispersions. Our experiments suggest that the antibacterial activity of nanodiamond is linked to the presence of partially oxidized and negatively charged surfaces, specifically those containing acid anhydride groups. Furthermore, proteins were found to control the bactericidal properties of nanodiamonds by covering these surface groups, which explains the previously reported biocompatibility of nanodiamonds. Our findings describe the discovery of an exciting property of partially oxidized nanodiamonds as a potent antibacterial agent.

The chemical energy unit partial oxidation reactor operation simulation modeling

NASA Astrophysics Data System (ADS)

Mrakin, A. N.; Selivanov, A. A.; Batrakov, P. A.; Sotnikov, D. G.

2018-01-01

The chemical energy unit scheme for synthesis gas, electric and heat energy production which is possible to be used both for the chemical industry on-site facilities and under field conditions is represented in the paper. The partial oxidation reactor gasification process mathematical model is described and reaction products composition and temperature determining algorithm flow diagram is shown. The developed software product verification showed good convergence of the experimental values and calculations according to the other programmes: the temperature determining relative discrepancy amounted from 4 to 5 %, while the absolute composition discrepancy ranged from 1 to 3%. The synthesis gas composition was found out practically not to depend on the supplied into the partial oxidation reactor (POR) water vapour enthalpy and compressor air pressure increase ratio. Moreover, air consumption coefficient α increase from 0.7 to 0.9 was found out to decrease synthesis gas target components (carbon and hydrogen oxides) specific yield by nearly 2 times and synthesis gas target components required ratio was revealed to be seen in the water vapour specific consumption area (from 5 to 6 kg/kg of fuel).

Oxide nucleation on thin films of copper during in situ oxidation in an electron microscope

NASA Technical Reports Server (NTRS)

Heinemann, K.; Rao, D. B.; Douglass, D. L.

1975-01-01

Single-crystal copper thin films were oxidized at an isothermal temperature of 425 C and at an oxygen partial pressure of 0.005 torr. Specimens were prepared by epitaxial vapor deposition onto polished faces of rocksalt and were mounted in a hot stage inside the ultrahigh-vacuum chamber of a high-resolution electron microscope. An induction period of roughly 30 min was established which was independent of the film thickness but depended strongly on the oxygen partial pressure and to exposure to oxygen prior to oxidation. Neither stacking faults nor dislocations were found to be associated with the Cu2O nucleation sites. The experimental data, including results from oxygen dissolution experiments and from repetitive oxidation-reduction-oxidation sequences, fit well into the framework of an oxidation process involving the formation of a surface charge layer, oxygen saturation of the metal with formation of a supersaturated zone near the surface, and nucleation followed by surface diffusion of oxygen and bulk diffusion of copper for lateral and vertical oxide growth, respectively.

[Amnesic effect of nitrous oxide in gradual general anesthesia].

PubMed

Mouquet, W; Milhaud, A; Berlemont, D; Bachelet, Y

1989-05-01

The amnesic effect of nitrous oxide was studied in 50 women undergoing induced abortions under general anesthesia at a hospital in France. The request for general anesthesia was made by the practitioner, by psychologists working with the women, or by the women themselves. Patient ages ranged from 13-39 years and averaged 24. All patients were given 1 mg of dextromoramide. During the procedure a mixture of 50% nitrous oxide and 50% oxygen was delivered. The patient was asked to count to 200 and remember a list of 5 words, and questions were posed. The nitrous oxide was terminated at completion of the aspiration. Awakening occurred in under 5 minutes with nitrous oxide and oxygen and at around 10 minutes when halothane was added. 30 minutes after awakening the patient was questioned about the surgery and the preoperative talk and questions. None of the patients recalled insertion of the speculum. In 46 of the 50 cases a total or partial amnesia occurred. Among 20 patients given the nitrous oxide-oxygen mixture only, 15 experienced total, 4 partial, and 1 no amnesia. Among the 30 patients given the same gas mixture and halothane, 25 experienced total, 2 partial, and 3 no amnesia. Nitrous oxide has no effect on longterm memory and probably inhibits the 1st phase of memorization. There are several components of its mode of action: classic analgesia, a potentializing effect with morphinomimetics and other general anesthesias, and an amnesia of painful and disagreeable interventions.

Structural and electrical properties of sputter deposited ZnO thin films

NASA Astrophysics Data System (ADS)

Muhammed Shameem P., V.; Mekala, Laxman; Kumar, M. Senthil

2018-05-01

The growth of zinc oxide thin films having different oxygen content was achieved at ambient temperature by reactive dc magnetron sputtering technique and their structural and electrical properties are studied. The structural studies show that the films are polycrystalline with a preferential orientation of the grains along the c-axis [002], which increases with increase in oxygen partial pressure. The grain size and the surface roughness of the zinc oxide films are found to decrease with increasing oxygen partial pressure. It is observed that the resistivity of the zinc oxide films can be tuned from semiconducting to insulating regime by varying the oxygen content.

Effects of dissolved oxygen and pH on nitrous oxide production rates in autotrophic partial nitrification granules.

PubMed

Rathnayake, Rathnayake M L D; Oshiki, Mamoru; Ishii, Satoshi; Segawa, Takahiro; Satoh, Hisashi; Okabe, Satoshi

2015-12-01

The effects of dissolved oxygen (DO) and pH on nitrous oxide (N2O) production rates and pathways in autotrophic partial nitrification (PN) granules were investigated at the granular level. N2O was primarily produced by betaproteobacterial ammonia-oxidizing bacteria, mainly Nitrosomonas europaea, in the oxic surface layer (<200μm) of the autotrophic PN granules. N2O production increased with increasing bulk DO concentration owing to activation of the ammonia (i.e., hydroxylamine) oxidation in this layer. The highest N2O emissions were observed at pH 7.5, although the ammonia oxidation rate was unchanged between pH 6.5 and 8.5. Overall, the results of this study suggest that in situ analyses of PN granules are essential to gaining insight into N2O emission mechanisms in a granule. Copyright © 2015 Elsevier Ltd. All rights reserved.

Water Vapor Effects on Silica-Forming Ceramics

NASA Technical Reports Server (NTRS)

Opila, E. J.; Greenbauer-Seng, L. (Technical Monitor)

2000-01-01

Silica-forming ceramics such as SiC and Si3N4 are proposed for applications in combustion environments. These environments contain water vapor as a product of combustion. Oxidation of silica-formers is more rapid in water vapor than in oxygen. Parabolic oxidation rates increase with the water vapor partial pressure with a power law exponent value close to one. Molecular water vapor is therefore the mobile species in silica. Rapid oxidation rates and large amounts of gases generated during the oxidation reaction in high water vapor pressures may result in bubble formation in the silica and nonprotective scale formation. It is also shown that silica reacts with water vapor to form Si(OH)4(g). Silica volatility has been modeled using a laminar flow boundary layer controlled reaction equation. Silica volatility depends on the partial pressure of water vapor, the total pressure, and the gas velocity. Simultaneous oxidation and volatilization reactions have been modeled with paralinear kinetics.

Spin State Control of the Perovskite Rh/Co Oxides

PubMed Central

Terasaki, Ichiro; Shibasaki, Soichiro; Yoshida, Shin; Kobayashi, Wataru

2010-01-01

We show why and how the spin state of transition-metal ions affects the thermoelectric properties of transition-metal oxides by investigating two perovskite-related oxides. In the A-site ordered cobalt oxide Sr3YCo4O10.5, partial substitution of Ca for Sr acts as chemical pressure, which compresses the unit cell volume to drive the spin state crossover, and concomitantly changes the magnetization and thermopower. In the perovskite rhodium oxide LaRhO3, partial substitution of Sr for La acts as hole-doping, and the resistivity and thermopower decrease systematically with the Sr concentration. The thermopower remains large values at high temperatures (>150 μV/K at 800 K), which makes a remarkable contrast to La1−xSrxCoO3. We associate this with the stability of the low spin state of the Rh3+ ions.

A Self-Propagating Foaming Process of Porous Al-Ni Intermetallics Assisted by Combustion Reactions

PubMed Central

Kobashi, Makoto; Kanetake, Naoyuki

2009-01-01

The self-propagating foaming process of porous Al-Ni intermetallics was investigated. Aluminum and nickel powders were blended, and titanium and boron carbide powders were added as reactive exothermic agents. The blended powder was extruded to make a rod-shape precursor. Only one end of the rod precursor was heated to ignite the reaction. The reaction propagated spontaneously throughout the precursor. Pore formation took place at the same time as the reaction occurred. Adding the exothermic agent was effective to increase the porosity. Preheating the precursor before the ignition was also very effective to produce porous Al-Ni intermetallics with high porosity.

Combustion-Assisted Photonic Annealing of Printable Graphene Inks via Exothermic Binders.

PubMed

Secor, Ethan B; Gao, Theodore Z; Dos Santos, Manuel H; Wallace, Shay G; Putz, Karl W; Hersam, Mark C

2017-09-06

High-throughput and low-temperature processing of high-performance nanomaterial inks is an important technical challenge for large-area, flexible printed electronics. In this report, we demonstrate nitrocellulose as an exothermic binder for photonic annealing of conductive graphene inks, leveraging the rapid decomposition kinetics and built-in energy of nitrocellulose to enable versatile process integration. This strategy results in superlative electrical properties that are comparable to extended thermal annealing at 350 °C, using a pulsed light process that is compatible with thermally sensitive substrates. The resulting porous microstructure and broad liquid-phase patterning compatibility are exploited for printed graphene microsupercapacitors on paper-based substrates.

Joining of parts via magnetic heating of metal aluminum powders

DOEpatents

Baker, Ian

2013-05-21

A method of joining at least two parts includes steps of dispersing a joining material comprising a multi-phase magnetic metal-aluminum powder at an interface between the at least two parts to be joined and applying an alternating magnetic field (AMF). The AMF has a magnetic field strength and frequency suitable for inducing magnetic hysteresis losses in the metal-aluminum powder and is applied for a period that raises temperature of the metal-aluminum powder to an exothermic transformation temperature. At the exothermic transformation temperature, the metal-aluminum powder melts and resolidifies as a metal aluminide solid having a non-magnetic configuration.

Analysis of potential hazards associated with 241Am loaded resins from nitrate media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schulte, Louis D.; Rubin, Jim; Fife, Keith William

2016-02-19

LANL has been contacted to provide possible assistance in safe disposition of a number of 241Am-bearing materials associated with local industrial operations. Among the materials are ion exchange resins which have been in contact with 241Am and nitric acid, and which might have potential for exothermic reaction. The purpose of this paper is to analyze and define the resin forms and quantities to the extent possible from available data to allow better bounding of the potential reactivity hazard of the resin materials. An additional purpose is to recommend handling procedures to minimize the probability of an uncontrolled exothermic reaction.

New findings on the influence of carbon surface curvature on energetics of benzene adsorption from aqueous solutions

NASA Astrophysics Data System (ADS)

Wiśniewski, Marek; Werengowska-Ciećwierz, Karolina; Terzyk, Artur P.

2015-01-01

Immersional measurements of benzene adsorption form dilute aqueous solutions are reported for the first time together with the measurements of the enthalpy of benzene adsorption. Benzene adsorption from aqueous solution is an exothermic process. Our results show that with the decrease in carbon nanotube diameter the process becomes more exothermic, and the enthalpy of benzene adsorption correlates with the BET surface area and the electrostatic field strength of the tubes. Possible explanations of the results are proposed, and the most probable is that the change in carbon hybridisation with curvature leads to creation of stronger energetically adsorption sites than observed for graphite.

Characterization of Hydrogen Interactions with δ-Pu using Electronic Structure Theory

NASA Astrophysics Data System (ADS)

Taylor, Christopher D.; Hernandez, Sarah C.

2012-02-01

The generalized gradient approximation to density functional theory was used to study surface, bulk, defect, and reaction states of hydrogen in δ-Pu. The quasi-disordered anti-ferromagnetic arrangement gave a volume of 24.1 å^3 and a bulk modulus of 48.1 GPa for δ-Pu, in reasonable agreement with the experimental values of 24.9 å^3 and 30-35 GPa. This arrangement was thus subsequently used for all calculations. We have determined that hydrogen interactions with δ-Pu are exothermic in character at all levels ranging from dissociative chemisorption to interstitial absorption, the formation of hydrogen-vacancy complexes, and generation of a hydride phase. The exothermic character of these interactions appears to be the reason for the rapid hydriding reaction, which has been determined experimentally to be essentially a barrierless process. The anionic character is observed to be retained. Our studies also indicate that vacancies do not appear to be strong traps for hydrogen, since the interstitial absorption sites are exothermic in nature. We will propose a scheme by which hydrogen interacts with Pu. Results will be compared with previous studies in the literature where available.

Exothermic low temperature sintering of Cu nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mittal, Jagjiwan; Lin, Kwang-Lung, E-mail: matkllin@mail.ncku.edu.tw

2015-11-15

Sintering of the Cu nanoparticle at low temperatures resulted in exothermic behavior after its initiation. The calorimetry study of the heating of a 20 nm copper nanoparticles agglomerate revealed the evolution of 41.17 J/g of heat between 170 °C and 270 °C. High resolution transmission electron microscopy (HRTEM) images indicated that the heat generation was accompanied by sintering. The surface energy of the 20 nm copper nanoparticles was estimated to be 1.23 × 10{sup 3} erg/cm{sup 2} based on the heat released during sintering. The in situ high resolution transmission electron microscope (HRTEM) investigation showed that vigorous sintering occurred betweenmore » 217 and 234 °C, which took place through the dislocation sintering mechanism. - Highlights: • Calorimetry showed exothermic behavior during heating of Cu nanoparticles between 170 and 270 °C. • Heat released due to the sintering of Cu nanoparticles was demonstrated by HRTEM. • Surface energy of 20 nm copper nanoparticles was estimated to be 1.23 × 10{sup 3} erg/cm{sup 2} during sintering. • Growth in crystallite sizes during sintering is disclosed by X-ray diffraction. • In situ HRTEM heating study showed occurrence of sintering through dislocation mechanism.« less

Low-cost single-crystal turbine blades, volume 2

NASA Technical Reports Server (NTRS)

Strangman, T. E.; Dennis, R. E.; Heath, B. R.

1984-01-01

The overall objectives of Project 3 were to develop the exothermic casting process to produce uncooled single-crystal (SC) HP turbine blades in MAR-M 247 and higher strength derivative alloys and to validate the materials process and components through extensive mechanical property testing, rig testing, and 200 hours of endurance engine testing. These Program objectives were achieved. The exothermic casting process was successfully developed into a low-cost nonproperietary method for producing single-crystal castings. Single-crystal MAR-M 247 and two derivatives DS alloys developed during this project, NASAIR 100 and SC Alloy 3, were fully characterized through mechanical property testing. SC MAR-M 247 shows no significant improvement in strength over directionally solidified (DS) MAR-M 247, but the derivative alloys, NASAIR 100 and Alloy 3, show significant tensile and fatigue improvements. Firtree testing, holography, and strain-gauge rig testing were used to determine the effects of the anisotropic characteristics of single-crystal materials. No undesirable characteristics were found. In general, the single-crystal material behaved similarly to DS MAR-M 247. Two complete engine sets of SC HP turbine blades were cast using the exothermic casting process and fully machined. These blades were successfully engine-tested.

Warming preterm infants in the delivery room: polyethylene bags, exothermic mattresses or both?

PubMed

McCarthy, Lisa K; O'Donnell, Colm P F

2011-12-01

To compare the admission temperature of infants treated with polyethylene bags alone to infants treated with exothermic mattresses in addition to bags in the delivery room. We prospectively studied infants born at <31 weeks' gestation who were placed in bags at birth. Some infants were also placed on mattresses. Admission axillary temperatures were measured in all infants on admission to the neonatal intensive care. We compared the temperatures of infants treated with bags alone to those treated with mattresses and bags. We studied 43 infants: 15 were treated with bags while 28 were treated with a bag and mattress. Mean admission temperature was similar between the groups. Hypothermia and hyperthermia occurred more frequently in infants treated with a bag and mattress, and more infants treated with a bag had admission temperatures 36.5-37.5°C. The use of exothermic mattresses in addition to polyethylene bags, particularly in younger, smaller newborns, may result in more hypothermia and hyperthermia on admission. A randomised controlled trial is necessary to determine which strategy results in more infants having admission temperatures in the normal range. © 2011 The Author(s)/Acta Paediatrica © 2011 Foundation Acta Paediatrica.

Influence of heat losses on nonlinear fingering dynamics of exothermic autocatalytic fronts

NASA Astrophysics Data System (ADS)

D'Hernoncourt, J.; De Wit, A.

2010-06-01

Across traveling exothermic autocatalytic fronts, a density jump can be observed due to changes in composition and temperature. These density changes are prone to induce buoyancy-driven convection around the front when the propagation takes place in absence of gel within the gravity field. Most recent experiments devoted to studying such reaction-diffusion-convection dynamics are performed in Hele-Shaw cells, two glass plates separated by a thin gap width and filled by the chemical solutions. We investigate here the influence of heat losses through the walls of such cells on the nonlinear fingering dynamics of exothermic autocatalytic fronts propagating in vertical Hele-Shaw cells. We show that these heat losses increase tip splittings and modify the properties of the flow field. A comparison of the differences between the dynamics in reactors with respectively insulating and conducting walls is performed as a function of the Lewis number Le, the Newton cooling coefficient α quantifying the amplitude of heat losses and the width of the system. We find that tip splitting is enhanced for intermediate values of α while coarsening towards one single finger dominates for insulated systems or large values of α leading to situations equivalent to isothermal ones.

Advancing the frontiers in nanocatalysis, biointerfaces, and renewable energy conversion by innovations of surface techniques.

PubMed

Somorjai, Gabor A; Frei, Heinz; Park, Jeong Y

2009-11-25

The challenge of chemistry in the 21st century is to achieve 100% selectivity of the desired product molecule in multipath reactions ("green chemistry") and develop renewable energy based processes. Surface chemistry and catalysis play key roles in this enterprise. Development of in situ surface techniques such as high-pressure scanning tunneling microscopy, sum frequency generation (SFG) vibrational spectroscopy, time-resolved Fourier transform infrared methods, and ambient pressure X-ray photoelectron spectroscopy enabled the rapid advancement of three fields: nanocatalysts, biointerfaces, and renewable energy conversion chemistry. In materials nanoscience, synthetic methods have been developed to produce monodisperse metal and oxide nanoparticles (NPs) in the 0.8-10 nm range with controlled shape, oxidation states, and composition; these NPs can be used as selective catalysts since chemical selectivity appears to be dependent on all of these experimental parameters. New spectroscopic and microscopic techniques have been developed that operate under reaction conditions and reveal the dynamic change of molecular structure of catalysts and adsorbed molecules as the reactions proceed with changes in reaction intermediates, catalyst composition, and oxidation states. SFG vibrational spectroscopy detects amino acids, peptides, and proteins adsorbed at hydrophobic and hydrophilic interfaces and monitors the change of surface structure and interactions with coadsorbed water. Exothermic reactions and photons generate hot electrons in metal NPs that may be utilized in chemical energy conversion. The photosplitting of water and carbon dioxide, an important research direction in renewable energy conversion, is discussed.

Pure rotational CARS thermometry studies of low-temperature oxidation kinetics in air and ethene-air nanosecond pulse discharge plasmas

NASA Astrophysics Data System (ADS)

Zuzeek, Yvette; Choi, Inchul; Uddi, Mruthunjaya; Adamovich, Igor V.; Lempert, Walter R.

2010-03-01

Pure rotational CARS thermometry is used to study low-temperature plasma assisted fuel oxidation kinetics in a repetitive nanosecond pulse discharge in ethene-air at stoichiometric and fuel lean conditions at 40 Torr pressure. Air and fuel-air mixtures are excited by a burst of high-voltage nanosecond pulses (peak voltage, 20 kV; pulse duration, ~ 25 ns) at a 40 kHz pulse repetition rate and a burst repetition rate of 10 Hz. The number of pulses in the burst is varied from a few pulses to a few hundred pulses. The results are compared with the previously developed hydrocarbon-air plasma chemistry model, modified to incorporate non-empirical scaling of the nanosecond discharge pulse energy coupled to the plasma with number density, as well as one-dimensional conduction heat transfer. Experimental time-resolved temperature, determined as a function of the number of pulses in the burst, is found to agree well with the model predictions. The results demonstrate that the heating rate in fuel-air plasmas is much faster compared with air plasmas, primarily due to energy release in exothermic reactions of fuel with O atoms generated by the plasma. It is found that the initial heating rate in fuel-air plasmas is controlled by the rate of radical (primarily O atoms) generation and is nearly independent of the equivalence ratio. At long burst durations, the heating rate in lean fuel air-mixtures is significantly reduced when all fuel is oxidized.

Instruments for Characterizing Carbon and Sulfur-Resistant Core-Shell Redox Catalysts for Combined Hydrocarbon Reforming and Water-Splitting

DTIC Science & Technology

2015-11-22

SECURITY CLASSIFICATION OF: This project aims to investigate a novel core-shell redox catalyst for combined methane partial oxidation and water...Properly designed redox catalyst are shown to be highly effective for syngas production (from methane ) and water-splitting. The resulting syngas has a...27709-2211 redox catalyst, methane partial oxidation, water-splitting REPORT DOCUMENTATION PAGE 11. SPONSOR/MONITOR’S REPORT NUMBER(S) 10. SPONSOR

Partial oxidation of dimethyl ether using the structured catalyst Rh/Al2O3/Al prepared through the anodic oxidation of aluminum.

PubMed

Yu, B Y; Lee, K H; Kim, K; Byun, D J; Ha, H P; Byun, J Y

2011-07-01

The partial oxidation of dimethyl ether (DME) was investigated using the structured catalyst Rh/Al2O3/Al. The porous Al2O3 layer was synthesized on the aluminum plate through anodic oxidation in an oxalic-acid solution. It was observed that about 20 nm nanopores were well developed in the Al2O3 layer. The thickness of Al2O3 layer can be adjusted by controlling the anodizing time and current density. After pore-widening and hot-water treatment, the Al2O3/Al plate was calcined at 500 degrees C for 3 h. The obtained delta-Al2O3 had a specific surface area of 160 m2/g, making it fit to be used as a catalyst support. A microchannel reactor was designed and fabricated to evaluate the catalytic activity of Rh/Al2O3/Al in the partial oxidation of DME. The structured catalyst showed an 86% maximum hydrogen yield at 450 degrees C. On the other hand, the maximum syngas yield by a pack-bed-type catalyst could be attained by using a more than fivefold Rh amount compared to that used in the structured Rh/Al2O3/Al catalyst.

Separation medium containing thermally exfoliated graphite oxide

NASA Technical Reports Server (NTRS)

Prud'homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor); Herrera-Alonso, Margarita (Inventor)

2012-01-01

A separation medium, such as a chromatography filling or packing, containing a modified graphite oxide material, which is a thermally exfoliated graphite oxide with a surface area of from about 300 m.sup.2/g to 2600 m.sup.2/g, wherein the thermally exfoliated graphite oxide has a surface that has been at least partially functionalized.

Mechanistic Insights into the Catalytic Oxidation of Carboxylic Acids on Au/TiO 2: Partial Oxidation of Propionic and Butyric Acid to Gold Ketenylidene through Unsaturated Acids

DOE Office of Scientific and Technical Information (OSTI.GOV)

McEntee, Monica; Tang, Wenjie; Neurock, Matthew

Here, the partial oxidation of model C 2–C 4 (acetic, propionic, and butyric) carboxylic acids on Au/TiO 2 catalysts consisting of Au particles ~3 nm in size was investigated using transmission infrared spectroscopy and density functional theory. All three acids readily undergo oxidative dehydrogenation on Au/TiO 2. Propionic and butyric acid dehydrogenate at the C2–C3 positions, whereas acetic acid dehydrogenates at the C1–C2 position. The resulting acrylate and crotonate intermediates are subsequently oxidized to form β-keto acids that decarboxylate. All three acids form a gold ketenylidene intermediate, Au 2C=C=O, along the way to their full oxidation to form CO 2.more » Infrared measurements of Au 2C=C=O formation as a function of time provides a surface spectroscopic probe of the kinetics for the activation and oxidative dehydrogenation of the alkyl groups in the carboxylate intermediates that form.« less

The effect of sub-oxide phases on the transparency of tin-doped gallium oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, K.; Schelhas, L. T.; Siah, S. C.

2016-10-03

There have been a number of studies on the fabrication of Sn-doped gallium oxide (Ga 2O 3:Sn) films with both conductive and transparent properties using a variety of deposition methods. However, often, synthesis results in films that are not transparent. In this paper, we examine the mechanisms underlying these results in Ga 2O 3:Sn thin films prepared at various growth temperatures, Sn concentrations, and oxygen partial pressures. With X-ray absorption spectroscopy, transmission electron microscopy and energy dispersive spectroscopy, we find that when films are grown under the oxygen deficient conditions there are Ga sub-oxide and SnOx phases in the Gamore » 2O 3:Sn thin film. These Ga sub-oxide phases are only found in non-transparent films, and so we infer that the Ga sub-oxide is responsible for the non-transparency. These observations suggest that to obtain transparent Ga 2O 3:Sn, films deposition or subsequent annealing must be carefully controlled in both temperature and oxygen partial pressure to avoid the formation of Ga sub-oxide phases.« less

Mechanistic Insights into the Catalytic Oxidation of Carboxylic Acids on Au/TiO 2: Partial Oxidation of Propionic and Butyric Acid to Gold Ketenylidene through Unsaturated Acids

DOE PAGES

McEntee, Monica; Tang, Wenjie; Neurock, Matthew; ...

2014-12-12

Here, the partial oxidation of model C 2–C 4 (acetic, propionic, and butyric) carboxylic acids on Au/TiO 2 catalysts consisting of Au particles ~3 nm in size was investigated using transmission infrared spectroscopy and density functional theory. All three acids readily undergo oxidative dehydrogenation on Au/TiO 2. Propionic and butyric acid dehydrogenate at the C2–C3 positions, whereas acetic acid dehydrogenates at the C1–C2 position. The resulting acrylate and crotonate intermediates are subsequently oxidized to form β-keto acids that decarboxylate. All three acids form a gold ketenylidene intermediate, Au 2C=C=O, along the way to their full oxidation to form CO 2.more » Infrared measurements of Au 2C=C=O formation as a function of time provides a surface spectroscopic probe of the kinetics for the activation and oxidative dehydrogenation of the alkyl groups in the carboxylate intermediates that form.« less

The effect of sub-oxide phases on the transparency of tin-doped gallium oxide

DOE PAGES

Lim, K.; Schelhas, L. T.; Siah, S. C.; ...

2016-10-07

There have been a number of studies on the fabrication of Sn-doped gallium oxide (Ga 2O 3:Sn) films with both conductive and transparent properties using a variety of deposition methods. However, often, synthesis results in films that are not transparent. In this paper, we examine the mechanisms underlying these results in Ga 2O 3:Sn thin films prepared at various growth temperatures, Sn concentrations, and oxygen partial pressures. With X-ray absorption spectroscopy, transmission electron microscopy and energy dispersive spectroscopy, we find that when films are grown under the oxygen deficient conditions there are Ga sub-oxide and SnO x phases in themore » Ga 2O 3:Sn thin film. These Ga sub-oxide phases are only found in non-transparent films, and so we infer that the Ga sub-oxide is responsible for the non-transparency. Furthermore, these observations suggest that to obtain transparent Ga 2O 3:Sn, films deposition or subsequent annealing must be carefully controlled in both temperature and oxygen partial pressure to avoid the formation of Ga sub-oxide phases.« less

The influence of oscillations on product selectivity during the palladium-catalysed phenylacetylene oxidative carbonylation reaction.

PubMed

Novakovic, Katarina; Grosjean, Christophe; Scott, Stephen K; Whiting, Andrew; Willis, Mark J; Wright, Allen R

2008-02-07

This paper reports on the influence of oscillations on product selectivity as well as the dynamics of product formation during the palladium-catalysed phenylacetylene oxidative carbonylation reaction in a catalytic system (PdI2, KI, Air, NaOAc in methanol). The occurrence of the pH oscillations is related to PdI2 granularity and the initial pH drop after phenylacetylene addition. To achieve pH and reaction exotherm oscillations regulation of the amount of PdI2 is required, ensuring that the initial pH does not fall significantly below 1 after phenylacetylene addition. Experiments in both oscillatory and non-oscillatory pH regimes were performed in an HEL SIMULAR reaction calorimeter with the concentration-time profiles measured using a GC-MS. It is demonstrated that when operating in an oscillatory pH regime product formation may be suppressed until oscillations occur after which there is a steep increase in the formation of Z-2-phenyl-but-2-enedioic acid dimethyl ester. When operating in non-oscillatory pH mode the products are formed steadily over time with the main products being Z-2-phenyl-but-2-enedioic acid dimethyl ester, 2-phenyl-acrylic acid methyl ester and E-3-phenyl-acrylic acid methyl ester.

Radiation damage and annealing in plutonium tetrafluoride

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCoy, Kaylyn; Casella, Amanda; Sinkov, Sergey

Plutonium tetrafluoride that was separated prior to 1966 at the Hanford Site in Washington State was analyzed at the Pacific Northwest National Laboratory (PNNL) in 2015 and 2016. The plutonium tetrafluoride, as received, was an off-normal color and considering the age of the plutonium, there were questions about the condition of the material. These questions had to be answered in order to determine the suitability of the material for future use or long-term storage. Therefore, Thermogravimetric/Differential Thermal Analysis and X-ray Diffraction evaluations were conducted to determine the plutonium’s crystal structure, oxide content, and moisture content; these analyses reported that themore » plutonium was predominately amorphous and tetrafluoride, with an oxide content near ten percent. Freshly fluorinated plutonium tetrafluoride is known to be monoclinic. During the initial Thermogravimetric/Differential Thermal analyses, it was discovered that an exothermic event occurred within the material near 414°C. X-ray Diffraction analyses were conducted on the annealed tetrafluoride. The X-ray Diffraction analyses indicated that some degree of recrystallization occurred in conjunction with the 414°C event. The following commentary describes the series of Thermogravimetric/Differential Thermal and X-ray Diffraction analyses that were conducted as part of this investigation at PNNL, in collaboration with the University of Utah Nuclear Engineering Program.« less

Kinetics of (reversible) internal reforming of methane in solid oxide fuel cells under stationary and APU conditions

NASA Astrophysics Data System (ADS)

Timmermann, H.; Sawady, W.; Reimert, R.; Ivers-Tiffée, E.

The internal reforming of methane in a solid oxide fuel cell (SOFC) is investigated and modeled for flow conditions relevant to operation. To this end, measurements are performed on anode-supported cells (ASC), thereby varying gas composition (y CO = 4-15%, yH2 = 5 - 17 % , yCO2 = 6 - 18 % , yH2O = 2 - 30 % , yCH4 = 0.1 - 20 %) and temperature (600-850 °C). In this way, operating conditions for both stationary applications (methane-rich pre-reformate) as well as for auxiliary power unit (APU) applications (diesel-POX reformate) are represented. The reforming reaction is monitored in five different positions alongside the anodic gas channel by means of gas chromatography. It is shown that methane is converted in the flow field for methane-rich gas compositions, whereas under operation with diesel reformate the direction of the reaction is reversed for temperatures below 675 °C, i.e. (exothermic) methanation occurs along the anode. Using a reaction model, a rate equation for reforming could be derived which is also valid in the case of methanation. By introducing this equation into the reaction model the methane conversion along a catalytically active Ni-YSZ cermet SOFC anode can be simulated for the operating conditions specified above.

Activation barriers for series of exothermic homologous reactions. V. Boron group diatomic species reactions

NASA Astrophysics Data System (ADS)

Blue, Alan S.; Belyung, David P.; Fontijn, Arthur

1997-09-01

Semiempirical configuration interaction (SECI) theory is used to predict activation barriers E, as defined by k(T)=ATn exp(-E/RT). Previously SECI has been applied to homologous series of oxidation reactions of s1, s2, and s2p1 metal atoms. Here it is extended to oxidation reactions of diatomic molecules containing one s2p1 atom. E values are calculated for the reactions of BH, BF, BCl, AlF, AlCl, AlBr, GaF, GaI, InCl, InBr, InI, TlF, TlCl, TlBr, and TlI with O2, CO2, SO2, or N2O. These values correlate with the sums of the ionization potentials and Σ-Π promotion energies of the former minus the electron affinities of the latter. In the earlier work n was chosen somewhat arbitrarily, which affected the absolute values of E. Here it is shown that examination of available experimental and theoretical results allows determination of the best values of n. Using this approach yields n=1.9 for the present series. For the seven reactions which have been studied experimentally, the average deviation of the SECI activation barrier prediction from experiment is 4.0 kJ mol-1. Energy barriers are calculated for another 52 reactions.

Novel electrical energy storage system based on reversible solid oxide cells: System design and operating conditions

NASA Astrophysics Data System (ADS)

Wendel, C. H.; Kazempoor, P.; Braun, R. J.

2015-02-01

Electrical energy storage (EES) is an important component of the future electric grid. Given that no other widely available technology meets all the EES requirements, reversible (or regenerative) solid oxide cells (ReSOCs) working in both fuel cell (power producing) and electrolysis (fuel producing) modes are envisioned as a technology capable of providing highly efficient and cost-effective EES. However, there are still many challenges and questions from cell materials development to system level operation of ReSOCs that should be addressed before widespread application. This paper presents a novel system based on ReSOCs that employ a thermal management strategy of promoting exothermic methanation within the ReSOC cell-stack to provide thermal energy for the endothermic steam/CO2 electrolysis reactions during charging mode (fuel producing). This approach also serves to enhance the energy density of the stored gases. Modeling and parametric analysis of an energy storage concept is performed using a physically based ReSOC stack model coupled with thermodynamic system component models. Results indicate that roundtrip efficiencies greater than 70% can be achieved at intermediate stack temperature (680 °C) and elevated stack pressure (20 bar). The optimal operating condition arises from a tradeoff between stack efficiency and auxiliary power requirements from balance of plant hardware.

Radiation damage and annealing in plutonium tetrafluoride

DOE PAGES

McCoy, Kaylyn; Casella, Amanda; Sinkov, Sergey; ...

2017-08-03

A sample of plutonium tetrafluoride that was separated prior to 1966 at the Hanford Site in Washington State was analyzed at the Pacific Northwest National Laboratory (PNNL) in 2015 and 2016. The plutonium tetrafluoride, as received, was an unusual color and considering the age of the plutonium, there were questions about the condition of the material. These questions had to be answered in order to determine the suitability of the material for future use or long-term storage. Therefore, thermogravimetric/differential thermal analysis and X-ray diffraction evaluations were conducted to determine the plutonium's crystal structure, oxide content, and moisture content; these analysesmore » reported that the plutonium was predominately amorphous and tetrafluoride, with an oxide content near ten percent. Freshly fluorinated plutonium tetrafluoride is known to be monoclinic. And during the initial thermogravimetric/differential thermal analyses, it was discovered that an exothermic event occurred within the material near 414 °C. X-ray diffraction analyses were conducted on the annealed tetrafluoride. The X-ray diffraction analyses indicated that some degree of recrystallization occurred in conjunction with the 414 °C event. This commentary describes the series of thermogravimetric/differential thermal and X-ray diffraction analyses that were conducted as part of this investigation at PNNL.« less

Effects of pH and seasonal temperature variation on simultaneous partial nitrification and anammox in free-water surface wetlands.

PubMed

He, Yuling; Tao, Wendong; Wang, Ziyuan; Shayya, Walid

2012-11-15

Design considerations to enhance simultaneous partial nitrification and anammox in constructed wetlands are largely unknown. This study examined the effects of pH and seasonal temperature variation on simultaneous partial nitrification and anammox in two free-water surface wetlands. In order to enhance partial nitrification and inhibit nitrite oxidation, furnace slag was placed on the rooting substrate to maintain different pH levels in the wetland water. The wetlands were batch operated for dairy wastewater treatment under oxygen-limited conditions at a cycle time of 7 d. Fluorescence in situ hybridization analysis found that aerobic ammonium oxidizing bacteria and anammox bacteria accounted for 42-73% of the bacterial populations in the wetlands, which was the highest relative abundance of ammonium oxidizing and anammox bacteria in constructed wetlands enhancing simultaneous partial nitrification and anammox. The two wetlands removed total inorganic nitrogen efficiently, 3.36-3.38 g/m(2)/d in the warm season with water temperatures at 18.9-24.9 °C and 1.09-1.50 g/m(2)/d in the cool season at 13.8-18.9 °C. Plant uptake contributed 2-45% to the total inorganic nitrogen removal in the growing season. A seasonal temperature variation of more than 6 °C would affect simultaneous partial nitrification and anammox significantly. Significant pH effects were identified only when the temperatures were below 18.9 °C. Anammox was the limiting stage of simultaneous partial nitrification and anammox in the wetlands. Water pH should be controlled along with influent ammonium concentration and temperature to avoid toxicity of free ammonia to anammox bacteria. Copyright © 2012 Elsevier Ltd. All rights reserved.

Oxidation and Condensation of Zinc Fume From Zn-CO 2-CO-H 2O Streams Relevant to Steelmaking Off-Gas Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bronson, Tyler Mark; Ma, Naiyang; Zhu, Liang Zhu

Here the objective of this research was to study the condensation of zinc vapor to metallic zinc and zinc oxide solid under varying environments to investigate the feasibility of in-process separation of zinc from steelmaking off-gas dusts. Water vapor content, temperature, degree of cooling, gas composition, and initial zinc partial pressure were varied to simulate the possible conditions that can occur within steelmaking off-gas systems, limited to Zn-CO 2-CO-H 2O gas compositions. The temperature of deposition and the effect of rapidly quenching the gas were specifically studied. A homogeneous nucleation model for applicable experiments was applied to the analysis of the experimental data. It was determined that under the experimental conditions, oxidation of zinc vapor by H 2O or CO 2 does not occur above 1108 K (835 °C) even for highly oxidizing streams (CO 2/CO = 40/7). Rate expressions that correlate CO 2 and H 2O oxidation rates to gas composition, partial pressure of water vapor, temperature, and zinc partial pressure were determined to be as follows: Ratemore » $$ \\left(\\frac{mol}{m^2s}\\right) $$ = 406 exp $$ \\left(\\frac{-50.2 kJ/mol}{RT}\\right) $$ (pZnpCO 2 $-$ PCO/K eqCO 2) $$\\frac{mol}{m^2 x s}$$ Rate $$ \\left(\\frac{mol}{m^2s}\\right) $$ = 32.9 exp $$ \\left(\\frac{-13.7 kJ/mol}{RT}\\right) $$ (pZnPH 2O $-$ PH 2/K eqH 2O) $$\\frac{mol}{m^2 x s}$$. It was proven that a rapid cooling rate (500 K/s) significantly increases the ratio of metallic zinc to zinc oxide as opposed to a slow cooling rate (250 K/s). SEM analysis found evidence of heterogeneous growth of ZnO as well as of homogeneous formation of metallic zinc. The homogeneous nucleation model fit well with experiments where only metallic zinc deposited. An expanded model with rates of oxidation by CO 2 and H 2O as shown was combined with the homogenous nucleation model and then compared with experimental data. The calculated results based on the model gave a reasonable fit to the measured data. For the conditions used in this study, the rate equations for the oxidation of zinc by carbon dioxide and water vapor as well as the homogeneous nucleation model of metallic zinc were applicable for various temperatures, zinc partial pressures, CO 2:CO ratios, and H 2O partial pressures.« less

Oxidation and Condensation of Zinc Fume From Zn-CO 2-CO-H 2O Streams Relevant to Steelmaking Off-Gas Systems

DOE PAGES

Bronson, Tyler Mark; Ma, Naiyang; Zhu, Liang Zhu; ...

2017-01-23

Here the objective of this research was to study the condensation of zinc vapor to metallic zinc and zinc oxide solid under varying environments to investigate the feasibility of in-process separation of zinc from steelmaking off-gas dusts. Water vapor content, temperature, degree of cooling, gas composition, and initial zinc partial pressure were varied to simulate the possible conditions that can occur within steelmaking off-gas systems, limited to Zn-CO 2-CO-H 2O gas compositions. The temperature of deposition and the effect of rapidly quenching the gas were specifically studied. A homogeneous nucleation model for applicable experiments was applied to the analysis of the experimental data. It was determined that under the experimental conditions, oxidation of zinc vapor by H 2O or CO 2 does not occur above 1108 K (835 °C) even for highly oxidizing streams (CO 2/CO = 40/7). Rate expressions that correlate CO 2 and H 2O oxidation rates to gas composition, partial pressure of water vapor, temperature, and zinc partial pressure were determined to be as follows: Ratemore » $$ \\left(\\frac{mol}{m^2s}\\right) $$ = 406 exp $$ \\left(\\frac{-50.2 kJ/mol}{RT}\\right) $$ (pZnpCO 2 $-$ PCO/K eqCO 2) $$\\frac{mol}{m^2 x s}$$ Rate $$ \\left(\\frac{mol}{m^2s}\\right) $$ = 32.9 exp $$ \\left(\\frac{-13.7 kJ/mol}{RT}\\right) $$ (pZnPH 2O $-$ PH 2/K eqH 2O) $$\\frac{mol}{m^2 x s}$$. It was proven that a rapid cooling rate (500 K/s) significantly increases the ratio of metallic zinc to zinc oxide as opposed to a slow cooling rate (250 K/s). SEM analysis found evidence of heterogeneous growth of ZnO as well as of homogeneous formation of metallic zinc. The homogeneous nucleation model fit well with experiments where only metallic zinc deposited. An expanded model with rates of oxidation by CO 2 and H 2O as shown was combined with the homogenous nucleation model and then compared with experimental data. The calculated results based on the model gave a reasonable fit to the measured data. For the conditions used in this study, the rate equations for the oxidation of zinc by carbon dioxide and water vapor as well as the homogeneous nucleation model of metallic zinc were applicable for various temperatures, zinc partial pressures, CO 2:CO ratios, and H 2O partial pressures.« less

Enhanced ammonia removal at room temperature by pH controlled partial nitrification and subsequent anaerobic ammonium oxidation.

PubMed

Durán, U; del Val Río, A; Campos, J L; Mosquera-Corral, A; Méndez, R

2014-01-01

The Anammox-based processes are suitable for the treatment of wastewaters characterized by a low carbon to nitrogen (C/N) ratio. The application of the Anammox process requires the availability of an effluent with a NO2- -N/NH4+ -N ratio composition around 1 g g-1, which involves the necessity of a previous step where the partial nitrification is performed. In this step, the inhibition of the nitrite-oxidizing bacteria (NOB) is crucial. In the present work, a combined partial nitrification-ANaerobic AMmonia OXidation (Anammox) two-units system operated at room temperature (20 degreeC) has been tested for the nitrogen removal of pre-treated pig slurry. To achieve the successful partial nitrification and inhibit the NOB activity, different ammonium/inorganic carbon (NH4+/IC) ratios were assayed from 1.19 to 0.82g NH4+-Ng-1 HCO3-C. This procedure provoked a decrease of the pH value to 6.0 to regulate the inhibitory effect over ammonia-oxidizing bacteria caused by free ammonia. Simultaneously, the NOB experienced the inhibitory effect of free nitrous acid which avoided the presence of nitrate in the effluent. The NH4+/IC ratio which allowed the obtaining of the desired effluent composition (50% of both ammonium and nitrite) was 0.82 +/- 0.02 g NH4+-N g-1 HCO3- -C. The Anammox reactor was fed with the effluent of the partial nitrification unit containing a NO2 -N/NH4+ -N ratio of 1 g g-1' where a nitrogen loading rate of 0.1 g N L-1 d-1 was efficiently removed.

Oxygen binding to partially nitrosylated hemoglobin.

PubMed

Fago, Angela; Crumbliss, Alvin L; Hendrich, Michael P; Pearce, Linda L; Peterson, Jim; Henkens, Robert; Bonaventura, Celia

2013-09-01

Reactions of nitric oxide (NO) with hemoglobin (Hb) are important elements in protection against nitrosative damage. NO in the vasculature is depleted by the oxidative reaction with oxy Hb or by binding to deoxy Hb to generate partially nitrosylated Hb (Hb-NO). Many aspects of the formation and persistence of Hb-NO are yet to be clarified. In this study, we used a combination of EPR and visible absorption spectroscopy to investigate the interactions of partially nitrosylated Hb with O2. Partially nitrosylated Hb samples had predominantly hexacoordinate NO-heme geometry and resisted oxidation when exposed to O2 in the absence of anionic allosteric effectors. Faster oxidation occurred in the presence of 2,3-diphosphoglycerate (DPG) or inositol hexaphosphate (IHP), where the NO-heme derivatives had higher levels of pentacoordinate heme geometry. The anion-dependence of the NO-heme geometry also affected O2 binding equilibria. O2-binding curves of partially nitrosylated Hb in the absence of anions were left-shifted at low saturations, indicating destabilization of the low O2 affinity T-state of the Hb by increasing percentages of NO-heme, much as occurs with increasing levels of CO-heme. Samples containing IHP showed small decreases in O2 affinity, indicating shifts toward the low-affinity T-state and formation of inert α-NO/β-met tetramers. Most remarkably, O2-equilibria in the presence of the physiological effector DPG were essentially unchanged by up to 30% NO-heme in the samples. As will be discussed, under physiological conditions the interactions of Hb with NO provide protection against nitrosative damage without impairing O2 transport by Hb's unoccupied heme sites. This article is part of a Special Issue entitled: Oxygen Binding and Sensing Proteins. Copyright © 2013 Elsevier B.V. All rights reserved.

Partial oxidation (“aging”) and surface modification decrease the toxicity of nano-sized zero valent iron.

EPA Science Inventory

Nanosize zero-valent iron (nZVI) is used as a redox-active catalyst for in situ remediation of contaminated ground waters. In aqueous environments, nZVI oxidizes over time (i.e., “ages”) to magnetite and other oxides. For remediation, hi...

Ladder polymers for use as high temperature stable resins or coatings

NASA Technical Reports Server (NTRS)

Meador, Mary Ann (Inventor)

1990-01-01

An object of the invention is to synthesize a new class of ladder and partial ladder polymers. In accordance with the invention, the new class of ladder and partial ladder polymers are synthesized by polymerizing a bis-dienophile with a bis-diene. Another object of the invention is to provide a fabricated, electrically conducting, void free composite comprising the new class of the ladder and partial ladder polymers described above. The novelty of the invention relates to a new class of ladder and partial ladder polymers and a process for synthesizing these polymers. These polymers are soluble in common organic solvents and are characterized with a unique dehydration property at temperatures of 300 to 400 C to provide thermo-oxidatively stable pentiptycene units along the polymeric backbone. These polymers are further characterized with high softening points and good thermo-oxidative stability properties. Thus these polymers have potential as processable, matrix resins for high temperature composite applications.

Method for converting hydrocarbon fuel into hydrogen gas and carbon dioxide

DOEpatents

Clawson, Lawrence G.; Mitchell, William L.; Bentley, Jeffrey M.; Thijssen, Johannes H. J.

2000-01-01

A method for converting hydrocarbon fuel into hydrogen gas and carbon dioxide within a reformer 10 is disclosed. According to the method, a stream including an oxygen-containing gas is directed adjacent to a first vessel 18 and the oxygen-containing gas is heated. A stream including unburned fuel is introduced into the oxygen-containing gas stream to form a mixture including oxygen-containing gas and fuel. The mixture of oxygen-containing gas and unburned fuel is directed tangentially into a partial oxidation reaction zone 24 within the first vessel 18. The mixture of oxygen-containing gas and fuel is further directed through the partial oxidation reaction zone 24 to produce a heated reformate stream including hydrogen gas and carbon monoxide. Steam may also be mixed with the oxygen-containing gas and fuel, and the reformate stream from the partial oxidation reaction zone 24 directed into a steam reforming zone 26. High- and low-temperature shift reaction zones 64,76 may be employed for further fuel processing.

Surface studies of thermionic cathodes and the mechanism of operation of an impregnated tungsten cathode

NASA Technical Reports Server (NTRS)

Forman, R.

1976-01-01

The surface properties of conventional impregnated cathodes were investigated by the use of Auger spectroscopy and work function measurements, and these were compared with a synthesized barium or barium oxide coated tungsten surface. The barium and barium oxide coated surfaces were prepared by evaporating barium onto a tungsten surface that can be heated to elevated temperatures. Multilayer or monolayer coverages can be investigated using this technique. The results of this study show that the surface of an impregnated tungsten cathode is identical to that observed for a synthesized monolayer or partial monolayer of barium on partially oxidized tungsten, using the criteria of identical Auger patterns and work functions. Desorption measurements of barium from a tungsten surface were also made. These results in conjunction with Auger and work function data were interpreted to show that throughout most of its life an impregnated cathode operating in the range of 1100 C has a partial monolayer rather than a monolayer of barium on its surface.

Combustion synthesis of ceramic-metal composite materials in microgravity

NASA Technical Reports Server (NTRS)

Moore, John

1995-01-01

Combustion synthesis, self-propagating high temperature synthesis (SHS) or reactive synthesis provides an attractive alternative to conventional methods of producing advanced materials since this technology is based on the ability of highly exothermic reactions to be self sustaining and, therefore, energetically efficient. The exothermic SHS reaction is initiated at the ignition temperature, T(sub ig), and generates heat which is manifested in a maximum or combustion temperature, T(sub c), which can exceed 3000 K . Such high combustion temperatures are capable of melting and/or volatilizing reactant and product species and, therefore, present an opportunity for producing structure and property modification and control through liquid-solid, vapor-liquid-solid, and vapor-solid transformations.

Heat recovery from sorbent-based CO.sub.2 capture

DOEpatents

Jamal, Aqil; Gupta, Raghubir P

2015-03-10

The present invention provides a method of increasing the efficiency of exothermic CO.sub.2 capture processes. The method relates to withdrawing heat generated during the exothermic capture of CO.sub.2 with various sorbents via heat exchange with a working fluid. The working fluid is provided at a temperature and pressure such that it is in the liquid state, and has a vaporization temperature in a range such that the heat arising from the reaction of the CO.sub.2 and the sorbent causes a phase change from liquid to vapor state in whole or in part and transfers heat from to the working fluid. The resulting heated working fluid may subsequently be used to generate power.

Middle atmosphere heating by exothermic chemical reactions involving odd-hydrogen species

NASA Technical Reports Server (NTRS)

Mlynczak, Martin G.; Solomon, Susan

1991-01-01

The rate of heating which occurs in the middle atmosphere due to four exothermic reactions involving members of the odd-hydrogen family is calculated. The following reactions are considered: O + OH yields O2 + H; H + O2 + M yields HO2 + M; H + O3 yields OH + O2; and O + HO2 yields OH + O2. It is shown that the heating rates due to these reactions rival the oxygen-related heating rates conventionally considered in middle-atmosphere models. The conversion of chemical potential energy into molecular translational energy (heat) by these odd-hydrogen reactions is shown to be a significant energy source in the middle atmosphere that has not been previously considered.

Ameliorative role of gemfibrozil against partial abdominal aortic constriction-induced cardiac hypertrophy in rats.

PubMed

Singh, Amrit Pal; Singh, Randhir; Krishan, Pawan

2015-04-01

Fibrates are peroxisome proliferator-activated receptor-α agonists and are clinically used for treatment of dyslipidemia and hypertriglyceridemia. Fenofibrate is reported as a cardioprotective agent in various models of cardiac dysfunction; however, limited literature is available regarding the role of gemfibrozil as a possible cardioprotective agent, especially in a non-obese model of cardiac remodelling. The present study investigated the role of gemfibrozil against partial abdominal aortic constriction-induced cardiac hypertrophy in rats. Cardiac hypertrophy was induced by partial abdominal aortic constriction in rats and they survived for 4 weeks. The cardiac hypertrophy was assessed by measuring left ventricular weight to body weight ratio, left ventricular wall thickness, and protein and collagen content. The oxidative stress in the cardiac tissues was assessed by measuring thiobarbituric acid-reactive substances, superoxide anion generation, and reduced glutathione level. The haematoxylin-eosin and picrosirius red staining was used to observe cardiomyocyte diameter and collagen deposition, respectively. Moreover, serum levels of cholesterol, high-density lipoproteins, triglycerides, and glucose were also measured. Gemfibrozil (30 mg/kg, p.o.) was administered since the first day of partial abdominal aortic constriction and continued for 4 weeks. The partial abdominal aortic constriction-induced cardiac oxidative stress and hypertrophy are indicated by significant change in various parameters used in the present study that were ameliorated with gemfibrozil treatment in rats. No significant change in serum parameters was observed between various groups used in the present study. It is concluded that gemfibrozil ameliorates partial abdominal aortic constriction-induced cardiac oxidative stress and hypertrophy and in rats.

Catalytic Steam and Partial Oxidation Reforming of Liquid Fuels for Application in Improving the Efficiency of Internal Combustion Engines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brookshear, Daniel William; Pihl, Josh A.; Szybist, James P.

Here, this study investigated the potential for catalytically reforming liquid fuels in a simulated exhaust gas recirculation (EGR) mixture loop for the purpose of generating reformate that could be used to increase stoichiometric combustion engine efficiency. The experiments were performed on a simulated exhaust flow reactor using a Rh/Al 2O 3 reformer catalyst, and the fuels evaluated included iso-octane, ethanol, and gasoline. Both steam reforming and partial oxidation reforming were examined as routes for the production of reformate. Steam reforming was determined to be an ineffective option for reforming in an EGR loop, because of the high exhaust temperatures (inmore » excess of 700 °C) required to produce adequate concentrations of reformate, regardless of fuel. However, partial oxidation reforming is capable of producing hydrogen concentrations as high as 10%–16%, depending on fuel and operating conditions in the simulated EGR gas mixture. Meanwhile, measurements of total fuel enthalpy retention were shown to have favorable energetics under a range of conditions, although a tradeoff between fuel enthalpy retention and reformate production was observed. Of the three fuels evaluated, iso-octane exhibited the best overall performance, followed by ethanol and then gasoline. Overall, it was found that partial oxidation reforming of liquid fuels in a simulated EGR mixture over the Rh/Al 2O 3 catalyst demonstrated sufficiently high reformate yields and favorable energetics to warrant further evaluation in the EGR system of a stoichiometric combustion engine.« less

Catalytic Steam and Partial Oxidation Reforming of Liquid Fuels for Application in Improving the Efficiency of Internal Combustion Engines

DOE PAGES

Brookshear, Daniel William; Pihl, Josh A.; Szybist, James P.

2018-02-07

Here, this study investigated the potential for catalytically reforming liquid fuels in a simulated exhaust gas recirculation (EGR) mixture loop for the purpose of generating reformate that could be used to increase stoichiometric combustion engine efficiency. The experiments were performed on a simulated exhaust flow reactor using a Rh/Al 2O 3 reformer catalyst, and the fuels evaluated included iso-octane, ethanol, and gasoline. Both steam reforming and partial oxidation reforming were examined as routes for the production of reformate. Steam reforming was determined to be an ineffective option for reforming in an EGR loop, because of the high exhaust temperatures (inmore » excess of 700 °C) required to produce adequate concentrations of reformate, regardless of fuel. However, partial oxidation reforming is capable of producing hydrogen concentrations as high as 10%–16%, depending on fuel and operating conditions in the simulated EGR gas mixture. Meanwhile, measurements of total fuel enthalpy retention were shown to have favorable energetics under a range of conditions, although a tradeoff between fuel enthalpy retention and reformate production was observed. Of the three fuels evaluated, iso-octane exhibited the best overall performance, followed by ethanol and then gasoline. Overall, it was found that partial oxidation reforming of liquid fuels in a simulated EGR mixture over the Rh/Al 2O 3 catalyst demonstrated sufficiently high reformate yields and favorable energetics to warrant further evaluation in the EGR system of a stoichiometric combustion engine.« less

Operation of mixed conducting metal oxide membrane systems under transient conditions

DOEpatents

Carolan, Michael Francis [Allentown, PA

2008-12-23

Method of operating an oxygen-permeable mixed conducting membrane having an oxidant feed side, an oxidant feed surface, a permeate side, and a permeate surface, which method comprises controlling the differential strain between the permeate surface and the oxidant feed surface at a value below a selected maximum value by varying the oxygen partial pressure on either or both of the oxidant feed side and the permeate side of the membrane.

Oxidation of SiC/BN/SiC Composites in Reduced Oxygen Partial Pressures

NASA Technical Reports Server (NTRS)

Opila, Elizabeth J.; Boyd, Meredith

2010-01-01

SiC fiber-reinforced SiC composites with a BN interphase are proposed for use as leading edge structures of hypersonic vehicles. The durability of these materials under hypersonic flight conditions is therefore of interest. Thermogravimetric analysis was used to characterize the oxidation kinetics of both the constituent fibers and composite coupons at four temperatures: 816, 1149, 1343, and 1538 C (1500, 2100, 2450, and 2800 F) and in oxygen partial pressures between 5% and 0.1% (balance argon) at 1 atm total pressure. One edge of the coupons was ground off so the effects of oxygen ingress into the composite could be monitored by post-test SEM and EDS. Additional characterization of the oxidation products was conducted by XPS and TOF-SIMS. Under most conditions, the BN oxidized rapidly, leading to the formation of borosilicate glass. Rapid initial oxidation followed by volatilization of boria lead to protective oxide formation and further oxidation was slow. At 1538C in 5% oxygen, both the fibers and coupons exhibited borosilicate glass formation and bubbling. At 1538C in 0.1% oxygen, active oxidation of both the fibers and the composites was observed leading to rapid SiC degradation. BN oxidation at 1538C in 0.1% oxygen was not significant.

Colloidal inorganic nanocrystals: Nucleation, growth and biological applications

NASA Astrophysics Data System (ADS)

Lynch, Jared James

Colloidal inorganic nanocrystals are a class of material whose size ranges from a few nanometers to a hundred nanometers in dimension. These nanocrystals have size dependent properties that differ significantly from the bulk material counterparts. Due to their unique physical properties colloidal inorganic nanocrystals have several promising applications in a diverse range of areas, such as biomedical diagnosis, catalysis, plasmonics, high-density data storage and solar energy conversion. This dissertation presents the study of the formation of iron oxide nanocrystals under the influence of solvent and Ar gas bubbles, the phase transfer of metal oxide nanocrystals into water using inorganic ions, and the doping of semiconductor CdS/ZnS core/shell nanocrystals with copper and silver ions. First, the formation of iron oxide nanocrystals is investigated in the presence of boiling solvent or Ar bubbles. Using a non-injection based synthesis method, the thermal decomposition of iron oleate was studied under various reaction conditions, and the role of the bubbles on the nucleation and growth of iron oxide nanocrystals was determined. Kinetics studies were used to elucidate how latent heat transfer from the bubbles allows for "active monomers" to form preferentially from exothermic reactions taking place during nucleation. General insights into colloidal inorganic nanocrystal formation are discussed. Second, a non-injection based synthesis for CdS/ZnS core/shell nanocrystals is used to make high quality semiconductor particles which are intentionally doped with Cu or Ag ions. The Ag ions effect on the optical properties of the CdS/ZnS nanocrystals is investigated. The absorption and fluorescence of the samples is measured as a function of time and temperature. Proposed mechanisms for the observations are given and thoroughly discussed. Comparisons between previous results for Cu doped CdS/ZnS nanocrystals are also made to further understand how doping of semiconductor nanocrystals can be realized. Finally, a novel phase transfer process is demonstrated using inorganic salts, such as sodium arsenite, to make water soluble metal oxide nanocrystals. The water soluble iron oxide nanocrystals are fully characterized by several complementary techniques and then used in cellular studies. The arsenite-coated iron oxide composite nanocrystals (AICN) are shown to be effective cancer therapy agents.

Interfacial bonding stabilizes rhodium and rhodium oxide nanoparticles on layered Nb oxide and Ta oxide supports.

PubMed

Strayer, Megan E; Binz, Jason M; Tanase, Mihaela; Shahri, Seyed Mehdi Kamali; Sharma, Renu; Rioux, Robert M; Mallouk, Thomas E

2014-04-16

Metal nanoparticles are commonly supported on metal oxides, but their utility as catalysts is limited by coarsening at high temperatures. Rhodium oxide and rhodium metal nanoparticles on niobate and tantalate supports are anomalously stable. To understand this, the nanoparticle-support interaction was studied by isothermal titration calorimetry (ITC), environmental transmission electron microscopy (ETEM), and synchrotron X-ray absorption and scattering techniques. Nanosheets derived from the layered oxides KCa2Nb3O10, K4Nb6O17, and RbTaO3 were compared as supports to nanosheets of Na-TSM, a synthetic fluoromica (Na0.66Mg2.68(Si3.98Al0.02)O10.02F1.96), and α-Zr(HPO4)2·H2O. High surface area SiO2 and γ-Al2O3 supports were also used for comparison in the ITC experiments. A Born-Haber cycle analysis of ITC data revealed an exothermic interaction between Rh(OH)3 nanoparticles and the layered niobate and tantalate supports, with ΔH values in the range -32 kJ·mol(-1) Rh to -37 kJ·mol(-1) Rh. In contrast, the interaction enthalpy was positive with SiO2 and γ-Al2O3 supports. The strong interfacial bonding in the former case led to "reverse" ripening of micrometer-size Rh(OH)3, which dispersed as 0.5 to 2 nm particles on the niobate and tantalate supports. In contrast, particles grown on Na-TSM and α-Zr(HPO4)2·H2O nanosheets were larger and had a broad size distribution. ETEM, X-ray absorption spectroscopy, and pair distribution function analyses were used to study the growth of supported nanoparticles under oxidizing and reducing conditions, as well as the transformation from Rh(OH)3 to Rh nanoparticles. Interfacial covalent bonding, possibly strengthened by d-electron acid/base interactions, appear to stabilize Rh(OH)3, Rh2O3, and Rh nanoparticles on niobate and tantalate supports.

The influence of cladding on fission gas release from irradiated U-Mo monolithic fuel

NASA Astrophysics Data System (ADS)

Burkes, Douglas E.; Casella, Amanda J.; Casella, Andrew M.

2017-04-01

The monolithic uranium-molybdenum (U-Mo) alloy has been proposed as a fuel design capable of converting the world's highest power research reactors from use of high enriched uranium to low enriched uranium. However, a zirconium (Zr) diffusion barrier must be used to eliminate interactions that form between the U-Mo monolith and aluminum alloy 6061 (AA6061) cladding during fabrication and are enhanced during irradiation. One aspect of fuel development and qualification is to demonstrate an appropriate understanding of the extent of fission product release from the fuel under anticipated service environments. An exothermic reaction has previously been observed between the AA6061 cladding and Zr diffusion layer. In this paper, two fuel segments with different irradiation history were subjected to specified thermal profiles under a controlled atmosphere using a thermogravimetric/differential thermal analyzer coupled with a mass spectrometer inside a hot cell. Samples from each segment were tested with cladding and without cladding to investigate the effect, if any, that the exothermic reaction has on fission gas release mechanisms. Measurements revealed there is an instantaneous effect of the cladding/Zr exothermic reaction, but not necessarily a cumulative effect above approximately 973 K (700 °C). The mechanisms responsible for fission gas release events are discussed.

In vitro pulp chamber temperature rise from irradiation and exotherm of flowable composites.

PubMed

Baroudi, Kusai; Silikas, Nick; Watts, David C

2009-01-01

The aim of this study was to investigate the pulpal temperature rise induced during the polymerization of flowable and non-flowable composites using light-emitting diode (LED) and halogen (quartz-tungsten-halogen) light-curing units (LCUs). Five flowable and three non-flowable composites were examined. Pulpal temperature changes were recorded over 10 min in a sample primary tooth by a thermocouple. A conventional quartz-tungsten-halogen source and two LEDs, one of which was programmable, were used for light curing the resin composites. Three repetitions per material were made for each LCU. There was a wide range of temperature rises among the materials (P < 0.05). Temperature rises ranged between 1.3 degrees C for Filtek Supreme irradiated by low-power LED and 4.5 degrees C for Grandio Flow irradiated by high-power LED. The highest temperature rises were observed with both the LED high-power and soft-start LCUs. The time to reach the exothermic peak varied significantly between the materials (P < 0.05). Pulpal temperature rise is related to both the radiant energy output from LCUs and the polymerization exotherm of resin composites. A greater potential risk for heat-induced pulp damage might be associated with high-power LED sources. Flowable composites exhibited higher temperature rises than non-flowable materials, because of higher resin contents.

The influence of cladding on fission gas release from irradiated U-Mo monolithic fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burkes, Douglas E.; Casella, Amanda J.; Casella, Andrew M.

2017-04-01

The monolithic uranium-molybdenum (U-Mo) alloy has been proposed as a fuel design capable of converting the world’s highest power research reactors from use of high enriched uranium to low enriched uranium. However, a zirconium (Zr) diffusion barrier must be used to eliminate interactions that form during fabrication and are enhanced during irradiation between the U-Mo monolith and aluminum alloy 6061 (AA6061) cladding. One aspect of fuel development and qualification is to demonstrate appropriate understanding of the extent of fission product release from the fuel under anticipated service environments. An exothermic reaction has previously been observed between the AA6061 cladding andmore » Zr diffusion layer. In this paper, two fuel segments with different irradiation history were subjected to specified thermal profiles under a controlled atmosphere using a thermogravimetric/differential thermal analyzer coupled with a mass spectrometer inside a hot cell. Samples from each segment were tested with cladding and without cladding to investigate the effect, if any, that the exothermic reaction has on fission gas release mechanisms. Measurements revealed there is an instantaneous effect of the cladding/Zr exothermic reaction, but not necessarily a cumulative effect above approximately 973 K (700 oC). The mechanisms responsible for fission gas release events are discussed.« less

Nitrification and occurrence of salt-tolerant nitrifying bacteria in the Negev desert soils.

PubMed

Nejidat, Ali

2005-03-01

Ammonia oxidation potential, major ammonia oxidizers and occurrence of salt-tolerant nitrifying bacteria were studied in soil samples collected from diverse ecosystems along the northern Negev desert. Great diversity in ammonia oxidation potential was observed among the soil samples, and ammonia oxidizers were the rate-limiting step of nitrification. Denaturing gradient gel electrophoresis and partial 16S rRNA gene sequences indicate that members of the genus Nitrosospira are the major ammonia oxidizers in the natural desert soil samples. Upon enrichment with different salt concentrations, salt-tolerant nitrifying enrichments were established from several soil samples. In two enrichments, nitrification was not inhibited by 400 mM NaCl. Electrophoretic analysis and partial 16S rRNA gene sequences indicate that Nitrosomonas species were dominant in the 400 mM salt enrichment. The results point towards the potential of the desert ecosystem as a source of stress-tolerant nitrifying bacteria or other microorganisms with important properties.

Laser-induced fluorescence studies of excited Sr reactions: II. Sr(3P1)+CH3F, C2H5F, C2H4F2

NASA Astrophysics Data System (ADS)

Teule, J. M.; Janssen, M. H. M.; Bulthuis, J.; Stolte, S.

1999-06-01

The vibrational and rotational energy distributions of ground state SrF(X 2Σ) formed in the reactions of electronically excited Sr(3P1) with methylfluoride, ethylfluoride, and 1,1-difluoroethane have been studied by laser-induced fluorescence. Although the reactions of ground state Sr with these reactants are exothermic, no SrF products are observed for those reactions in this study. The fraction of available energy disposed into the sum of rotational and vibrational energy of the SrF(X 2Σ) product is approximately the same for all three reactions, i.e., 40%. The reaction of Sr(3P1) with CH3F results in very low vibrational excitation in the SrF reaction product. The product vibration increases in going to C2H5F and C2H4F2. It is concluded that the alkyl group influences the energy disposal mechanism in these reactions, and some suggestions are given for a partial explanation of the observations.

Towards a Microbial Thermoelectric Cell

PubMed Central

Rodríguez-Barreiro, Raúl; Abendroth, Christian; Vilanova, Cristina; Moya, Andrés; Porcar, Manuel

2013-01-01

Microbial growth is an exothermic process. Biotechnological industries produce large amounts of heat, usually considered an undesirable by-product. In this work, we report the construction and characterization of the first microbial thermoelectric cell (MTC), in which the metabolic heat produced by a thermally insulated microbial culture is partially converted into electricity through a thermoelectric device optimized for low ΔT values. A temperature of 41°C and net electric voltage of around 250–600 mV was achieved with 1.7 L baker’s yeast culture. This is the first time microbial metabolic energy has been converted into electricity with an ad hoc thermoelectric device. These results might contribute towards developing a novel strategy to harvest excess heat in the biotechnology industry, in processes such as ethanol fermentation, auto thermal aerobic digestion (ATAD) or bioremediation, which could be coupled with MTCs in a single unit to produce electricity as a valuable by-product of the primary biotechnological product. Additionally, we propose that small portable MTCs could be conceived and inoculated with suitable thermophilic of hyperthermophilic starter cultures and used for powering small electric devices. PMID:23468862

Production of ZrC Matrix for Use in Gas Fast Reactor Composite Fuels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vasudevamurthy, Gokul; Knight, Travis W.; Roberts, Elwyn

2007-07-01

Zirconium carbide is being considered as a candidate for inert matrix material in composite nuclear fuel for Gas fast reactors due to its favorable characteristics. ZrC can be produced by the direct reaction of pure zirconium and graphite powders. Such a reaction is exothermic in nature. The reaction is self sustaining once initial ignition has been achieved. The heat released during the reaction is high enough to complete the reaction and achieve partial sintering without any external pressure applied. External heat source is required to achieve ignition of the reactants and maintain the temperature close to the adiabatic temperature tomore » achieve higher levels of sintering. External pressure is also a driving force for sintering. In the experiments described, cylindrical compacts of ZrC were produced by direct combustion reaction. External induction heating combined with varying amounts of external applied pressure was employed to achieve varying degrees of density/porosity. The effect of reactant particle size on the product characteristics was also studied. The samples were characterized for density/porosity, composition and microstructure. (authors)« less

Enthalpy of mixing of liquid systems for lead free soldering: Ni-Sb-Sn system.

PubMed

Elmahfoudi, A; Fürtauer, S; Sabbar, A; Flandorfer, H

2012-04-20

The partial and integral enthalpies of mixing of liquid ternary Ni-Sb-Sn alloys were determined along five sections x Sb / x Sn  = 3:1, x Sb / x Sn  = 1:1, x Sb / x Sn  = 1:3, x Ni / x Sn  = 1:4, and x Ni / x Sb  = 1:4 at 1000 °C in a large compositional range using drop calorimetry techniques. The mixing enthalpy of Ni-Sb alloys was determined at the same temperature and described by a Redlich-Kister polynomial. The other binary data were carefully evaluated from literature values. Our measured ternary data were fitted on the basis of an extended Redlich-Kister-Muggianu model for substitutional solutions. Additionally, a comparison of these results to the extrapolation model of Toop is given. The entire ternary system shows exothermic values of Δ mix H ranging from approx. -1300 J/mol, the minimum in the Sb-Sn binary system down to approx. -24,500 J/mol towards Ni-Sb. No significant ternary interaction could be deduced from our data.

Staged heating by oxidation of carbonaceous material

DOEpatents

Knell, Everett W.; Green, Norman W.

1978-01-31

A carbonaceous material is pyrolyzed in the presence of a particulate source of heat obtained by the partial oxidation of a carbon containing solid residue of the carbonaceous material. The heat obtained from the oxidation of the carbon containing solid residue is maximized by preheating the carbon containing solid residue with a hot gas stream obtained by oxidizing the gaseous combustion products of the carbon containing solid residue.

Low cost, formable, high T(sub c) superconducting wire

NASA Technical Reports Server (NTRS)

Smialek, James L. (Inventor)

1991-01-01

A ceramic superconductivity part such as a wire is produced through the partial oxidation of a specially formulated copper alloy in the core. The alloys contain low level quantities of rare earth and alkaline earth dopant elements. Upon oxidation at high temperature, superconducting oxide phases are formed as a thin film.

Cyclic Catalytic Upgrading of Chemical Species Using Metal Oxide Materials

NASA Technical Reports Server (NTRS)

White, James H. (Inventor); Rolfe, Sara L. (Inventor); Schutte, Erick J. (Inventor)

2013-01-01

Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having the following formulas: (a) Ce(sub x)B(sub y)B'(sub z)B''O(sub gamma; wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, and/or Fe; B''=Cu; 0.01

Cyclic catalytic upgrading of chemical species using metal oxide materials

DOEpatents

White, James H; Schutte, Erick J; Rolfe, Sara L

2013-05-07

Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having the following formulas: (a) Ce.sub.xB.sub.yB'.sub.zB''O.sub..delta., wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, and/or Fe; B''=Cu; 0.01

Description of the behavior of dichloroalkanes-containing solutions with three [bXmpy][BF4] isomers, using the experimental information of thermodynamic properties, 1H NMR spectral and the COSMO-RS-methodology.

PubMed

Fernández, Luis; Ortega, Juan; Palomar, José; Toledo, Francisco; Marrero, Elena

2015-02-26

This work studies the binaries of 1-butyl-X-methylpyridinium tetrafluoroborate [bXmpy][BF4] (X = 2, 3, and 4) with four 1,ω-dichloroalkanes, ω = 1-4, using the results obtained for the mixing properties h(E) and v(E) at two temperatures. The three isomers of the ionic liquid (IL) are weakly miscible with the 1,ω-dichloroalkanes when ω ≥ 5 and moderately soluble for ω = 4. The v(E)s of all the binaries present contractive effects, v(E) < 0, which are more pronounced with increasing temperature; the variation in v(E) with ω is positive, although this changes after ω = 4 due to problems of immiscibility. The energetic effects of the mixing process are exothermic in the solutions with the shorter dichloroalkanes, ω = 1 and 2, and this effect increases slightly with temperature. However, mildly exothermic effects are found in the binaries with larger halides, where (dh(E)/dT) > 0. The experimental data are correlated with a suitable equation. The study is completed with (1)H NMR measurements of both the pure compounds and some of the solutions, which showed minor diamagnetic shifts with increasing IL compositions, related to the anisotropy of the pyridine ring. The variation in h(E) with ω for a same IL, due to an increase in the contact surfaces, is related to the reduction in polarity which, in turn, depends on the smaller chemical shifts of the pure dihalide compounds. The COSMO-RS method determines the energetic effects of the mixing process and predicts an exothermic contribution for the electrostatic Misfit-interaction which is quantitatively very similar for the three IL isomers. The differences proposed by the model are mainly reflected in the van der Waals interactions, which are exothermic and clearly influenced by the position of the methylene group in the IL. The contribution made by hydrogen bonds is negligible.

A Hydrazine Leak Sensor Based on Chemically Reactive Thermistors

NASA Technical Reports Server (NTRS)

Davis, Dennis D.; Mast, Dion J.; Baker, David L.

1999-01-01

Leaks in the hydrazine supply system of the Shuttle APU can result in hydrazine ignition and fire in the aft compartment of the Shuttle. Indication of the location of a leak could provide valuable information required for operational decisions. WSTF has developed a small, single use sensor for detection of hydrazine leaks. The sensor is composed of a thermistor bead coated with copper(II) oxide (CuO) dispersed in a clay or alumina binder. The CuO-coated thermistor is one of a pair of closely located thermistors, the other being a reference. On exposure to hydrazine the CuO reacts exothermically with the hydrazine and increases the temperature of the coated-thermistor by several degrees. The temperature rise is sensed by a resistive bridge circuit and an alarm registered by data acquisition software. Responses of this sensor to humidity changes, hydrazine concentration, binder characteristics, distance from a liquid leak, and ambient pressure levels as well as application of this sensor concept to other fluids are presented.

A study of ignition of metal impregnated carbons: the influence of oxygen content in the activated carbon matrix.

PubMed

van der Merwe, M M; Bandosz, T J

2005-02-01

A study of the reason for the early ignition of coconut-based impregnated carbon in comparison with the peat-based impregnated carbon was conducted. The surface features of carbons were evaluated using various physicochemical methods. The metal analysis of the initial carbon indicated that the content of potassium was higher in the coconut-based carbon. The surface functional group analysis revealed the presence of similar surface species; however, the peat-based carbon was more acidic in its chemical nature. Since the oxygen content was higher in the peat-based carbon, the early ignition of the coconut-based material was attributed to its higher affinity to chemisorb oxygen, which leads to exothermic effects. This conclusion was confirmed by performing oxidation of coconut-based carbon prior to impregnation. This process increased the ignition temperature for Cu/Cr impregnated coconut-based material from 186 to 289 degrees C and for the Cu/Zn/Mo impregnated carbon from 235 to 324 degrees C.

Thermal shock testing for assuring reliability of glass-sealed microelectronic packages

NASA Technical Reports Server (NTRS)

Thomas, Walter B., III; Lewis, Michael D.

1991-01-01

Tests were performed to determine if thermal shocking is destructive to glass-to-metal seal microelectronic packages and if thermal shock step stressing can compare package reliabilities. Thermal shocking was shown to be not destructive to highly reliable glass seals. Pin-pull tests used to compare the interfacial pin glass strengths showed no differences between thermal shocked and not-thermal shocked headers. A 'critical stress resistance temperature' was not exhibited by the 14 pin Dual In-line Package (DIP) headers evaluated. Headers manufactured in cryogenic nitrogen based and exothermically generated atmospheres showed differences in as-received leak rates, residual oxide depths and pin glass interfacial strengths; these were caused by the different manufacturing methods, in particular, by the chemically etched pins used by one manufacturer. Both header types passed thermal shock tests to temperature differentials of 646 C. The sensitivity of helium leak rate measurements was improved up to 70 percent by baking headers for two hours at 200 C after thermal shocking.

Thermal characteristic of limonite ore upon calcination and reduction

NASA Astrophysics Data System (ADS)

Febriana, Eni; Manaf, Azwar; Prasetyo, A. B.; Mayangsari, W.

2018-05-01

Thermal characteristics of the limonite laterite ore types have been studied using TG / DTA. There are four endothermic peaks at 250, 646, 900, and 1023 °C with a total mass loss of 10.07wt%. These four peaks correspond to the XRD results on samples calcined at 600-1000 °C. Analysis of TG / DTA to the mixture of limonite and graphite showed two endothermic reaction peaks at 641 and 900 °C and an exothermic peak at 1180 °C. Reduction of the limonite-graphite mixture was done by heating at 800-1100 °C for 1 hour, and the reduced samples were analyzed using XRD. The results indicate that the reduction process proceed completely at higher temperatures, indicated by the increasing intensity of kamacite and Fe metal phase, and the decrease of peak intensity of carbon due to reaction with metal oxides. At 1100 °C, intensity of Fe-metal decreased due to sintering of Fe which may occur because the temperature was too high.

On the thermal runaway of combustible fluids in lagging material

NASA Astrophysics Data System (ADS)

McIntosh, A. C.; Griffiths, J. F.

1995-01-01

This paper presents the mathematical foundations for a simple theory for investigating the phenomenon of ignition of flammable fluids in lagging material that are used for insulation of hot pipework, for transport of heat transfer fluids, or other similar situations. Experiments with porous material impregnated with a flammable fluid have simulated the self-heating known to occur when combustible liquids leak from a hot pipe into lagging surrounding the pipe or are split from another source on to the lagging. A theory to explain these findings is presented which shows that there is a watershed temperature beyond which substantial self-heating will take place. Although the theory does not take account of diffusion, it simulates the main physics of the phenomenon-that is, combustible fluid, which normally in the open air would evaporate and not be a hazard, can, within a porous medium, remain dispersed within the porous structure long enough for the exothermic oxidation to develop into ignition.

Experiments Developed to Study Microgravity Smoldering Combustion

NASA Technical Reports Server (NTRS)

Vergilii, Franklin

2001-01-01

The overall objective of the Microgravity Smoldering Combustion (MSC) research program is to understand and predict smoldering combustion under normal and microgravity (near-zero-gravity) conditions to help prevent and control smolder-originated fires, in both environments. Smoldering is defined as a nonflaming, self-sustaining, propagating, exothermic surface reaction. If a material is sufficiently permeable, smoldering is not confined to its outer surface, but can propagate as a reaction wave through the interior of the material. The MSC program will accomplish its goals by conducting smolder experiments on the ground and in a space-based laboratory, and developing theoretical models of the process. Space-based experiments are necessary because smoldering is a very slow process and, consequently, its study in a microgravity environment requires extended periods of time that can only be achieved in space. Smoldering can occur in a variety of processes ranging from the smolder of porous insulating materials to underground coal combustion. Many materials can sustain smoldering, including wood, cloth, foams, tobacco, other dry organic materials, and charcoal. The ignition, propagation, transition to flaming, and extinction of the smolder reaction are controlled by complex, thermochemical mechanisms that are not well understood. As with many forms of combustion, gravity affects the availability of the oxidizer and the transport of heat, and therefore, the rate of combustion. The smoldering combustion of porous materials has been studied both experimentally and theoretically, usually in the context of fire safety. Smoldering encompasses a number of fundamental processes, including heat and mass transfer in a porous media; endothermic pyrolysis of combustible material; ignition, propagation, and extinction of heterogeneous exothermic reactions at the solid-gas pore interface; and the onset of gas phase reactions (flaming) from existing surface reactions. Smoldering presents a serious fire risk because the combustion can propagate slowly in a material's interior and go undetected for long periods of time. It typically yields a substantially higher conversion of fuel to toxic compounds than does flaming (though more slowly), and may undergo a sudden transition to flaming.

Acute dermal abscesses caused by Serratia marcescens.

PubMed

Soria, Xavier; Bielsa, Isabel; Ribera, Miquel; Herrero, María José; Domingo, Helena; Carrascosa, José Manuel; Ferrándiz, Carlos

2008-05-01

Primary acute cutaneous infections caused by Serratia marcescens are extremely unusual. Nevertheless, Serratia infections are especially frequent in chronic granulomatous disease, which is a primary immunodeficiency that affects phagocytic cells of the innate immune system. We report a young man without history of infections, who developed multiple dermal abscesses on a leg with chronic lymphoedema attributed to S marcescens. Laboratory investigations showed a delayed partial neutrophilic oxidative function. It is remarkable that the patient did not have any other infections during childhood, when most of the innate immune deficiencies are diagnosed, and he had no history of granulomatous lesions. We hypothesize that the delayed neutrophilic oxidative function could be explained by a partial neutrophilic oxidative function, which could be enough to maintain the patient asymptomatic until this infection.

Chemical Looping Technology: Oxygen Carrier Characteristics.

PubMed

Luo, Siwei; Zeng, Liang; Fan, Liang-Shih

2015-01-01

Chemical looping processes are characterized as promising carbonaceous fuel conversion technologies with the advantages of manageable CO2 capture and high energy conversion efficiency. Depending on the chemical looping reaction products generated, chemical looping technologies generally can be grouped into two types: chemical looping full oxidation (CLFO) and chemical looping partial oxidation (CLPO). In CLFO, carbonaceous fuels are fully oxidized to CO2 and H2O, as typically represented by chemical looping combustion with electricity as the primary product. In CLPO, however, carbonaceous fuels are partially oxidized, as typically represented by chemical looping gasification with syngas or hydrogen as the primary product. Both CLFO and CLPO share similar operational features; however, the optimum process configurations and the specific oxygen carriers used between them can vary significantly. Progress in both CLFO and CLPO is reviewed and analyzed with specific focus on oxygen carrier developments that characterize these technologies.

Optical conductivity of partially oxidized graphene from first principles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nasehnia, F., E-mail: f.nasehnia@gmail.com; Seifi, M., E-mail: Seifi@guilan.ac.ir

2015-07-07

We investigate the geometry, electronic structure, and optical properties of partially oxidized graphene using density functional theory. Our calculations show that oxygen atoms are chemisorbed on graphene plane and distort carbon atoms vertically, with almost no change in the in-plane structure. The ground state configurations for different oxygen coverages ranging from 2% to 50% (O/C ratio) are calculated and show the strong tendency of oxygen adatoms to aggregate and form discrete islands on graphene plane. It is found that the opened band gap due to oxygen functionalization depends on the oxygen density and the adsorption configuration. The gap is notmore » significant for oxygen densities lower than 8%. The optical conductivities are calculated in the infrared, visible, and ultraviolet regions and show different characteristic features depending on the degree of oxidation. These results imply that optical measurement techniques can be employed to monitor oxidation (or reduction) process as contact-free methods.« less

Oxygen partial pressure influenced structural and optical properties of DC magnetron sputtered ZrO{sub 2} films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kondaiah, P.; Madhavi, V.; Uthanna, S.

2013-02-05

Thin films of zirconium oxide (ZrO{sub 2}) were deposited on (100) p-silicon and quartz substrates by sputtering of metallic zirconium target under different oxygen partial pressures in the range 8 Multiplication-Sign 10{sup -3}-6 Multiplication-Sign 10{sup -2}Pa. The effect of oxygen partial pressure on the structural and optical properties of the deposited films was systematically investigated. The deposition rate of the films decreased from 3.3 to 1.83 nm/min with the increase of oxygen partial pressure from 8 Multiplication-Sign 10{sup -3}-6 Multiplication-Sign 10{sup -2}Pa respectively. The X-ray diffraction profiles revealed that the films exhibit (111) refection of zirconium oxide in monoclinic phase.more » The optical band gap of the films increased from 5.62 to 5.80 eV and refractive index increased from 2.01 to 2.08 with the increase of oxygen partial pressure from 8 Multiplication-Sign 10{sup -3}-6 Multiplication-Sign 10{sup -2}Pa respectively.« less

Effect of graphene oxide ratio on the cell adhesion and growth behavior on a graphene oxide-coated silicon substrate

NASA Astrophysics Data System (ADS)

Jeong, Jin-Tak; Choi, Mun-Ki; Sim, Yumin; Lim, Jung-Taek; Kim, Gil-Sung; Seong, Maeng-Je; Hyung, Jung-Hwan; Kim, Keun Soo; Umar, Ahmad; Lee, Sang-Kwon

2016-09-01

Control of living cells on biocompatible materials or on modified substrates is important for the development of bio-applications, including biosensors and implant biomaterials. The topography and hydrophobicity of substrates highly affect cell adhesion, growth, and cell growth kinetics, which is of great importance in bio-applications. Herein, we investigate the adhesion, growth, and morphology of cultured breast cancer cells on a silicon substrate, on which graphene oxides (GO) was partially formed. By minimizing the size and amount of the GO-containing solution and the further annealing process, GO-coated Si samples were prepared which partially covered the Si substrates. The coverage of GO on Si samples decreases upon annealing. The behaviors of cells cultured on two samples have been observed, i.e. partially GO-coated Si (P-GO) and annealed partially GO-coated Si (Annealed p-GO), with a different coverage of GO. Indeed, the spreading area covered by the cells and the number of cells for a given culture period in the incubator were highly dependent on the hydrophobicity and the presence of oxygenated groups on GO and Si substrates, suggesting hydrophobicity-driven cell growth. Thus, the presented method can be used to control the cell growth via an appropriate surface modification.

Thermochemical CO2 splitting via redox cycling of ceria reticulated foam structures with dual-scale porosities.

PubMed

Furler, Philipp; Scheffe, Jonathan; Marxer, Daniel; Gorbar, Michal; Bonk, Alexander; Vogt, Ulrich; Steinfeld, Aldo

2014-06-14

Efficient heat transfer of concentrated solar energy and rapid chemical kinetics are desired characteristics of solar thermochemical redox cycles for splitting CO2. We have fabricated reticulated porous ceramic (foam-type) structures made of ceria with dual-scale porosity in the millimeter and micrometer ranges. The larger void size range, with dmean = 2.5 mm and porosity = 0.76-0.82, enables volumetric absorption of concentrated solar radiation for efficient heat transfer to the reaction site during endothermic reduction, while the smaller void size range within the struts, with dmean = 10 μm and strut porosity = 0-0.44, increases the specific surface area for enhanced reaction kinetics during exothermic oxidation with CO2. Characterization is performed via mercury intrusion porosimetry, scanning electron microscopy, and thermogravimetric analysis (TGA). Samples are thermally reduced at 1773 K and subsequently oxidized with CO2 at temperatures in the range 873-1273 K. On average, CO production rates are ten times higher for samples with 0.44 strut porosity than for samples with non-porous struts. The oxidation rate scales with specific surface area and the apparent activation energy ranges from 90 to 135.7 kJ mol(-1). Twenty consecutive redox cycles exhibited stable CO production yield per cycle. Testing of the dual-scale RPC in a solar cavity-receiver exposed to high-flux thermal radiation (3.8 kW radiative power at 3015 suns) corroborated the superior performance observed in the TGA, yielding a shorter cycle time and a mean solar-to-fuel energy conversion efficiency of 1.72%.

Nanoporous Silicon Combustion: Observation of Shock Wave and Flame Synthesis of Nanoparticle Silica.

PubMed

Becker, Collin R; Gillen, Greg J; Staymates, Matthew E; Stoldt, Conrad R

2015-11-18

The persistent hydrogen termination present in nanoporous silicon (nPS) is unique compared to other forms of nanoscale silicon (Si) which typically readily form a silicon dioxide passivation layer. The hydrogen terminated surface combined with the extremely high surface area of nPS yields a material capable of powerful exothermic reactions when combined with strong oxidizers. Here, a galvanic etching mechanism is used to produce nPS both in bulk Si wafers as well as in patterned regions of Si wafers with microfabricated ignition wires. An explosive composite is generated by filling the pores with sodium perchlorate (NaClO4). Using high-speed video including Schlieren photography, a shock wave is observed to propagate through air at 1127 ± 116 m/s. Additionally, a fireball is observed above the region of nPS combustion which persists for nearly 3× as long when reacted in air compared to N2, indicating that highly reactive species are generated that can further combust with excess oxygen. Finally, reaction products from either nPS-NaClO4 composites or nPS alone combusted with only high pressure O2 (400 psig) gas as an oxidizer are captured in a calorimeter bomb. The products in both cases are similar and verified by transmission electron microscopy (TEM) to include nano- to micrometer scale SiOx particles. This work highlights the complex oxidation mechanism of nPS composites and demonstrates the ability to use a solid state reaction to create a secondary gas phase combustion.

Convergent modulation of singlet and triplet excited states of phosphine-oxide hosts through the management of molecular structure and functional-group linkages for low-voltage-driven electrophosphorescence.

PubMed

Han, Chunmiao; Zhang, Zhensong; Xu, Hui; Xie, Guohua; Li, Jing; Zhao, Yi; Deng, Zhaopeng; Liu, Shiyong; Yan, Pengfei

2013-01-02

The controllable tuning of the excited states in a series of phosphine-oxide hosts (DPExPOCzn) was realized through introducing carbazolyl and diphenylphosphine-oxide (DPPO) moieties to adjust the frontier molecular orbitals, molecular rigidity, and the location of the triplet excited states by suppressing the intramolecular interplay of the combined multi-insulating and meso linkage. On increasing the number of substituents, simultaneous lowering of the first singlet energy levels (S(1)) and raising of the first triplet energy levels (T(1), about 3.0 eV) were achieved. The former change was mainly due to the contribution of the carbazolyl group to the HOMOs and the extended conjugation. The latter change was due to an enhanced molecular rigidity and the shift of the T(1) states from the diphenylether group to the carbazolyl moieties. This kind of convergent modulation of excited states not only facilitates the exothermic energy transfer to the dopants in phosphorescent organic light-emitting diodes (PHOLEDs), but also realizes the fine-tuning of electrical properties to achieve the balanced carrier injection and transportation in the emitting layers. As the result, the favorable performance of blue-light-emitting PHOLEDs was demonstrated, including much-lower driving voltages of 2.6 V for onset and 3.0 V at 100 cd m(-2), as well as a remarkably improved E.Q.E. of 12.6%. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A combined gas cooled nuclear reactor and fuel cell cycle

NASA Astrophysics Data System (ADS)

Palmer, David J.

Rising oil costs, global warming, national security concerns, economic concerns and escalating energy demands are forcing the engineering communities to explore methods to address these concerns. It is the intention of this thesis to offer a proposal for a novel design of a combined cycle, an advanced nuclear helium reactor/solid oxide fuel cell (SOFC) plant that will help to mitigate some of the above concerns. Moreover, the adoption of this proposal may help to reinvigorate the Nuclear Power industry while providing a practical method to foster the development of a hydrogen economy. Specifically, this thesis concentrates on the importance of the U.S. Nuclear Navy adopting this novel design for its nuclear electric vessels of the future with discussion on efficiency and thermodynamic performance characteristics related to the combined cycle. Thus, the goals and objectives are to develop an innovative combined cycle that provides a solution to the stated concerns and show that it provides superior performance. In order to show performance, it is necessary to develop a rigorous thermodynamic model and computer program to analyze the SOFC in relation with the overall cycle. A large increase in efficiency over the conventional pressurized water reactor cycle is realized. Both sides of the cycle achieve higher efficiencies at partial loads which is extremely important as most naval vessels operate at partial loads as well as the fact that traditional gas turbines operating alone have poor performance at reduced speeds. Furthermore, each side of the cycle provides important benefits to the other side. The high temperature exhaust from the overall exothermic reaction of the fuel cell provides heat for the reheater allowing for an overall increase in power on the nuclear side of the cycle. Likewise, the high temperature helium exiting the nuclear reactor provides a controllable method to stabilize the fuel cell at an optimal temperature band even during transients helping to increase performance and reduce degradation of the fuel cell. It also provides the high temperature needed to efficiently produce hydrogen for the fuel cell. Moreover, the inclusion of a highly reliable and electrically independent fuel cell is particularly important as the ship will have the ability to divert large amounts of power from the propulsion system to energize high energy weapon pulse loads without disturbing vital parts of the C4ISR systems or control panels. Ultimately, the thesis shows that the combined cycle is mutually beneficial to each side of the cycle and overall critically needed for our future.

Low-cost directionally-solidified turbine blades, volume 1

NASA Technical Reports Server (NTRS)

Sink, L. W.; Hoppin, G. S., III; Fujii, M.

1979-01-01

A low cost process of manufacturing high stress rupture strength directionally-solidified high pressure turbine blades was successfully developed for the TFE731-3 Turbofan Engine. The basic processing parameters were established using MAR-M 247 and employing the exothermic directional-solidification process in trial castings of turbine blades. Nickel-based alloys were evaluated as directionally-solidified cast blades. A new turbine blade, disk, and associated components were then designed using previously determined material properties. Engine tests were run and the results were analyzed and compared to the originally established goals. The results showed that the stress rupture strength of exothermically heated, directionally-solidified MAR-M 247 turbine blades exceeded program objectives and that the performance and cost reduction goals were achieved.

Boundary-layer development and transition due to free-stream exothermic reactions in shock-induced flows

NASA Technical Reports Server (NTRS)

Hall, J. L.

1974-01-01

A study of the effect of free-stream thermal-energy release from shock-induced exothermic reactions on boundary-layer development and transition is presented. The flow model is that of a boundary layer developing behind a moving shock wave in two-dimensional unsteady flow over a shock-tube wall. Matched sets of combustible hydrogen-oxygen-nitrogen mixtures and inert hydrogen-nitrogen mixtures were used to obtain transition data over a range of transition Reynolds numbers from 1,100,000 to 21,300,000. The heat-energy is shown to significantly stabilize the boundary layer without changing its development character. A method for application of this data to flat-plate steady flows is included.

Method of forming low cost, formable High T(subc) superconducting wire

NASA Technical Reports Server (NTRS)

Smialek, James L. (Inventor)

1989-01-01

A ceramic superconductivity part, such as a wire, is produced through the partial oxidation of a specially formulated copper alloy in a core. The alloys contains low level of quantities of rare earth and alkaline earth dopant elements. Upon oxidation at high temperatures, and superconducting oxide phases are formed as a thin film.

Catalysis by Atomic-Sized Centers: Methane Activation for Partial Oxidation and Combustion

DTIC Science & Technology

2012-05-09

cation it replaces in the host oxide. For example, a La dopant in CeO2 is a low-valence dopant because La is trivalent when it combines with oxygen...Kim, H. M. Lee, R. G. S. Pala, and H. Metiu, Oxidative dehydrogenation of methanol to formaldehyde by isolated vanadium, molybdenum, and chromium

Anaerobic oxidation of [1,2-14C]Dichloroethene under Mn(IV)-reducing conditions

USGS Publications Warehouse

Bradley, Paul M.; Landmeyer, James E.; Dinicola, Richard S.

1998-01-01

Anaerobic oxidation of [1,2-14C]dichloroethene to14CO2 under Mn(IV)-reducing conditions was demonstrated. The results indicate that oxidative degradation of partially chlorinated solvents like dichloroethene can be significant even under anoxic conditions and demonstrate the potential importance of Mn(IV) reduction for remediation of chlorinated groundwater contaminants.

Gravity Effects Observed In Partially Premixed Flames

NASA Technical Reports Server (NTRS)

Puri, Ishwar K.; Aggarwal, Suresh K.; Lock, Andrew J.; Gauguly, Ranjan; Hegde, Uday

2003-01-01

Partially premixed flames (PPFs) contain a rich premixed fuel air mixture in a pocket or stream, and, for complete combustion to occur, they require the transport of oxidizer from an appropriately oxidizer-rich (or fuel-lean) mixture that is present in another pocket or stream. Partial oxidation reactions occur in fuel-rich portions of the mixture and any remaining unburned fuel and/or intermediate species are consumed in the oxidizer-rich portions. Partial premixing, therefore, represents that condition when the equivalence ratio (phi) in one portion of the flowfield is greater than unity, and in another section its value is less than unity. In general, for combustion to occur efficiently, the global equivalence ratio is in the range fuel-lean to stoichiometric. These flames can be established by design by placing a fuel-rich mixture in contact with a fuel-lean mixture, but they also occur otherwise in many practical systems, which include nonpremixed lifted flames, turbulent nonpremixed combustion, spray flames, and unwanted fires. Other practical applications of PPFs are reported elsewhere. Although extensive experimental studies have been conducted on premixed and nonpremixed flames under microgravity, there is a absence of previous experimental work on burner stabilized PPFs in this regard. Previous numerical studies by our group employing a detailed numerical model showed gravity effects to be significant on the PPF structure. We report on the results of microgravity experiments conducted on two-dimensional (established on a Wolfhard-Parker slot burner) and axisymmetric flames (on a coannular burner) that were investigated in a self-contained multipurpose rig. Thermocouple and radiometer data were also used to characterize the thermal transport in the flame.

In situ metrology to characterize water vapor delivery during atomic layer deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahmido, Tariq, E-mail: tariq.ahmido@nist.gov; Kimes, William A.; Sperling, Brent A.

Water is often employed as the oxygen source in metal oxide atomic layer deposition (ALD) processes. It has been reported that variations in the amount of water delivered during metal oxide ALD can impact the oxide film properties. Hence, one contribution to optimizing metal oxide ALD processes would be to identify methods to better control water dose. The development of rapid, quantitative techniques for in situ water vapor measurements during ALD processes would be beneficial to achieve this goal. In this report, the performance of an in situ tunable diode laser absorption spectroscopy (TDLAS) scheme for performing rapid, quantitative watermore » partial pressure measurements in a representative quarter-inch ALD delivery line is described. This implementation of TDLAS, which utilizes a near-infrared distributed-feedback diode laser and wavelength modulation spectroscopy, provides measurements of water partial pressure on a timescale comparable to or shorter than the timescale of the gas dynamics in typical ALD systems. Depending on the degree of signal averaging, this TDLAS system was capable of measuring the water partial pressure with a detection limit in the range of ∼0.80 to ∼0.08 Pa. The utility of this TDLAS scheme was demonstrated by using it to identify characteristics of a representative water delivery system that otherwise would have been difficult to predict. Those characteristics include (1) the magnitude and time dependence of the pressure transient that can occur during water injection, and (2) the dependence of the steady-state water partial pressure on the carrier gas flow rate and the setting of the water ampoule flow restriction.« less

Incorporation of noble metals into aerogels

DOEpatents

Hair, L.M.; Sanner, R.D.; Coronado, P.R.

1998-12-22

Aerogels or xerogels containing atomically dispersed noble metals for applications such as environmental remediation are disclosed. New noble metal precursors, such as Pt--Si or Pd(Si--P){sub 2}, have been created to bridge the incompatibility between noble metals and oxygen, followed by their incorporation into the aerogel or xerogel through sol-gel chemistry and processing. Applications include oxidation of hydrocarbons and reduction of nitrogen oxide species, complete oxidation of volatile organic carbon species, oxidative membranes for photocatalysis and partial oxidation for synthetic applications.

Incorporation of noble metals into aerogels

DOEpatents

Hair, Lucy M.; Sanner, Robert D.; Coronado, Paul R.

1998-01-01

Aerogels or xerogels containing atomically dispersed noble metals for applications such environmental remediation. New noble metal precursors, such as Pt--Si or Pd(Si--P).sub.2, have been created to bridge the incompatibility between noble metals and oxygen, followed by their incorporation into the aerogel or xerogel through sol-gel chemistry and processing. Applications include oxidation of hydrocarbons and reduction of nitrogen oxide species, complete oxidation of volatile organic carbon species, oxidative membranes for photocatalysis and partial oxidation for synthetic applications.

Low-Degree Partial Melting Experiments of CR and H Chondrite Compositions: Implications for Asteroidal Magmatism Recorded in GRA 06128 and GRA 06129 T

NASA Technical Reports Server (NTRS)

Usui, T.; Jones, John H.; Mittlefehldt, D. W.

2010-01-01

Studies of differentiated meteorites have revealed a diversity of differentiation processes on their parental asteroids; these differentiation mechanisms range from whole-scale melting to partial melting without the core formation [e.g., 1]. Recently discovered paired achondrites GRA 06128 and GRA 06129 (hereafter referred to as GRA) represent unique asteroidal magmatic processes. These meteorites are characterized by high abundances of sodic plagioclase and alkali-rich whole-rock compositions, implying that they could originate from a low-degree partial melt from a volatile-rich oxidized asteroid [e.g., 2, 3, 4]. These conditions are consistent with the high abundances of highly siderophile elements, suggesting that their parent asteroid did not segregate a metallic core [2]. In this study, we test the hypothesis that low-degree partial melts of chondritic precursors under oxidizing conditions can explain the whole-rock and mineral chemistry of GRA based on melting experiments of synthesized CR- and H-chondrite compositions.

Oxygen partial pressure dependence of thermoelectric power factor in polycrystalline n-type SrTiO3: Consequences for long term stability in thermoelectric oxides

NASA Astrophysics Data System (ADS)

Sharma, Peter A.; Brown-Shaklee, Harlan J.; Ihlefeld, Jon F.

2017-04-01

The Seebeck coefficient and electrical conductivity have been measured as functions of oxygen partial pressure over the range of 10-22 to 10-1 atm at 1173 K for a 10% niobium-doped SrTiO3 ceramic with a grain size comparable to the oxygen diffusion length. Temperature-dependent measurements performed from 320 to 1275 K for as-prepared samples reveal metallic-like conduction and good thermoelectric properties. However, upon exposure to progressively increasing oxygen partial pressure, the thermoelectric power factor decreased over time scales of 24 h, culminating in a three order of magnitude reduction over the entire operating range. Identical measurements on single crystal samples show negligible changes in the power factor so that the instability of ceramic samples is primarily tied to the kinetics of grain boundary diffusion. This work provides a framework for understanding the stability of thermoelectric properties in oxides under different atmospheric conditions. The control of the oxygen atmosphere remains a significant challenge in oxide thermoelectrics.

Partial oxidation of landfill leachate in supercritical water: Optimization by response surface methodology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gong, Yanmeng; Wang, Shuzhong; Xu, Haidong

Highlights: • Partial oxidation of landfill leachate in supercritical water was investigated. • The process was optimized by Box–Behnken design and response surface methodology. • GY{sub H2}, TRE and CR could exhibit up to 14.32 mmol·gTOC{sup −1}, 82.54% and 94.56%. • Small amounts of oxidant can decrease the generation of tar and char. - Abstract: To achieve the maximum H{sub 2} yield (GY{sub H2}), TOC removal rate (TRE) and carbon recovery rate (CR), response surface methodology was applied to optimize the process parameters for supercritical water partial oxidation (SWPO) of landfill leachate in a batch reactor. Quadratic polynomial models formore » GY{sub H2}, CR and TRE were established with Box–Behnken design. GY{sub H2}, CR and TRE reached up to 14.32 mmol·gTOC{sup −1}, 82.54% and 94.56% under optimum conditions, respectively. TRE was invariably above 91.87%. In contrast, TC removal rate (TR) only changed from 8.76% to 32.98%. Furthermore, carbonate and bicarbonate were the most abundant carbonaceous substances in product, whereas CO{sub 2} and H{sub 2} were the most abundant gaseous products. As a product of nitrogen-containing organics, NH{sub 3} has an important effect on gas composition. The carbon balance cannot be reached duo to the formation of tar and char. CR increased with the increase of temperature and oxidation coefficient.« less

Acrolein oxidizes the cytosolic and mitochondrial thioredoxins in human endothelial cells.

PubMed

Szadkowski, Adam; Myers, Charles R

2008-01-14

Acrolein is a reactive aldehyde that is a widespread environmental pollutant and can be generated endogenously from lipid peroxidation. The thioredoxin (Trx) system in endothelial cells plays a major role in the maintenance of cellular thiol redox balance, and is critical for cell survival. Normally, cells maintain the cytosolic (Trx1) and mitochondrial (Trx2) thioredoxins largely in the reduced state. In human microvascular endothelial cells, Trx1 was more sensitive than Trx2 to oxidation by acrolein. A 30-min exposure to 2.5 microM acrolein caused partial oxidation of Trx1 but not Trx2. The active site dithiol of Trx1 was essentially completely oxidized by 5 microM acrolein whereas 12.5 microM was required for complete oxidation of Trx2. Partial recovery of the Trx1 redox status was observed over a 4h acrolein-free recovery period, with increases in the reduced form and decreases in the fully oxidized form. For cells treated with 2.5 or 5 microM acrolein the recovery did not require protein synthesis, whereas protein synthesis was required for the return of reduced Trx1 in cells treated with 12.5 microM acrolein. Pretreatment of cells with N-acetylcysteine (NAC) resulted in partial protection of Trx1 from oxidation by acrolein. In cells treated with acrolein for 30 min, followed by a 14- to 16-h acrolein-free period, small but significant cytotoxic effects were observed with 2.5 microM acrolein whereas all cells were adversely affected by >or= 12.5 microM. NAC pretreatment significantly decreased the percentage of stressed cells subsequently exposed to 5 or 12.5 microM acrolein. Given the critical role of the thioredoxins in cell survival, the ability of acrolein to oxidize both thioredoxins should be taken into account for a thorough understanding of its cytotoxic effects.

Fuel cell-fuel cell hybrid system

DOEpatents

Geisbrecht, Rodney A.; Williams, Mark C.

2003-09-23

A device for converting chemical energy to electricity is provided, the device comprising a high temperature fuel cell with the ability for partially oxidizing and completely reforming fuel, and a low temperature fuel cell juxtaposed to said high temperature fuel cell so as to utilize remaining reformed fuel from the high temperature fuel cell. Also provided is a method for producing electricity comprising directing fuel to a first fuel cell, completely oxidizing a first portion of the fuel and partially oxidizing a second portion of the fuel, directing the second fuel portion to a second fuel cell, allowing the first fuel cell to utilize the first portion of the fuel to produce electricity; and allowing the second fuel cell to utilize the second portion of the fuel to produce electricity.

SYNTHESIS OF PARTIAL-OXYGENATED HYDROCARBONS USING PHOTOCATALYSIS IN A LAMINAR FALLING FILM SLURRY REACTOR

EPA Science Inventory

The search for "Green" alternative processes for the oxidation of hydrocarbons selectively to partial oxygenates has been the subject of intense chemical research for many years. The USEPA is currently investigating an alternative synthesis pathway for the production of alcoho...

SYNTHESIS OF PARTIALLY-OXYGENATED HYDROCARBONS USING PHOTOCATALYSIS IN A LAMINAR FALLING FILM SLURRY REACTOR

EPA Science Inventory

The search for "Green" alternative processes for the oxidation of hydrocarbons selectively to partial oxygenates has been the subject of intense chemical research for many years. The USEPA is currently investigating an alternative synthesis pathway for the production of alcoho...

Strategy for Passivating Char Efficiently at the Pilot Scale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dunning, Timothy C

Fast pyrolysis is a promising pathway for the commercialization of liquid transportation fuels from biomass. Fast pyrolysis is performed at moderate heat (450-600 degrees Celcius) in an oxygen-deficient environment. One of the products of fast pyrolysis is biochar, which is often used as a heat source or as a soil amendment. Biochar is a partially reacted solid that is created in the production of bio-oil during fast pyrolysis. Biochar produced at these conditions contains significant quantities of carbon that adsorb oxygen when exposed to air. Biochar adsorption of oxygen is an exothermic process that may generate sufficient heat for combustionmore » in ambient air. Biochar is also a self-insulating material which compounds the effects of heat generated internally. These factors lead to safety concerns and material handling difficulties. The Thermochemical Process Development Unit at the National Renewable Energy Laboratory operates a pilot plant that may be configured for fast pyrolysis, gasification, and will be introducing catalytic fast pyrolysis capabilities in 2018. The TCPDU designed and installed a system to introduce oxygen to collected biochar systematically for a controlled passivation. Biochar is collected and cooled in an oxygen deficient environment during fast pyrolysis. Oxygen is then introduced to the biochar on a mass flow basis. A sparger imbedded within the biochar sample near the bottom of the bed flows air diluted with nitrogen into the char bed, and excess gasses are removed from the top of the collection drum, above the char bed. Pressure within the collection drum is measured indicating adequate flow through filters. Sample weight is recorded before and after passivation. During passivation, temperature is measured at 18 points within the char bed. Oxygen content and temperature are measured leaving the char bed. Maximum temperature parameters were established to ensure operator safety during biochar passivation. Extensive passivation data was collected on pine and blended feedstocks and has been analyzed to characterize the exotherm of char samples. Observations and data collected while passivating char will be discussed.« less

In-situ study of the gas-phase composition and temperature of an intermediate-temperature solid oxide fuel cell anode surface fed by reformate natural gas

NASA Astrophysics Data System (ADS)

Santoni, F.; Silva Mosqueda, D. M.; Pumiglia, D.; Viceconti, E.; Conti, B.; Boigues Muñoz, C.; Bosio, B.; Ulgiati, S.; McPhail, S. J.

2017-12-01

An innovative experimental setup is used for in-depth and in-operando characterization of solid oxide fuel cell anodic processes. This work focuses on the heterogeneous reactions taking place on a 121 cm2 anode-supported cell (ASC) running with a H2, CH4, CO2, CO and steam gas mixture as a fuel, using an operating temperature of 923 K. The results have been obtained by analyzing the gas composition and temperature profiles along the anode surface in different conditions: open circuit voltage (OCV) and under two different current densities, 165 mA cm-2 and 330 mA cm-2, corresponding to 27% and 54% of fuel utilization, respectively. The gas composition and temperature analysis results are consistent, allowing to monitor the evolution of the principal chemical and electrochemical reactions along the anode surface. A possible competition between CO2 and H2O in methane internal reforming is shown under OCV condition and low current density values, leading to two different types of methane reforming: Steam Reforming and Dry Reforming. Under a current load of 40 A, the dominance of exothermic reactions leads to a more marked increase of temperature in the portion of the cell close to the inlet revealing that current density is not uniform along the anode surface.

The aluminium and iodine pentoxide reaction for the destruction of spore forming bacteria.

PubMed

Clark, Billy R; Pantoya, Michelle L

2010-10-21

The threat of biological weapons is a major concern in the present day and has led to studying methods to neutralize spore forming bacteria. A new technique involves the use of a thermite reaction that exhibits biocidal properties to limit bacterial growth. The objective was to examine the influence on bacteria growth upon spore exposure to thermite reactions with and without biocidal properties. Three thermites are considered: two that have biocidal properties (aluminium (Al) combined with iodine pentoxide (I(2)O(5)) and Al combined with silver oxide (Ag(2)O)); and, one that produces a highly exothermic reaction but has no biocidal properties (Al combined with iron oxide (Fe(2)O(3))). Results show that Al + I(2)O(5) is extremely effective at neutralizing spores after only one hour of exposure. The temperature generated by the reaction was not determined to be an influential factor affecting spore growth kinetics. Further analysis of the thermite reactions revealed that the Al + I(2)O(5) reaction produces iodine gas that effectively interacts with the spores and neutralizes bacteria growth, while the Al + Ag(2)O reaction temperature does not vaporize silver. In the condensed phase silver does not interact with the spores enough to neutralize bacteria growth. This study gives evidence that a thermite can be used as a stable transportation and delivery system for biocidal gas.

Removal of pyrene and benzo(a)pyrene micropollutant from water via adsorption by green synthesized iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Hassan, Saad S. M.; Abdel-Shafy, Hussein I.; Mansour, Mona S. M.

2018-03-01

Polycyclic aromatic hydrocarbons (PAHs) in water are classified as organic micropollutants, which are carcinogenic even in very low concentration (ppb). In this study the green synthesized iron oxide nanoparticles (IONPs) were green synthesized at room temperature by using pomegranate peel extract. The green synthesized IONPs were used for adsorbing benzo(a)pyrene and pyrene (PAHs) from water. Factors affecting the adsorption were investigated. These factors are: nanoparticles dose, pH, temperature, and initial concentration of PAHs. The overall results showed that the maximum adsorption capacities of IONPs towards pyrene and benzo(a)pyrene were 2.8 and 0.029 mg g-1, respectively. The thermodynamic study indicated an exothermic adsorption process of pyrene and benzo(a)pyrene. The kinetic and isotherm studies were carried out. The obtained data revealed that the adsorption process follows a pseudo-second order mechanism and obeys Langmuir isotherm model. In addition, the IONPs proved to be a potential candidate for the adsorption of pyrene and benzo(a)pyrene even after five cycles of use and regeneration. The investigation was extended using semi-pilot plant to remove the studied PAHs from artificially contaminated water. The results showed that the IONPs was capable to remove the pyrene and benzo (a) pyrene at the rate of 98.5 and 99%, respectively. It also can be used as disinfectant.

Material distribution in light water reactor-type bundles tested under severe accident conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Noack, V.; Hagen, S.J.L.; Hofmann, P.

1997-02-01

Severe fuel damage experiments simulating small-break loss-of-coolant accidents have been carried out in the CORA out-of-pile test facility at Forschungszentrum Karlsruhe. Rod bundles with electrically heated fuel rod simulators containing annular UO{sub 2} pellets, UO{sub 2} full pellet rods, and absorber rods of two kinds (Ag/In/Cd to represent pressurized water reactor conditions and B{sub 4}C to represent boiling water reactor and VVER-1000 fuel elements) were subjected to temperature transients up to 2,300 K. A special method was applied to determine the axial mass distribution of bundle materials. The low-temperature melt formation by various interactions between zirconium and components of absorbermore » and spacer grids strongly influences the bundle degradation and material relocation. Absorber materials can separate from the fuel by a noncoherent relocation of the materials at different temperatures. The distributions of solidified materials in the different test bundles show a clear dependence on the axial temperature profile. Coolant channel blockages are observed mainly at the lower end of the bundle, i.e., near the lowest elevation at which an oxidation excursion resulting from the highly exothermic zirconium-steam reaction had been experienced. This elevation corresponds with a steep axial temperature gradient in the maximum temperature attained. Oxide layers on Zircaloy result in reduced melt formation.« less

Crystallization behavior of the Li2S-P2S5 glass electrolyte in the LiNi1/3Mn1/3Co1/3O2 positive electrode layer.

PubMed

Tsukasaki, Hirofumi; Mori, Yota; Otoyama, Misae; Yubuchi, So; Asano, Takamasa; Tanaka, Yoshinori; Ohno, Takahisa; Mori, Shigeo; Hayashi, Akitoshi; Tatsumisago, Masahiro

2018-04-18

Sulfide-based all-solid-state lithium batteries are a next-generation power source composed of the inorganic solid electrolytes which are incombustible and have high ionic conductivity. Positive electrode composites comprising LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC) and 75Li 2 S·25P 2 S 5 (LPS) glass electrolytes exhibit excellent charge-discharge cycle performance and are promising candidates for realizing all-solid-state batteries. The thermal stabilities of NMC-LPS composites have been investigated by transmission electron microscopy (TEM), which indicated that an exothermal reaction could be attributed to the crystallization of the LPS glass. To further understand the origin of the exothermic reaction, in this study, the precipitated crystalline phase of LPS glass in the NMC-LPS composite was examined. In situ TEM observations revealed that the β-Li 3 PS 4 precipitated at approximately 200 °C, and then Li 4 P 2 S 6 and Li 2 S precipitated at approximately 400 °C. Because the Li 4 P 2 S 6 and Li 2 S crystalline phases do not precipitate in the single LPS glass, the interfacial contact between LPS and NMC has a significant influence on both the LPS crystallization behavior and the exothermal reaction in the NMC-LPS composites.

A self-heating cartridge for molecular diagnostics.

PubMed

Liu, Changchun; Mauk, Michael G; Hart, Robert; Qiu, Xianbo; Bau, Haim H

2011-08-21

A disposable, water-activated, self-heating, easy-to-use, polymeric cartridge for isothermal nucleic acid amplification and visual fluorescent detection of the amplification products is described. The device is self-contained and does not require any special instruments to operate. The cartridge integrates chemical, water-triggered, exothermic heating with temperature regulation facilitated with a phase-change material (PCM) and isothermal nucleic acid amplification. The water flows into the exothermic reactor by wicking through a porous paper. The porous paper's characteristics control the rate of water supply, which in turn controls the rate of exothermic reaction. The PCM material enables the cartridge to maintain a desired temperature independent of ambient temperatures in the range between 20 °C and 40 °C. The utility of the cartridge is demonstrated by amplifying and detecting Escherichia coli DNA with loop mediated isothermal amplification (LAMP). The device can detect consistently as few as 10 target molecules in the sample. With proper modifications, the cartridge also can work with other isothermal nucleic acid amplification technologies for detecting nucleic acids associated with various pathogens borne in blood, saliva, urine, and other body fluids as well as in water and food. The device is suitable for use at home, in the field, and in poor-resource settings, where access to sophisticated laboratories is impractical, unaffordable, or nonexistent. This journal is © The Royal Society of Chemistry 2011

Instrument-free exothermic heating with phase change temperature control for paper microfluidic devices

NASA Astrophysics Data System (ADS)

Singleton, Jered; Zentner, Chris; Buser, Josh; Yager, Paul; LaBarre, Paul; Weigl, Bernhard H.

2013-03-01

Many infectious diseases, as well as some cancers, that affect global health are most accurately diagnosed through nucleic acid amplification and detection. There is a great need to simplify nucleic acid-based assay systems for use in global health in low-resource settings as well as in settings that do not have convenient access to laboratory staff and equipment such as doctors' offices and home care settings. In developing countries, unreliable electric power, inadequate supply chains, and lack of maintenance for complex diagnostic instruments are all common infrastructure shortfalls. Many elements of instrument-free, disposable, nucleic acid amplification assays have been demonstrated in recent years. However, the problem of instrument-free,1 low-cost, temperature-controlled chemical heating remains unsolved. In this paper we present the current status and results of work towards developing disposable, low-cost, temperature-controlled heaters designed to support isothermal nucleic acid amplification assays that are integrated with a two-dimensional paper network. Our approach utilizes the heat generated through exothermic chemical reactions and controls the heat through use of engineered phase change materials to enable sustained temperatures required for nucleic acid amplification. By selecting appropriate exothermic and phase change materials, temperatures can be controlled over a wide range, suitable for various isothermal amplification methods, and maintained for over an hour at an accuracy of +/- 1°C.

Instrument-free exothermic heating with phase change temperature control for paper microfluidic devices.

PubMed

Singleton, Jered; Zentner, Chris; Buser, Josh; Yager, Paul; LaBarre, Paul; Weigl, Bernhard H

2013-03-09

Many infectious diseases, as well as some cancers, that affect global health are most accurately diagnosed through nucleic acid amplification and detection. There is a great need to simplify nucleic acid-based assay systems for use in global health in low-resource settings as well as in settings that do not have convenient access to laboratory staff and equipment such as doctors' offices and home care settings. In developing countries, unreliable electric power, inadequate supply chains, and lack of maintenance for complex diagnostic instruments are all common infrastructure shortfalls. Many elements of instrument-free, disposable, nucleic acid amplification assays have been demonstrated in recent years. However, the problem of instrument-free, low-cost, temperature-controlled chemical heating remains unsolved. In this paper we present the current status and results of work towards developing disposable, low-cost, temperature-controlled heaters designed to support isothermal nucleic acid amplification assays that are integrated with a two-dimensional paper network. Our approach utilizes the heat generated through exothermic chemical reactions and controls the heat through use of engineered phase change materials to enable sustained temperatures required for nucleic acid amplification. By selecting appropriate exothermic and phase change materials, temperatures can be controlled over a wide range, suitable for various isothermal amplification methods, and maintained for over an hour at an accuracy of +/- 1°C.

Thermal explosion analysis of methyl ethyl ketone peroxide by non-isothermal and isothermal calorimetric applications.

PubMed

Chi, Jen-Hao; Wu, Sheng-Hung; Shu, Chi-Min

2009-11-15

In the past, process incidents attributed to organic peroxides (OPs) that involved near misses, over-pressures, runaway reactions, and thermal explosions occurred because of poor training, human error, incorrect kinetic assumptions, insufficient change management, and inadequate chemical knowledge in the manufacturing process. Calorimetric applications were employed broadly to test organic peroxides on a small-scale because of their thermal hazards, such as exothermic behavior and self-accelerating decomposition in the laboratory. In essence, methyl ethyl ketone peroxide (MEKPO) is highly reactive and exothermically unstable. In recent years, it has undergone many thermal explosions and runaway reaction incidents in the manufacturing process. Differential scanning calorimetry (DSC), vent sizing package 2 (VSP2), and thermal activity monitor (TAM) were employed to analyze thermokinetic parameters and safety index. The intent of the analyses was to facilitate the use of various auto-alarm equipments to detect over-pressure, over-temperature, and hazardous materials leaks for a wide spectrum of operations. Results indicated that MEKPO decomposition is detected at low temperatures (30-40 degrees C), and the rate of decomposition was shown to exponentially increase with temperature and pressure. Determining time to maximum rate (TMR), self-accelerating decomposition temperature (SADT), maximum temperature (T(max)), exothermic onset temperature (T(0)), and heat of decomposition (DeltaH(d)) was essential for identifying early-stage runaway reactions effectively for industries.

Exothermic double-disk dark matter

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCullough, Matthew; Randall, Lisa, E-mail: mccull@mit.edu, E-mail: randall@physics.harvard.edu

2013-10-01

If a subdominant component of dark matter (DM) interacts via long-range dark force carriers it may cool and collapse to form complex structures within the Milky Way galaxy, such as a rotating dark disk. This scenario was proposed recently and termed ''Double-Disk Dark Matter'' (DDDM). In this paper we consider the possibility that DDDM remains in a cosmologically long-lived excited state and can scatter exothermically on nuclei (ExoDDDM). We investigate the current status of ExoDDDM direct detection and find that ExoDDDM can readily explain the recently announced ∼ 3σ excess observed at CDMS-Si, with almost all of the 90% best-fitmore » parameter space in complete consistency with limits from other experiments, including XENON10 and XENON100. In the absence of isospin-dependent couplings, this consistency requires light DM with mass typically in the 5-15 GeV range. The hypothesis of ExoDDDM can be tested in direct detection experiments through its peaked recoil spectra, reduced annual modulation amplitude, and, in some cases, its novel time-dependence. We also discuss future direct detection prospects and additional indirect constraints from colliders and solar capture of ExoDDDM. As theoretical proof-of-principle, we combine the features of exothermic DM models and DDDM models to construct a complete model of ExoDDDM, exhibiting all the required properties.« less

Instrument-free exothermic heating with phase change temperature control for paper microfluidic devices

PubMed Central

Singleton, Jered; Zentner, Chris; Buser, Josh; Yager, Paul; LaBarre, Paul; Weigl, Bernhard H.

2014-01-01

Many infectious diseases, as well as some cancers, that affect global health are most accurately diagnosed through nucleic acid amplification and detection. There is a great need to simplify nucleic acid-based assay systems for use in global health in low-resource settings as well as in settings that do not have convenient access to laboratory staff and equipment such as doctors' offices and home care settings. In developing countries, unreliable electric power, inadequate supply chains, and lack of maintenance for complex diagnostic instruments are all common infrastructure shortfalls. Many elements of instrument-free, disposable, nucleic acid amplification assays have been demonstrated in recent years. However, the problem of instrument-free,1 low-cost, temperature-controlled chemical heating remains unsolved. In this paper we present the current status and results of work towards developing disposable, low-cost, temperature-controlled heaters designed to support isothermal nucleic acid amplification assays that are integrated with a two-dimensional paper network. Our approach utilizes the heat generated through exothermic chemical reactions and controls the heat through use of engineered phase change materials to enable sustained temperatures required for nucleic acid amplification. By selecting appropriate exothermic and phase change materials, temperatures can be controlled over a wide range, suitable for various isothermal amplification methods, and maintained for over an hour at an accuracy of +/- 1°C. PMID:25426269

Novel Nanometric Superstructures for Radiation and Magnetic Sensing

DTIC Science & Technology

2007-05-22

AAO Anodic aluminum oxide AFM Atomic force microscope AFRL Air...Ni nanowires in a 2 µm AAO film after aluminum oxide was partially dissolved; (c) part of the Bi nanowires in a 25 µm AAO template after aluminum ...conditions [R3]. In this process, after removing the thick aluminum oxide film obtained from the first long anodization , the aluminum surface

Stability of solid oxide fuel cell materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Armstrong, T.R.; Bates, J.L.; Chick, L.A.

1996-04-01

Interconnection materials in a solid oxide fuel cell are exposed to both highly oxidizing conditions at the cathode and to highly reducing conditions at the anode. The thermal expansion characteristics of substituted lanthanum and yttrium chromite interconnect materials were evaluated by dilatometry as a function of oxygen partial pressures from 1 atm to 10{sup -18} atm, controlled using a carbon dioxide/hydrogen buffer.

Impact of Silicon Nanocrystal Oxidation on the Nonmetallic Growth of Carbon Nanotubes.

PubMed

Rocks, Conor; Mitra, Somak; Macias-Montero, Manuel; Maguire, Paul; Svrcek, Vladimir; Levchenko, Igor; Ostrikov, Kostya; Mariotti, Davide

2016-07-27

Carbon nanotube (CNT) growth has been demonstrated recently using a number of nonmetallic semiconducting and metal oxide nanoparticles, opening up pathways for direct CNT synthesis from a number of more desirable templates without the need for metallic catalysts. However, CNT growth mechanisms using these nonconventional catalysts has been shown to largely differ and reamins a challenging synthesis route. In this contribution we show CNT growth from partially oxidized silicon nanocrystals (Si NCs) that exhibit quantum confinement effects using a microwave plasma enhanced chemical vapor deposition (PECVD) method. On the basis of solvent and a postsynthesis frgamentation process, we show that oxidation of our Si NCs can be easily controlled. We determine experimentally and explain with theoretical simulations that the Si NCs morphology together with a necessary shell oxide of ∼1 nm is vital to allow for the nonmetallic growth of CNTs. On the basis of chemical analysis post-CNT-growth, we give insight into possible mechanisms for CNT nucleation and growth from our partially oxidized Si NCs. This contribution is of significant importance to the improvement of nonmetallic catalysts for CNT growth and the development of Si NC/CNT interfaces.

Cyclic catalytic upgrading of chemical species using metal oxide materials

NASA Technical Reports Server (NTRS)

White, James H. (Inventor); Schutte, Erick J. (Inventor); Rolfe, Sara L. (Inventor)

2010-01-01

Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having one of the following formulas: (a) Ce.sub.xB.sub.yB'.sub.zB''O.sub..delta., wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, or Fe; B''=Cu; 0.01

Cyclic catalytic upgrading of chemical species using metal oxide materials

DOEpatents

White, James H.; Schutte, Erick J.; Rolfe, Sara L.

2010-11-02

Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having one of the following formulas: (a) Ce.sub.xB.sub.yB'.sub.zB''O.sub..delta., wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, or Fe; B''=Cu; 0.01

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, K.; Schelhas, L. T.; Siah, S. C.

There have been a number of studies on the fabrication of Sn-doped gallium oxide (Ga 2O 3:Sn) films with both conductive and transparent properties using a variety of deposition methods. However, often, synthesis results in films that are not transparent. In this paper, we examine the mechanisms underlying these results in Ga 2O 3:Sn thin films prepared at various growth temperatures, Sn concentrations, and oxygen partial pressures. With X-ray absorption spectroscopy, transmission electron microscopy and energy dispersive spectroscopy, we find that when films are grown under the oxygen deficient conditions there are Ga sub-oxide and SnO x phases in themore » Ga 2O 3:Sn thin film. These Ga sub-oxide phases are only found in non-transparent films, and so we infer that the Ga sub-oxide is responsible for the non-transparency. Furthermore, these observations suggest that to obtain transparent Ga 2O 3:Sn, films deposition or subsequent annealing must be carefully controlled in both temperature and oxygen partial pressure to avoid the formation of Ga sub-oxide phases.« less

Molybdenum disilicide composites reinforced with zirconia and silicon carbide

DOEpatents

Petrovic, John J.

1995-01-01

Compositions consisting essentially of molybdenum disilicide, silicon carbide, and a zirconium oxide component. The silicon carbide used in the compositions is in whisker or powder form. The zirconium oxide component is pure zirconia or partially stabilized zirconia or fully stabilized zirconia.

Kinetic and mechanistic study of bimetallic Pt-Pd/Al 2O 3 catalysts for CO and C 3H 6 oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hazlett, Melanie J.; Moses-Debusk, Melanie; Parks, III, James E.

2016-09-21

Low temperature combustion (LTC) diesel engines are being developed to meet increased fuel economy demands. However, some LTC engines emit higher levels of CO and hydrocarbons and therefore diesel oxidation catalyst (DOC) efficiency will be critical. Here, CO and propylene oxidation were studied, as representative LTC exhaust components, over model bimetallic Pt-Pd/γ-Al 2O 3 catalysts. During CO oxidation tests, monometallic Pt suffered the most extensive inhibition which was correlated to a greater extent of dicarbonyl species formation. Pd and Pd-rich bimetallics were inhibited by carbonate formation at higher temperatures. The 1:1 and 3:1 Pt:Pd bimetallic catalysts did not form themore » dicarbonyl species to the same extent as the monometallic Pt sample, and therefore did not suffer from the same level of inhibition. Similarly they also did not form carbonates to as large an extent as the Pd-rich samples and were therefore not as inhibited from this intermediate surface species at higher temperature. The Pd-rich samples were relatively poor propylene oxidation catalysts; and partial oxidation product accumulation deactivated these catalysts. Byproducts observed include acetone, ethylene, acetaldehyde, acetic acid, formaldehyde and CO. For CO and propylene co-oxidation, the onset of propylene oxidation was not observed until complete CO oxidation was achieved, and the bimetallics showed higher activity. In conclusion, this was again related to less extensive poisoning, less dicarbonyl species formation and less overall partial oxidation product accumulation.« less

Source identification of nitrous oxide on autotrophic partial nitrification in a granular sludge reactor.

PubMed

Rathnayake, R M L D; Song, Y; Tumendelger, A; Oshiki, M; Ishii, S; Satoh, H; Toyoda, S; Yoshida, N; Okabe, S

2013-12-01

Emission of nitrous oxide (N2O) during biological wastewater treatment is of growing concern since N2O is a major stratospheric ozone-depleting substance and an important greenhouse gas. The emission of N2O from a lab-scale granular sequencing batch reactor (SBR) for partial nitrification (PN) treating synthetic wastewater without organic carbon was therefore determined in this study, because PN process is known to produce more N2O than conventional nitrification processes. The average N2O emission rate from the SBR was 0.32 ± 0.17 mg-N L(-1) h(-1), corresponding to the average emission of N2O of 0.8 ± 0.4% of the incoming nitrogen load (1.5 ± 0.8% of the converted NH4(+)). Analysis of dynamic concentration profiles during one cycle of the SBR operation demonstrated that N2O concentration in off-gas was the highest just after starting aeration whereas N2O concentration in effluent was gradually increased in the initial 40 min of the aeration period and was decreased thereafter. Isotopomer analysis was conducted to identify the main N2O production pathway in the reactor during one cycle. The hydroxylamine (NH2OH) oxidation pathway accounted for 65% of the total N2O production in the initial phase during one cycle, whereas contribution of the NO2(-) reduction pathway to N2O production was comparable with that of the NH2OH oxidation pathway in the latter phase. In addition, spatial distributions of bacteria and their activities in single microbial granules taken from the reactor were determined with microsensors and by in situ hybridization. Partial nitrification occurred mainly in the oxic surface layer of the granules and ammonia-oxidizing bacteria were abundant in this layer. N2O production was also found mainly in the oxic surface layer. Based on these results, although N2O was produced mainly via NH2OH oxidation pathway in the autotrophic partial nitrification reactor, N2O production mechanisms were complex and could involve multiple N2O production pathways. Copyright © 2013 Elsevier Ltd. All rights reserved.

A Demonstration of Le Chatelier’s Principle on the Nanoscale

PubMed Central

2017-01-01

Photothermal desorption of molecules from plasmonic nanoparticles is an example of a light-triggered molecular release due to heating of the system. However, this phenomenon ought to work only if the molecule–nanoparticle interaction is exothermic in nature. In this study, we compare protein adsorption behavior onto gold nanoparticles for both endothermic and exothermic complexation reactions, and demonstrate that Le Chatelier’s principle can be applied to predict protein adsorption or desorption on nanomaterial surfaces. Polyelectrolyte-wrapped gold nanorods were used as adsorption platforms for two different proteins, which we were able to adsorb/desorb from the nanorod surface depending on the thermodynamics of their interactions. Furthermore, we show that the behaviors hold up under more complex biological environments such as fetal bovine serum. PMID:29104926

On the validity of the Arrhenius equation for electron attachment rate coefficients.

PubMed

Fabrikant, Ilya I; Hotop, Hartmut

2008-03-28

The validity of the Arrhenius equation for dissociative electron attachment rate coefficients is investigated. A general analysis allows us to obtain estimates of the upper temperature bound for the range of validity of the Arrhenius equation in the endothermic case and both lower and upper bounds in the exothermic case with a reaction barrier. The results of the general discussion are illustrated by numerical examples whereby the rate coefficient, as a function of temperature for dissociative electron attachment, is calculated using the resonance R-matrix theory. In the endothermic case, the activation energy in the Arrhenius equation is close to the threshold energy, whereas in the case of exothermic reactions with an intermediate barrier, the activation energy is found to be substantially lower than the barrier height.

Non-linear interaction of a detonation/vorticity wave

NASA Technical Reports Server (NTRS)

Lasseigne, D. G.; Jackson, T. L.; Hussaini, M. Y.

1991-01-01

The interaction of an oblique, overdriven detonation wave with a vorticity disturbance is investigated by a direct two-dimensional numerical simulation using a multi-domain, finite-difference solution of the compressible Euler equations. The results are compared to those of linear theory, which predict that the effect of exothermicity on the interaction is relatively small except possibly near a critical angle where linear theory no longer holds. It is found that the steady-state computational results agree with the results of linear theory. However, for cases with incident angle near the critical angle, moderate disturbance amplitudes, and/or sudden transient encounter with a disturbance, the effects of exothermicity are more pronounced than predicted by linear theory. Finally, it is found that linear theory correctly determines the critical angle.

Ballistic Motion of Enzymes that Catalyze Highly Exothermic Reactions

NASA Astrophysics Data System (ADS)

Tsekouras, Konstantinos; Pressé, Steve

Recently we proposed that the experimentally observed enhanced diffusion of enzymes catalyzing highly exothermic reactions is a consequence of their mechanism for dissipating reaction energy. More specifically, we proposed that reaction energy spreads out from the reaction site in the form of an acoustic wave which causes the enzyme to asymmetrically deform into the solvent. The solvent reaction propels the enzyme. However, it has been noted that in water, high viscosity should reduce enzyme momentum to zero within a few ps, so any diffusion increase should not be observable. Here we provide a model explaining how small volumetric expansions of biomolecules inside water may cause fluid compression that in turn creates regions of low fluid density around the biomolecule. We then investigate the dynamics of the biomolecule in the presence of these perturbations.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rabin, B.H.

This paper reports on a ceramic joining technique that has been developed that utilizes an exothermic combustion reaction to simultaneously synthesize the joint interlayer material and to bond together the ceramic workpieces. The method has been used to join SiC ceramics using Ti-C-Ni powder mixtures that ignite below 1200{degrees} C to form a TiC-Ni joining material. Thin layers of the powder reactants were prepared by tape casting, and joining was accomplished by heating in a hot-press to ignite the combustion reaction. during this process, localized exothermic heating of the joint region resulted in chemical interaction at the interface between themore » TiC-Ni and the SiC ceramic that contributed to bonding. Room-temperature four-point bending strengths of joints produced by this method have exceeded 100 MPa.« less

Carbon-coated magnetic palladium: applications in partial oxidation of alcohols and coupling reactions.

EPA Science Inventory

Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; catalyst can be used for oxidation of alcohols, amination reaction and arylation of aryl halides (cross coupli...

Molybdenum disilicide composites reinforced with zirconia and silicon carbide

DOEpatents

Petrovic, J.J.

1995-01-17

Compositions are disclosed consisting essentially of molybdenum disilicide, silicon carbide, and a zirconium oxide component. The silicon carbide used in the compositions is in whisker or powder form. The zirconium oxide component is pure zirconia or partially stabilized zirconia or fully stabilized zirconia.

PHOTOOXIDATION OF HYDROCARBONS TO PARTIAL OXYGENATES IN AN AQUEOUS ENVIRONMENT [EXHIBIT, POSTER

EPA Science Inventory

The USEPA is researching the use of alternative oxidation technologies (AOT's) as a catalytic process for the selective oxidation of hydrocarbon substrates. One AOT currently under investigation is the use of photocatalysis employed with a laminar thin-film falling reactor. Thi...

Regimes of an atmospheric pressure nanosecond repetitively pulsed discharge for methane partial oxidation

NASA Astrophysics Data System (ADS)

Maqueo, P. D. G.; Maier, M.; Evans, M. D. G.; Coulombe, S.; Bergthorson, J. M.

2018-04-01

The operation of a nanosecond repetitively pulsed discharge for partial oxidation of CH4 is characterized at atmospheric pressure and room temperature. Two regimes are observed: diffuse and filamentary. The first is a low power regime, characterized by low rotational temperatures around 400 K. The second is much more energetic with rotational temperatures close to 600 K. Both have vibrational temperatures of at least 10 times their rotational temperatures. The average electron number density was determined to be 8.9×1015 and 4.0×1017 cm-3, respectively, showing an increase in the ionization fraction in the more powerful filamentary regime. Results of CH4 conversion to H2, CO, CO2 and C2H6 are presented for the filamentary regime, while the diffuse regime shows no measurable conversion ability. As expected, oxidative mixtures show higher conversion ability than pure CH4. A maximum conversion efficiency of 26.3% and a maximum energy efficiency of 19.7% were reached for the oxidative mixtures.

Self-degradable Slag/Class F Fly Ash-Blend Cements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sugama, T.; Warren, J.; Butcher, T.

2011-03-01

Self-degradable slag/Class F fly ash blend pozzolana cements were formulated, assuming that they might serve well as alternative temporary fracture sealers in Enhanced Geothermal System (EGS) wells operating at temperatures of {ge} 200 C. Two candidate formulas were screened based upon material criteria including an initial setting time {ge} 60 min at 85 C, compressive strength {ge} 2000 psi for a 200 C autoclaved specimen, and the extent of self-degradation of cement heated at {ge} 200 C for it was contacted with water. The first screened dry mix formula consisted of 76.5 wt% slag-19.0 wt% Class F fly ash-3.8 wt%more » sodium silicate as alkali activator, and 0.7 wt% carboxymethyl cellulose (CMC) as the self-degradation promoting additive, and second formula comprised of 57.3 wt% slag, 38.2 wt% Class F fly ash, 3.8 wt% sodium silicate, and 0.7 wt% CMC. After mixing with water and autoclaving it at 200 C, the aluminum-substituted 1.1 nm tobermorite crystal phase was identified as hydrothermal reaction product responsible for the development of a compressive strength of 5983 psi. The 200 C-autoclaved cement made with the latter formula had the combined phases of tobermorite as its major reaction product and amorphous geopolymer as its minor one providing a compressive strength of 5271 psi. Sodium hydroxide derived from the hydrolysis of sodium silicate activator not only initiated the pozzolanic reaction of slag and fly ash, but also played an important role in generating in-situ exothermic heat that significantly contributed to promoting self-degradation of cementitious sealers. The source of this exothermic heat was the interactions between sodium hydroxide, and gaseous CO{sub 2} and CH{sub 3}COOH by-products generated from thermal decomposition of CMC at {ge} 200 C in an aqueous medium. Thus, the magnitude of this self-degradation depended on the exothermic temperature evolved in the sealer; a higher temperature led to a sever disintegration of sealer. The exothermic temperature was controlled by the extent of thermal decomposition of CMC, demonstrating that CMC decomposed at higher temperature emitted more gaseous reactants. Hence, such large emission enhanced the evolution of in-situ exothermic heat. In contrast, the excessive formation of geopolymer phase due to more incorporation of Class F fly ash into this cementitious system affected its ability to self-degrade, reflecting that there was no self-degradation. The geopolymer was formed by hydrothermal reactions between sodium hydroxide from sodium silicate and mullite in Class F fly ash. Thus, the major reason why geopolymer-based cementitiuos sealers did not degrade after heated sealers came in contact with water was their lack of free sodium hydroxide.« less

Isolation and Oxidative Properties of Intact Mitochondria Isolated from Spinach Leaves 1

PubMed Central

Douce, Roland; Moore, Antony L.; Neuburger, Michel

1977-01-01

A procedure was described for preparing intact mitochondria from spinach (Spinacia oleracea L.) leaves. These mitochondria oxidized succinate, malate, pyruvate, α-ketoglutarate, and NADH with good respiratory control and ADP/O ratios comparable to those observed with mitochondria from other plant tissues. Glycine was oxidized by the preparations. This oxidation linked to the mitochondrial electron transport chain, was coupled to three phosphorylation sites and was sensitive to electron transport and phosphorylation inhibitors. Cyanide completely inhibited the oxidation of NADH. The oxidation of succinate, malate, and glycine was only partially inhibited. Images PMID:16660151

Manufacture of ceramic tiles from fly ash

DOEpatents

Hnat, James G.; Mathur, Akshay; Simpson, James C.

1999-01-01

The present invention relates to a process for forming glass-ceramic tiles. Fly ash containing organic material, metal contaminants, and glass forming materials is oxidized under conditions effective to combust the organic material and partially oxidize the metallic contaminants and the glass forming materials. The oxidized glass forming materials are vitrified to form a glass melt. This glass melt is then formed into tiles containing metallic contaminants.

Nitrogen-doped partially reduced graphene oxide rewritable nonvolatile memory.

PubMed

Seo, Sohyeon; Yoon, Yeoheung; Lee, Junghyun; Park, Younghun; Lee, Hyoyoung

2013-04-23

As memory materials, two-dimensional (2D) carbon materials such as graphene oxide (GO)-based materials have attracted attention due to a variety of advantageous attributes, including their solution-processability and their potential for highly scalable device fabrication for transistor-based memory and cross-bar memory arrays. In spite of this, the use of GO-based materials has been limited, primarily due to uncontrollable oxygen functional groups. To induce the stable memory effect by ionic charges of a negatively charged carboxylic acid group of partially reduced graphene oxide (PrGO), a positively charged pyridinium N that served as a counterion to the negatively charged carboxylic acid was carefully introduced on the PrGO framework. Partially reduced N-doped graphene oxide (PrGODMF) in dimethylformamide (DMF) behaved as a semiconducting nonvolatile memory material. Its optical energy band gap was 1.7-2.1 eV and contained a sp2 C═C framework with 45-50% oxygen-functionalized carbon density and 3% doped nitrogen atoms. In particular, rewritable nonvolatile memory characteristics were dependent on the proportion of pyridinum N, and as the proportion of pyridinium N atom decreased, the PrGODMF film lost memory behavior. Polarization of charged PrGODMF containing pyridinium N and carboxylic acid under an electric field produced N-doped PrGODMF memory effects that followed voltage-driven rewrite-read-erase-read processes.

Oxidation of aqueous pharmaceuticals by pulsed corona discharge.

PubMed

Panorel, Iris; Preis, Sergei; Kornev, Iakov; Hatakka, Henry; Louhi-Kultanen, Marjatta

2013-01-01

Oxidation of aromatic compounds of phenolic (paracetamol, beta-oestradiol and salicylic acid) and carboxylic (indomethacin and ibuprofen) structure used in pharmaceutics was studied. Aqueous solutions were treated with pulsed corona discharge (PCD) as a means for advanced oxidation. Pulse repetition frequency, delivered energy dose and oxidation media were the main parameters studied for their influence on the process energy efficiency. The PCD treatment appeared to be effective in oxidation of the target compounds: complete degradation of pollutant together with partial mineralization was achieved at moderate energy consumption; oxidation proceeds faster in alkaline media. Low-molecular carboxylic acids were identified as ultimate oxidation by-products formed in the reaction.

Purification and Partial Characterization of Two Soluble NAD(P)H Dehydrogenases from Arum maculatum Mitochondria 1

PubMed Central

Chauveau, Michèle; Lance, Claude

1991-01-01

Two enzyme systems carrying out the oxidation of NAD(P)H in the presence of various electron acceptors have been isolated and partially characterized from the supernatant of frozen-thawed mitochondria from Arum maculatum spadices. The two systems contain flavoproteins and differ by their ability to oxidize NADH or NADPH, optimum pH and pI values, sensitivity to Ca2+ and EGTA, denaturation by 4 molar urea, molecular mass, and number of subunits. These properties, together with methodological considerations, are compatible with the location of these enzyme activities on the outer surface of the inner mitochondrial membrane, and support the hypothesis of the existence of two separate dehydrogenases responsible for the mitochondrial oxidation of cytosolic NADH and NADPH. Images Figure 1 Figure 3 Figure 7 PMID:16668075

An Illuminating Reaction.

ERIC Educational Resources Information Center

Matthews, Catherine E.

1996-01-01

Describes the use of carbide lights as an excellent mechanism for introducing or reviewing many basic chemistry concepts including elements and compounds, endothermic and exothermic reactions, physical and chemical changes, and balancing chemical equations. (JRH)

Exothermic Bond Breaking: A Persistent Misconception

ERIC Educational Resources Information Center

Galley, William C.

2004-01-01

The misconceptions regarding the nature of ATP hydrolysis and bond breaking are discussed. The students' knowledge in this area is quantitatively measured by a survey of over 600 biochemistry and physiology students.

Improvement of performance in low temperature solid oxide fuel cells operated on ethanol and air mixtures using Cu-ZnO-Al2O3 catalyst layer

NASA Astrophysics Data System (ADS)

Morales, M.; Espiell, F.; Segarra, M.

2015-10-01

Anode-supported single-chamber solid oxide fuel cells with and without Cu-ZnO-Al2O3 catalyst layers deposited on the anode support have been operated on ethanol and air mixtures. The cells consist of gadolinia-doped ceria electrolyte, Ni-doped ceria anode, and La0.6Sr0.4CoO3-δ-doped ceria cathode. Catalyst layers with different Cu-ZnO-Al2O3 ratios are deposited and sintered at several temperatures. Since the performance of single-chamber fuel cells strongly depends on catalytic properties of electrodes for partial oxidation of ethanol, the cells are electrochemically characterized as a function of the temperature, ethanol-air molar ratio and gas flow rate. In addition, catalytic activities of supported anode, catalytic layer-supported anode and cathode for partial oxidation of ethanol are analysed. Afterwards, the effect of composition and sintering temperature of catalyst layer on the cell performance are determined. The results indicate that the cell performance can be significantly enhanced using catalyst layers of 30:35:35 and 40:30:30 wt.% Cu-ZnO-Al2O3 sintered at 1100 °C, achieving power densities above 50 mW cm-2 under 0.45 ethanol-air ratio at temperatures as low as 450 °C. After testing for 15 h, all cells present a gradual loss of power density, without carbon deposition, which is mainly attributed to the partial re-oxidation of Ni at the anode.

Oxygen adsorption onto pure and doped Al surfaces--the role of surface dopants.

PubMed

Lousada, Cláudio M; Korzhavyi, Pavel A

2015-01-21

Using density functional theory (DFT) with the PBE0 density functional we investigated the role of surface dopants in the molecular and dissociative adsorption of O2 onto Al clusters of types Al50, Al50Alad, Al50X and Al49X, where X represents a dopant atom of the following elements Si, Mg, Cu, Sc, Zr, and Ti. Each dopant atom was placed on the Al(111) surface as an adatom or as a substitutional atom, in the last case replacing a surface Al atom. We found that for the same dopant geometry, the closer is the ionization energy of the dopant element to that of elemental Al, the more exothermic is the dissociative adsorption of O2 and the stronger are the bonds between the resulting O atoms and the surface. Additionally we show that the Mulliken concept of electronegativity can be applied in the prediction of the dissociative adsorption energy of O2 on the doped surfaces. The Mulliken modified second-stage electronegativity of the dopant atom is proportional to the exothermicity of the dissociative adsorption of O2. For the same dopant element in an adatom position the dissociation of O2 is more exothermic when compared to the case where the dopant occupies a substitutional position. These observations are discussed in view of the overlap population densities of states (OPDOS) computed as the overlap between the electronic states of the adsorbate O atoms and the clusters. It is shown that a more covalent character in the bonding between the Al surface and the dopant atom causes a more exothermic dissociation of O2 and stronger bonding with the O atoms when compared to a more ionic character in the bonding between the dopant and the Al surface. The extent of the adsorption site reconstruction is dopant atom dependent and is an important parameter for determining the mode of adsorption, adsorption energy and electronic structure of the product of O2 adsorption. The PBE0 functional could predict the existence of the O2 molecular adsorption product for many of the cases investigated here.

Polymerization stress evolution of a bulk-fill flowable composite under different compliances.

PubMed

Guo, Yongwen; Landis, Forrest A; Wang, Zhengzhi; Bai, Ding; Jiang, Li; Chiang, Martin Y M

2016-04-01

To use a compliance-variable instrument to simultaneously measure and compare the polymerization stress (PS) evolution, degree of conversion (DC), and exotherm of a bulk-fill flowable composite to a packable composite. A bulk-fill flowable composite (Filtek Bulk-fill, FBF) and a conventional packable composite (Filtek Z250, Z250) purchased from 3M ESPE were investigated. The composites were studied using a cantilever-beam based instrument equipped with an in situ near infrared (NIR) spectrometer and a microprobe thermocouple. The measurements were carried out under various instrumental compliances (ranging from 0.3327μm/N to 12.3215μm/N) that are comparable to the compliances of clinically prepared tooth cavities. Correlations between the PS and temperature change as well as the DC were interpreted. The maximum PS of both composites at 10min after irradiation decreased with the increase in the compliance of the cantilever beam. The FBF composite generated a lower final stress than the Z250 sample under instrumental compliances less than ca. 4μm/N; however, both materials generated statistically similar PS values at higher compliances. The reaction exotherm and the DC of both materials were found to be independent of compliance. The DC of the FBF sample was slightly higher than that of the packable Z250 composite while the peak exotherm of FBF was almost double that of the Z250 composite. For FBF, a characteristic drop in the PS was observed during the early stage of polymerization for all compliances studied which was not observed in the Z250 sample. This drop was shown to relate to the greater exotherm of the less-filled FBF sample relative to the Z250 composite. While the composites with lower filler content (low viscosity) are generally considered to have lower PS than the conventional packable composites, a bulk-fill flowable composite was shown to produce lower PS under a lower compliance of constraint as would be experienced if the composite was used as the base material in clinical procedures. Published by Elsevier Ltd.

Process of forming catalytic surfaces for wet oxidation reactions

NASA Technical Reports Server (NTRS)

Jagow, R. B. (Inventor)

1977-01-01

A wet oxidation process was developed for oxidizing waste materials, comprising dissolved ruthenium salt in a reactant feed stream containing the waste materials. The feed stream is introduced into a reactor, and the reactor contents are then raised to an elevated temperature to effect deposition of a catalytic surface of ruthenium black on the interior walls of the reactor. The feed stream is then maintained in the reactor for a period of time sufficient to effect at least partial oxidation of the waste materials.

Control of differential strain during heating and cooling of mixed conducting metal oxide membranes

DOEpatents

Carolan, Michael Francis

2007-12-25

Method of operating an oxygen-permeable mixed conducting membrane having an oxidant feed side and a permeate side, which method comprises controlling the differential strain between the oxidant feed side and the permeate side by varying either or both of the oxygen partial pressure and the total gas pressure on either or both of the oxidant feed side and the permeate side of the membrane while changing the temperature of the membrane from a first temperature to a second temperature.

Hydrogen-rich gas generator

NASA Technical Reports Server (NTRS)

Houseman, J.; Cerini, D. J. (Inventor)

1976-01-01

A process and apparatus are described for producing hydrogen-rich product gases. A spray of liquid hydrocarbon is mixed with a stream of air in a startup procedure and the mixture is ignited for partial oxidation. The stream of air is then heated by the resulting combustion to reach a temperature such that a signal is produced. The signal triggers a two way valve which directs liquid hydrocarbon from a spraying mechanism to a vaporizing mechanism with which a vaporized hydrocarbon is formed. The vaporized hydrocarbon is subsequently mixed with the heated air in the combustion chamber where partial oxidation takes place and hydrogen-rich product gases are produced.

Density functional theory study of ethylene partial oxidation on Ag 7 clusters

NASA Astrophysics Data System (ADS)

Yu, Hua-Gen

2006-11-01

The partial oxidation reaction of ethylene on neutral and anionic Ag 7 clusters has been studied using the BPW91 hybrid DFT method with the Stuttgart RSC97 relativistic pseudopotential for the 28-electron ionic core of Ag. The atomic oxygen reaction mechanism is mainly addressed. Results show that the reaction occurs via a stable oxametallacycle intermediate ( AgOCH4p, p = 0 or -1), but it involves small reaction barriers along the reaction path. The ZPE-corrected barrier heights are obtained as 0.7-6.5 kcal/mole. In addition, the structure and anionic effects of Ag 7 clusters are also discussed.

Characteristics of hydrogen produced by partial oxidation and auto-thermal reforming in a small methanol reformer

NASA Astrophysics Data System (ADS)

Horng, Rong-Fang; Chou, Huann-Ming; Lee, Chiou-Hwang; Tsai, Hsien-Te

This paper investigates experimentally, the transient characteristics of a small methanol reformer using partial oxidation (POX) and auto-thermal reforming (ATR) for fuel cell applications. The parameters varied were heating temperature, methanol supply rate, steady mode shifting temperature, O 2/C (O 2/CH 3OH) and S/C (H 2O/CH 3OH) molar ratios with the main aim of promoting a rapid response and a high flow rate of hydrogen. The experiments showed that a high steady mode shifting temperature resulted in a faster temperature rise at the catalyst outlet and vice versa and that a low steady mode shifting temperature resulted in a lower final hydrogen concentration. However, when the mode shifting temperature was too high, the hydrogen production response was not necessarily improved. It was subsequently shown that the optimum steady mode shifting temperature for this experimental set-up was approximately 75 °C. Further, the hydrogen concentration produced by the auto-thermal process was as high as 49.12% and the volume flow rate up to 23.0 L min -1 compared to 40.0% and 20.5 L min -1 produced by partial oxidation.

Some Ecological Mechanisms to Generate Habitability in Planetary Subsurface Areas by Chemolithotrophic Communities: The Ro Tinto Subsurface Ecosystem as a Model System

NASA Astrophysics Data System (ADS)

Fernández-Remolar, David C.; Gómez, Felipe; Prieto-Ballesteros, Olga; Schelble, Rachel T.; Rodríguez, Nuria; Amiols, Ricardo

2008-02-01

Chemolithotrophic communities that colonize subsurface habitats have great relevance for the astrobiological exploration of our Solar System. We hypothesize that the chemical and thermal stabilization of an environment through microbial activity could make a given planetary region habitable. The MARTE project ground-truth drilling campaigns that sampled cryptic subsurface microbial communities in the basement of the Ro Tinto headwaters have shown that acidic surficial habitats are the result of the microbial oxidation of pyritic ores. The oxidation process is exothermic and releases heat under both aerobic and anaerobic conditions. These microbial communities can maintain the subsurface habitat temperature through storage heat if the subsurface temperature does not exceed their maximum growth temperature. In the acidic solutions of the Ro Tinto, ferric iron acts as an effective buffer for controlling water pH. Under anaerobic conditions, ferric iron is the oxidant used by microbes to decompose pyrite through the production of sulfate, ferrous iron, and protons. The integration between the physical and chemical processes mediated by microorganisms with those driven by the local geology and hydrology have led us to hypothesize that thermal and chemical regulation mechanisms exist in this environment and that these homeostatic mechanisms could play an essential role in creating habitable areas for other types of microorganisms. Therefore, searching for the physicochemical expression of extinct and extant homeostatic mechanisms through physical and chemical anomalies in the Mars crust (i.e., local thermal gradient or high concentration of unusual products such as ferric sulfates precipitated out from acidic solutions produced by hypothetical microbial communities) could be a first step in the search for biological traces of a putative extant or extinct Mars biosphere.

Some ecological mechanisms to generate habitability in planetary subsurface areas by chemolithotrophic communities: the Río Tinto subsurface ecosystem as a model system.

PubMed

Fernández-Remolar, David C; Gómez, Felipe; Prieto-Ballesteros, Olga; Schelble, Rachel T; Rodríguez, Nuria; Amils, Ricardo

2008-02-01

Chemolithotrophic communities that colonize subsurface habitats have great relevance for the astrobiological exploration of our Solar System. We hypothesize that the chemical and thermal stabilization of an environment through microbial activity could make a given planetary region habitable. The MARTE project ground-truth drilling campaigns that sampled cryptic subsurface microbial communities in the basement of the Río Tinto headwaters have shown that acidic surficial habitats are the result of the microbial oxidation of pyritic ores. The oxidation process is exothermic and releases heat under both aerobic and anaerobic conditions. These microbial communities can maintain the subsurface habitat temperature through storage heat if the subsurface temperature does not exceed their maximum growth temperature. In the acidic solutions of the Río Tinto, ferric iron acts as an effective buffer for controlling water pH. Under anaerobic conditions, ferric iron is the oxidant used by microbes to decompose pyrite through the production of sulfate, ferrous iron, and protons. The integration between the physical and chemical processes mediated by microorganisms with those driven by the local geology and hydrology have led us to hypothesize that thermal and chemical regulation mechanisms exist in this environment and that these homeostatic mechanisms could play an essential role in creating habitable areas for other types of microorganisms. Therefore, searching for the physicochemical expression of extinct and extant homeostatic mechanisms through physical and chemical anomalies in the Mars crust (i.e., local thermal gradient or high concentration of unusual products such as ferric sulfates precipitated out from acidic solutions produced by hypothetical microbial communities) could be a first step in the search for biological traces of a putative extant or extinct Mars biosphere.

Adsorption of emerging contaminant metformin using graphene oxide.

PubMed

Zhu, Shuai; Liu, Yun-Guo; Liu, Shao-Bo; Zeng, Guang-Ming; Jiang, Lu-Hua; Tan, Xiao-Fei; Zhou, Lu; Zeng, Wei; Li, Ting-Ting; Yang, Chun-Ping

2017-07-01

The occurrence of emerging contaminants in our water resources poses potential threats to the livings. Due to the poor treatment in wastewater management, treatment technologies are needed to effectively remove these products for living organism safety. In this study, Graphene oxide (GO) was tested for the first time for its capacity to remove a kind of emerging wastewater contaminants, metformin. The research was conducted by using a series of systematic adsorption and kinetic experiments. The results indicated that GO could rapidly and efficiently reduce the concentration of metformin, which could provide a solution in handling this problem. The uptake of metformin on the graphene oxide was strongly dependent on temperature, pH, ionic strength, and background electrolyte. The adsorption kinetic experiments revealed that almost 80% removal of metformin was achieved within 20 min for all the doses studied, corresponding to the relatively high k 1 (0.232 min -1 ) and k 2 (0.007 g mg -1  min -1 ) values in the kinetic models. It indicated that the highest adsorption capacity in the investigated range (q m ) of GO for metformin was at pH 6.0 and 288 K. Thermodynamic study indicated that the adsorption was a spontaneous (ΔG 0  < 0) and exothermic (ΔH 0  < 0) process. The adsorption of metformin increased when the pH values changed from 4.0 to 6.0, and decreased adsorption were observed at pH 6.0-11.0. GO still exhibited excellent adsorption capacity after several desorption/adsorption cycles. Besides, both so-called π-π interactions and hydrogen bonds might be mainly responsible for the adsorption of metformin onto GO. Copyright © 2017 Elsevier Ltd. All rights reserved.

Oxidation reaction of polyether-based material and its suppression in lithium rechargeable battery using 4 V class cathode, LiNi1/3Mn1/3Co1/3O2.

PubMed

Kobayashi, Takeshi; Kobayashi, Yo; Tabuchi, Masato; Shono, Kumi; Ohno, Yasutaka; Mita, Yuichi; Miyashiro, Hajime

2013-12-11

The all solid-state lithium battery with polyether-based solid polymer electrolyte (SPE) is regarded as one of next-generation lithium batteries, and has potential for sufficient safety because of the flammable-electrolyte-free system. It has been believed that polyether-based SPE is oxidized at the polymer/electrode interface with 4 V class cathodes. Therefore, it has been used for electric devices such as organic transistor, and lithium battery under 3 V. We estimated decomposition reaction of polyether used as SPE of all solid-state lithium battery. We first identified the decomposed parts of polyether-based SPE and the conservation of most main chain framework, considering the results of SPE analysis after long cycle operations. The oxidation reaction was found to occur slightly at the ether bond in the main chain with the branched side chain. Moreover, we resolved the issue by introducing a self-sacrificing buffer layer at the interface. The introduction of sodium carboxymethyl cellulose (CMC) to the 4 V class cathode surface led to the suppression of SPE decomposition at the interface as a result of the preformation of a buffer layer from CMC, which was confirmed by the irreversible exothermic reaction during the first charge, using electrochemical calorimetry. The attained 1500 cycle operation is 1 order of magnitude longer than those of previously reported polymer systems, and compatible with those of reported commercial liquid systems. The above results indicate to proceed to an intensive research toward the realization of 4 V class "safe" lithium polymer batteries without flammable liquid electrolyte.

Study of Chromium Oxide Activities in EAF Slags

NASA Astrophysics Data System (ADS)

Yan, Baijun; Li, Fan; Wang, Hui; Sichen, Du

2016-02-01

The activity coefficients of chromium in Cu-Cr melts were determined by equilibrating liquid copper with solid Cr2O3 in CO-CO2 atmosphere. The temperature dependence of the activity coefficients of chromium in Cu-Cr melts could be expressed as lg γ_{Cr}(s)^{0} = { 3 2 5 9( ± 1 8 6} )/T - 0. 5 9( { ± 0. 1} ). Based on the above results, the activities of bivalent and trivalent chromium oxide in some slags at 1873 K (1600 °C) were measured. The slags were equilibrated with Cu-Cr melts under two oxygen partial pressures ( {p_{O}_{ 2} }} } = 6.9 × 10-4 and 1.8 × 10-6 Pa, respectively). The morphology of the quenched slags and the solubility of chromium oxide in the melts were investigated by EPMA, SEM, and XRD. Under both oxygen partial pressures, the slags were saturated by the solid solution MgAl2- x Cr x O4- δ . At the low oxygen partial pressure (1.8 × 10-6 Pa), the content of Cr in the liquid phase varied from 0.4 to 1.6 mass pct with the total Cr content in the slags increasing from 1.3 to 10.8 mass pct. At the high oxygen partial pressure (6.9 × 10-4 Pa), the content of Cr in the liquid phase decreased to the level of 0.2 to 0.6 mass pct. Both the activities of CrO and Cr2O3 in slag were found to increase approximately linearly with the increase of the total Cr content in slag. While the oxygen partial pressure had minor effect on the activity of Cr2O3 in the slag, it had significant effect on the activity of CrO.

Manufacture of ceramic tiles from fly ash

DOEpatents

Hnat, J.G.; Mathur, A.; Simpson, J.C.

1999-08-10

The present invention relates to a process for forming glass-ceramic tiles. Fly ash containing organic material, metal contaminants, and glass forming materials is oxidized under conditions effective to combust the organic material and partially oxidize the metallic contaminants and the glass forming materials. The oxidized glass forming materials are vitrified to form a glass melt. This glass melt is then formed into tiles containing metallic contaminants. 6 figs.

Recycling of Magnesium Alloy Employing Refining and Solid Oxide Membrane (SOM) Electrolysis

NASA Astrophysics Data System (ADS)

Guan, Xiaofei; Zink, Peter A.; Pal, Uday B.; Powell, Adam C.

2013-04-01

Pure magnesium was recycled from partially oxidized 50.5 wt pct Mg-Al scrap alloy and AZ91 Mg alloy (9 wt pct Al, 1 wt pct Zn). Refining experiments were performed using a eutectic mixture of MgF2-CaF2 molten salt (flux). During the experiments, potentiodynamic scans were performed to determine the electrorefining potentials for magnesium dissolution and magnesium bubble nucleation in the flux. The measured electrorefining potential for magnesium bubble nucleation increased over time as the magnesium content inside the magnesium alloy decreased. Potentiostatic holds and electrochemical impedance spectroscopy were employed to measure the electronic and ionic resistances of the flux. The electronic resistivity of the flux varied inversely with the magnesium solubility. Up to 100 pct of the magnesium was refined from the Mg-Al scrap alloy by dissolving magnesium and its oxide into the flux followed by argon-assisted evaporation of dissolved magnesium and subsequently condensing the magnesium vapor. Solid oxide membrane electrolysis was also employed in the system to enable additional magnesium recovery from magnesium oxide in the partially oxidized Mg-Al scrap. In an experiment employing AZ91 Mg alloy, only the refining step was carried out. The calculated refining yield of magnesium from the AZ91 alloy was near 100 pct.

Modularity of nitrogen-oxide reducing soil bacteria: linking phenotype to genotype.

PubMed

Roco, Constance A; Bergaust, Linda L; Bakken, Lars R; Yavitt, Joseph B; Shapleigh, James P

2017-06-01

Model denitrifiers convert NO3- to N 2 , but it appears that a significant fraction of natural populations are truncated, conducting only one or two steps of the pathway. To better understand the diversity of partial denitrifiers in soil and whether discrepancies arise between the presence of known N-oxide reductase genes and phenotypic features, bacteria able to reduce NO3- to NO2- were isolated from soil, N-oxide gas products were measured for eight isolates, and six were genome sequenced. Gas phase analyses revealed that two were complete denitrifiers, which genome sequencing corroborated. The remaining six accumulated NO and N 2 O to varying degrees and genome sequencing of four indicated that two isolates held genes encoding nitrate reductase as the only dissimilatory N-oxide reductase, one contained genes for both nitrate and nitric oxide reductase, and one had nitrate and nitrite reductase. The results demonstrated that N-oxide production was not always predicted by the genetic potential and suggested that partial denitrifiers could be readily isolated among soil bacteria. This supported the hypothesis that each N-oxide reductase could provide a selectable benefit on its own, and therefore, reduction of nitrate to dinitrogen may not be obligatorily linked to complete denitrifiers but instead a consequence of a functionally diverse community. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

Intercalation studies of zinc hydroxide chloride: Ammonia and amino acids

NASA Astrophysics Data System (ADS)

Arízaga, Gregorio Guadalupe Carbajal

2012-01-01

Zinc hydroxide chloride (ZHC) is a layered hydroxide salt with formula Zn5(OH)8Cl2·2H2O. It was tested as intercalation matrix for the first time and results were compared with intercalation products of the well-known zinc hydroxide nitrate and a Zn/Al layered double hydroxide. Ammonia was intercalated into ZHC, while no significant intercalation occurred in ZHN. Aspartic acid intercalation was only achieved by co-precipitation at pH=10 with ZHC and pH=8 with zinc hydroxide nitrate. Higher pH resistance in ZHC favored total deprotonation of both carboxylic groups of the Asp molecule. ZHC conferred more thermal protection against Asp combustion presenting exothermic peaks even at 452 °C while the exothermic event in ZHN was 366 °C and in the LDH at 276 °C.

Investigation of a lithium-halogen exchange flow process for the preparation of boronates by using a cryo-flow reactor.

PubMed

Newby, James A; Huck, Lena; Blaylock, D Wayne; Witt, Paul M; Ley, Steven V; Browne, Duncan L

2014-01-03

Conducting low-temperature organometallic reactions under continuous flow conditions offers the potential to more accurately control exotherms and thus provide more reproducible and scalable processes. Herein, progress towards this goal with regards to the lithium-halogen exchange/borylation reaction is reported. In addition to improving the scope of substrates available on a research scale, methods to improve reaction profiles and expedite purification of the products are also described. On moving to a continuous system, thermocouple measurements have been used to track exotherms and provide a level of safety for continuous processing of organometallic reagents. The use of an in-line continuous liquid-liquid separation device to circumvent labour intensive downstream off-line processing is also reported. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reactor for exothermic reactions

DOEpatents

Smith, Jr., Lawrence A.; Hearn, Dennis; Jones, Jr., Edward M.

1993-01-01

A liquid phase process for oligomerization of C.sub.4 and C.sub.5 isoolefins or the etherification thereof with C.sub.1 to C.sub.6 alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120.degree. to 300.degree. F. Wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

Method for conducting exothermic reactions

DOEpatents

Smith, L. Jr.; Hearn, D.; Jones, E.M. Jr.

1993-01-05

A liquid phase process for oligomerization of C[sub 4] and C[sub 5] isoolefins or the etherification thereof with C[sub 1] to C[sub 6] alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120 to 300 F. wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

Method for conducting exothermic reactions

DOEpatents

Smith, Jr., Lawrence; Hearn, Dennis; Jones, Jr., Edward M.

1993-01-01

A liquid phase process for oligomerization of C.sub.4 and C.sub.5 isoolefins or the etherification thereof with C.sub.1 to C.sub.6 alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120.degree. to 300.degree. F. wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

Reactor for exothermic reactions

DOEpatents

Smith, L.A. Jr.; Hearn, D.; Jones, E.M. Jr.

1993-03-02

A liquid phase process is described for oligomerization of C[sub 4] and C[sub 5] isoolefins or the etherification thereof with C[sub 1] to C[sub 6] alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120 to 300 F. Wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

Effect of cyclophosphamide on the solid form of mannitol during lyophilization.

PubMed

Patel, Krupaliben; Munjal, Bhushan; Bansal, Arvind K

2017-04-01

Mannitol is a commonly used bulking agent in lyophilized formulations. It can crystallize into multiple solid forms during lyophilization thereby exhibiting phase heterogeneity and variability in product performance. In this manuscript, we studied the effect of cyclophosphamide (CPA), an anticancer drug, on the solid form of mannitol during lyophilization from aqueous solutions. Freeze-concentration studies were performed in the DSC while lyophilization was performed in a lab scale freeze dryer. DSC experiments revealed two-stage crystallization of mannitol (1.5% w/v) during freeze-concentration, evident as two distinct exothermic events (at -18.2°C and -30°C) in the cooling curve. This was complemented by two eutectic melting endotherms in the subsequent heating curve. Addition of CPA (4.0% w/v) completely inhibited the exotherm at -18.2°C, but enhanced the enthalpy of exotherm at -30°C by five folds. Likewise, only one eutectic melting endotherm was observed in the subsequent heating curve. Lyophilization of the solution containing only mannitol, yielded a mixture of β- (major) and δ- (minor) polymorphs of mannitol. However, in the presence of CPA, only δ-polymorph was observed in the lyophilized sample. This selective favoring of the metastable δ-polymorph over the stable β-polymorph, was explained by altered freezing kinetics of the solution in presence of CPA. The study provides mechanistic insights into solute crystallization behaviour during lyophilization of multi-component systems. Copyright © 2017. Published by Elsevier B.V.

Thermodynamic analysis of Bacillus subtilis endospore protonation using isothermal titration calorimetry

NASA Astrophysics Data System (ADS)

Harrold, Zoë R.; Gorman-Lewis, Drew

2013-05-01

Bacterial proton and metal adsorption reactions have the capacity to affect metal speciation and transport in aqueous environments. We coupled potentiometric titration and isothermal titration calorimetry (ITC) analyses to study Bacillus subtilis spore-proton adsorption. We modeled the potentiometric data using a four and five-site non-electrostatic surface complexation model (NE-SCM). Heats of spore surface protonation from coupled ITC analyses were used to determine site specific enthalpies of protonation based on NE-SCMs. The five-site model resulted in a substantially better model fit for the heats of protonation but did not significantly improve the potentiometric titration model fit. The improvement observed in the five-site protonation heat model suggests the presence of a highly exothermic protonation reaction circa pH 7 that cannot be resolved in the less sensitive potentiometric data. From the log Ks and enthalpies we calculated corresponding site specific entropies. Log Ks and site concentrations describing spore surface protonation are statistically equivalent to B. subtilis cell surface protonation constants. Spore surface protonation enthalpies, however, are more exothermic relative to cell based adsorption suggesting a different bonding environment. The thermodynamic parameters defined in this study provide insight on molecular scale spore-surface protonation reactions. Coupled ITC and potentiometric titrations can reveal highly exothermic, and possibly endothermic, adsorption reactions that are overshadowed in potentiometric models alone. Spore-proton adsorption NE-SCMs derived in this study provide a framework for future metal adsorption studies.

Differential Scanning Calorimetry and Evolved Gas Analysis of Hydromagnesite

NASA Technical Reports Server (NTRS)

Lauer, H. V., Jr.; Golden, D. C.; Ming, Douglas W.; Boynton, W. V.

1999-01-01

Volatile-bearing minerals (e.g., Fe-oxyhydroxides, phyllosilicates, carbonates and sulfates) may be important phases on the surface of Mars. In order to characterize these phases the Thermal and Evolved Gas Analyzer (TEGA) flying on the Mars'98 lander will perform analyses on surface samples from Mars. Hydromagnesite [Mg5(CO3)4(OH)2.4H2O] is considered a good standard mineral to examine as a Mars soil analog component because it evolves both H2O and CO2 at temperatures between 0 and 600 C. Our aim here is to interpret the DSC signature of hydromagnesite under ambient pressure and 20 sccm N2 flow in the range 25 to 600 C. The DSC curve for hydromagnesite under the above conditions consists of three endothermic peaks at temperatures 296, 426, and 548 and one sharp exotherm at 511 C. X-ray analysis of the sample at different stop temperatures suggested that the exotherm corresponded with the formation of crystalline magnesite. The first endotherm was due to dehydration of hydromagnesite, and then the second one was due to the decomposition of carbonate, immediately followed by the formation of magnesite (exotherm) and its decomposition to periclase (last endotherm). Evolution of water and CO2 were consistent with the observed enthalpy changes. A library of such DSC-evolved gas curves for putative Martian minerals are currently being acquired in order to facilitate the interpretation of results obtained by a robotic lander.

Interaction of the dietary pigment curcumin with hemoglobin: energetics of the complexation.

PubMed

Basu, Anirban; Kumar, Gopinatha Suresh

2014-08-01

Thermodynamics of the interaction of the chemotherapeutic and chemopreventive dietary pigment, curcumin, with hemoglobin was studied by isothermal titration calorimetry. The binding was characterized to be exothermic. At 293.15 K, the equilibrium constant for curcumin-Hb complexation was found to be (4.88 ± 0.06) × 10(5) M(-1). The binding stoichiometry was calculated to be 1.08 ± 0.05, confirming a 1:1 complexation. The binding was driven by a large negative standard molar enthalpy change (ΔH(0) = -118.45 ± 0.05 kJ mol(-1)) and an unfavorable standard molar entropy change (TΔS(0) = -86.53 ± 0.01 kJ mol(-1)) at 293.15 K. Increasing the temperature favoured the binding, and the magnitude of the negative standard molar heat capacity change suggested the involvement of significant hydrophobic forces in the binding process. With increasing salt concentration, the magnitude of the equilibrium constant decreased slightly; and the complexation mostly involved non-polyelectrolytic forces contributing about 92-94% of the standard molar Gibbs energy change. DSC studies revealed that curcumin binding caused a partial unfolding of the protein.

Plasma homocysteine is associated with increased oxidative stress and antioxidant enzyme activity in welders.

PubMed

Liu, Hung-Hsin; Shih, Tung-Sheng; Huang, Hsin-Ru; Huang, Shih-Chien; Lee, Lien-Hsiung; Huang, Yi-Chia

2013-01-01

The purpose of this study was to examine the association of vitamin B6 status and plasma homocysteine with oxidative stress and antioxidant capacities in welders. Workers were divided into either the welding exposure group (n = 57) or the nonexposure controls (n = 42) based on whether they were employed as welders. There were no significant differences in vitamin B₆ status and plasma homocysteine concentration between the welding exposure group and the nonexposure controls. The welding exposure group had significantly higher levels of oxidized low-density lipoprotein cholesterol and lower erythrocyte glutathione concentration and superoxide dismutase (SOD) activities when compared to nonexposure controls. Plasma pyridoxal 5'-phosphate concentration did not correlate with oxidative stress indicators or antioxidant capacities in either group. However, plasma homocysteine significantly correlated with total antioxidant capacity (TAC) (partial r(s) = -0.34, P < 0.05) and erythrocyte SOD activities (partial r(s) = 0.29, P < 0.05) after adjusting for potential confounders in the welding exposure group. In the welding exposure group, adequate vitamin B₆ status was not associated with oxidative stress or antioxidant capacities. However, elevated plasma homocysteine seemed to be a major contributing factor to antioxidant capacities (TAC and erythrocyte SOD activities) in welders.

Neutral complexes as oxidants for the reduced form of parsley (Petroselinum crispum) [2Fe--2S] ferredoxin. Evidence for partial blocking by redox-inactive Cr(III) complexes.

PubMed Central

Adzamli, I K; Kim, H O; Sykes, A G

1982-01-01

The 1 : 1 reactions of three neutral Co(III) oxidants, Co(acac)3, Co(NH3)3(NO2)3 and Co(acac)2(NH3)(NO2), with reduced parsley (Petroselinum crispum) [2Fe--2S] ferredoxin (which carries a substantial negative charge), have been studied at 25 degrees C, pH 8.0 (Tris/HCl), I0.10 (NaCl). Whereas it has previously been demonstrated that with Co(NH3)6+ as oxidant the reaction if completely blocked by redox-inactive Cr(NH3)63+, the neutral oxidants are only partially blocked by this same complex. The effects of three Cr(III) complexes, Cr(NH3)63+%, Cr(en)33+ and (en)2Cr . mu(OH,O2CCH3) . CR(en)24+ have been investigated. Kinetic data for the response of 3+, neutral, as well as 1--oxidants to the presence of 3+ (and 4+) Cr(III) complexes can now be rationalized in terms of a single functional site on the protein for electron transfer. Electrostatics have a significant influence on association at this site. PMID:7115307

Influence of Oxygen Partial Pressure during Processing on the Thermoelectric Properties of Aerosol-Deposited CuFeO₂.

PubMed

Stöcker, Thomas; Exner, Jörg; Schubert, Michael; Streibl, Maximilian; Moos, Ralf

2016-03-24

In the field of thermoelectric energy conversion, oxide materials show promising potential due to their good stability in oxidizing environments. Hence, the influence of oxygen partial pressure during synthesis on the thermoelectric properties of Cu-Delafossites at high temperatures was investigated in this study. For these purposes, CuFeO₂ powders were synthetized using a conventional mixed-oxide technique. X-ray diffraction (XRD) studies were conducted to determine the crystal structures of the delafossites associated with the oxygen content during the synthesis. Out of these powders, films with a thickness of about 25 µm were prepared by the relatively new aerosol-deposition (AD) coating technique. It is based on a room temperature impact consolidation process (RTIC) to deposit dense solid films of ceramic materials on various substrates without using a high-temperature step during the coating process. On these dense CuFeO₂ films deposited on alumina substrates with electrode structures, the Seebeck coefficient and the electrical conductivity were measured as a function of temperature and oxygen partial pressure. We compared the thermoelectric properties of both standard processed and aerosol deposited CuFeO₂ up to 900 °C and investigated the influence of oxygen partial pressure on the electrical conductivity, on the Seebeck coefficient and on the high temperature stability of CuFeO₂. These studies may not only help to improve the thermoelectric material in the high-temperature case, but may also serve as an initial basis to establish a defect chemical model.

The partial pressure of oxygen affects biomarkers of oxidative stress in cultured rainbow trout (Oncorhynchus mykiss) hepatocytes.

PubMed

Finne, E F; Olsvik, P A; Berntssen, M H G; Hylland, K; Tollefsen, K E

2008-09-01

Oxidative stress, the imbalance between production of reactive oxygen species and the cellular detoxification of these reactive compounds, is believed to be involved in the pathology of various diseases. Several biomarkers for oxidative stress have been proposed to serve as tools in toxicological and ecotoxicological research. Not only may exposure to various pro-oxidants create conditions of cellular oxidative stress, but hyperoxic conditions may also increase the production of reactive oxygen species. The objective of the current study was to determine the extent to which differences in oxygen partial pressure would affect biomarkers of oxidative stress in a primary culture of hepatocytes from rainbow trout (Oncorhynchus mykiss). Membrane integrity, metabolic activity, levels of total and oxidized glutathione (tGSH/GSSG) was determined, as well as mRNA expression levels of the antioxidant enzymes superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GSH-Px), glutathione reductase (GSSG-R), gamma-glutamyl-cystein synthetase (GCS) and thioredoxin (TRX). The results show that different biomarkers of oxidative stress are affected when the cell culture is exposed to atmospheric oxygen, and that changes such as increased GSSG content and induction of GSSG-R and GSH-Px can be reduced by culturing the cells under lower oxygen tension. Oxygen tension may thus influence results of in vitro based cell research and is particularly important when assessing parameters in the antioxidant defence system. Further research is needed to establish the magnitude of this effect in different cellular systems.

The oxidation of copper catalysts during ethylene epoxidation.

PubMed

Greiner, M T; Jones, T E; Johnson, B E; Rocha, T C R; Wang, Z J; Armbrüster, M; Willinger, M; Knop-Gericke, A; Schlögl, R

2015-10-14

The oxidation of copper catalysts during ethylene epoxidation was characterized using in situ photoemission spectroscopy and electron microscopy. Gas chromatography, proton-transfer reaction mass spectrometry and electron-ionization mass spectrometry were used to characterize the catalytic properties of the oxidized copper. We find that copper corrodes during epoxidation in a 1 : 1 mixture of oxygen and ethylene. The catalyst corrosion passes through several stages, beginning with the formation of an O-terminated surface, followed by the formation of Cu2O scale and eventually a CuO scale. The oxidized catalyst exhibits measurable activity for ethylene epoxidation, but with a low selectivity of <3%. Tests on pure Cu2O and CuO powders confirm that the oxides intrinsically exhibit partial-oxidation activity. Cu2O was found to form acetaldehyde and ethylene epoxide in roughly equal amounts (1.0% and 1.2% respectively), while CuO was found to form much less ethyl aldehyde than ethylene epoxide (0.1% and 1.0%, respectively). Metallic copper catalysts were examined in extreme dilute-O2 epoxidation conditions to try and keep the catalyst from oxidizing during the reaction. It was found that in feed of 1 part O2 to 2500 parts C2H4 (PO2 = 1.2 × 10(-4) mbar) the copper surface becomes O-terminated. The O-terminated surface was found to exhibit partial-oxidation selectivity similar to that of Cu2O. With increasing O2 concentration (>8/2500) Cu2O forms and eventually covers the surface.

Treatment of CELSS and PCELSS waste to produce nutrients for plant growth. [Controlled Ecological Life Support Systems and Partially Controlled Ecological Life Support Systems

NASA Technical Reports Server (NTRS)

Modell, M.; Meissner, H.; Karel, M.; Carden, J.; Lewis, S.

1981-01-01

The research program entitled 'Development of a Prototype Experiment for Treating CELSS (Controlled Ecological Life Support Systems) and PCELSS (Partially Controlled Ecological Life Support Systems) Wastes to Produce Nutrients for Plant Growth' consists of two phases: (1) the development of the neccessary facilities, chemical methodologies and models for meaningful experimentation, and (2) the application of what methods and devices are developed to the interfacing of waste oxidation with plant growth. Homogeneous samples of freeze-dried human feces and urine have been prepared to ensure comparability of test results between CELSS waste treatment research groups. A model of PCELSS food processing wastes has been developed, and an automated gas chromatographic system to analyze oxidizer effluents was designed and brought to operational status. Attention is given the component configuration of the wet oxidation system used by the studies.

Positron annihilation and X-ray diffraction studies on tin oxide thin films

NASA Astrophysics Data System (ADS)

Prabakar, K.; Abhaya, S.; Krishnan, R.; Kalavathi, S.; Dash, S.; Jayapandian, J.; Amarendra, G.

2009-04-01

Positron annihilation spectroscopy along with glancing incidence X-ray diffraction have been used to investigate tin oxide thin films grown on Si by pulsed laser deposition. The films were prepared at room temperature and at 670 K under oxygen partial pressure. As-grown samples are amorphous and are found to contain large concentration of open volume sites (vacancy defects). Post-deposition annealing of as-grown samples at 970 K is found to drastically reduce the number of open volume sites and the film becomes crystalline. However, film grown under elevated temperature and under partial pressure of oxygen is found to exhibit a lower S-parameter, indicating lower defect concentration. Based on the analysis of experimental positron annihilation results, the defect-sensitive S-parameter and the overlayer thickness of tin oxide thin films are deduced. S- W correlation plots exhibit distinct positron trapping defect states in three samples.

Structural, electronic and optical properties of CO adsorbed on the defective anatase TiO2 (101) surface; a DFT study

NASA Astrophysics Data System (ADS)

Rafique, Muhammad; Shuai, Yong; Hassan, Muhammad

2017-08-01

This paper illustrates the study of stable structural, electronic and optical properties of carbon mono oxide (CO) molecule adsorbed on pure anatase TiO2 (101) surface and CO molecule adsorbed on defective anatase TiO2 (101) surface containing oxygen (O) atom subsurface vacancy using first-principles study calculations based on density functional theory (DFT) method. A foreign molecule CO was added in the interstitial space of anatase TiO2 (101) surface. It was observed that, adsorption of CO molecule is not favorable on pure anatase TiO2 (101) surface, however adsorption process is improved when subsurface contains O atom vacancy defect. In case of anatase TiO2 (101) surface containing subsurface vacancy, adsorption process is exothermic, resulting in stable structures. The adsorption energies calculated for CO molecules adsorbed at O2c site, at defect site and at Ti5c site of anatase surface containing subsurface O vacancy are 0.16 eV (at O2c), 0.32 eV (at defect site) and 0.43 eV (at Ti5c) site. DOS and PDOS plots are calculated for all the structures. Results indicated that CO molecule adsorption introduces surface states at the Fermi energy level (EF) as shown in partial density of states (PDOS) plots. The dielectric matrix and absorption coefficient (α) for defective anatase TiO2 (101) surface, CO adsorbed at O2c site, at defect site and at Ti5C site of anatase TiO2 (101) surface containing O atom subsurface vacancy has been calculated within the random phase approximation (RPA) using VASP (Vienna ab-initio simulation package) code. It was observed that upon CO adsorption at defective anatase surface, real and imaginary dielectric function peaks were shifted towards lower energy level and a small absorption peak was observed at 1.1 eV energy level which is not present in case of defective anatase (101) surface. CO adsorption produces a red shift in the absorption spectrum of anatase TiO2 (101) surface containing subsurface O atom vacancy.

The benzylperoxyl radical as a source of hydroxyl and phenyl radicals.

PubMed

Sander, Wolfram; Roy, Saonli; Bravo-Rodriguez, Kenny; Grote, Dirk; Sanchez-Garcia, Elsa

2014-09-26

The benzyl radical (1) is a key intermediate in the combustion and tropospheric oxidation of toluene. Because of its relevance, the reaction of 1 with molecular oxygen was investigated by matrix-isolation IR and EPR spectroscopy as well as computational methods. The primary reaction product of 1 and O2 is the benzylperoxyl radical (2), which exists in several conformers that can easily interconvert even at cryogenic temperatures. Photolysis of radical 2 at 365 nm results in a formal [1,3]-H migration and subsequent cleavage of the O-O bond to produce a hydrogen-bonded complex between the hydroxyl radical and benzaldehyde (4). Prolonged photolysis produces the benzoyl radical (5) and water, which finally yield the phenyl radical (7), CO, and H2O. Thus, via a sequence of exothermic reactions 1 is transformed into radicals of even higher reactivity, such as OH and 7. Our results have implications for the development of models for the highly complicated process of combustion of aromatic compounds. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gas Suppression via Copper Interlayers in Magnetron Sputtered Al-Cu2O Multilayers.

PubMed

Kinsey, Alex H; Slusarski, Kyle; Sosa, Steven; Weihs, Timothy P

2017-07-05

The use of thin-foil, self-propagating thermite reactions to bond components successfully depends on the ability to suppress gas generation and avoid pore formation during the exothermic production of brazes. To study the mechanisms of vapor production in diluted thermites, thin film multilayer Al-Cu-Cu 2 O-Cu foils are produced via magnetron sputtering, where the Cu layer thickness is systematically increased from 0 to 100 nm in 25 nm increments. The excess Cu layers act as diffusion barriers, limiting the transport of oxygen from the oxide to the Al fuel, as determined by slow heating differential scanning calorimetry experiments. Furthermore, by adding excess Cu to the system, the temperature of the self-propagating thermite reactions drops below the boiling point of Cu, eliminating the metal vapor production. It is determined that Cu vapor production can be eliminated by increasing the Cu interlayer thickness above 50 nm. However, the porous nature of the final products suggests that only metal vapor production is suppressed via dilution. Gas generation via oxygen release is still capable of producing a porous reaction product.

Low archaeal diversity linked to subseafloor geochemical processes at the Lost City Hydrothermal Field, Mid-Atlantic Ridge.

PubMed

Schrenk, Matthew O; Kelley, Deborah S; Bolton, Sheryl A; Baross, John A

2004-10-01

The recently discovered Lost City Hydrothermal Field (LCHF) represents a new type of submarine hydrothermal system driven primarily by exothermic serpentinization reactions in ultramafic oceanic crust. Highly reducing, alkaline hydrothermal environments at the LCHF produce considerable quantities of hydrogen, methane and organic molecules through chemo- and biosynthetic reactions. Here, we report the first analyses of microbial communities inhabiting carbonate chimneys awash in warm, high pH fluids at the LCHF and the predominance of a single group of methane-metabolizing Archaea. The predominant phylotype, related to the Methanosarcinales, formed tens of micrometre-thick biofilms in regions adjacent to hydrothermal flow. Exterior portions of active structures harboured a diverse microbial community composed primarily of filamentous Eubacteria that resembled sulphide-oxidizing species. Inactive samples, away from regions of hydrothermal flow, contained phylotypes related to pelagic microorganisms. The abundance of organisms linked to the volatile chemistry at the LCHF hints that similar metabolic processes may operate in the subseafloor. These results expand the range of known geological settings that support biological activity to include submarine hydrothermal systems that are not dependent upon magmatic heat sources.

In silico kinetics of alkaline hydrolysis of 1,3,5-trinitro-1,3,5-triazinane (RDX): M06-2X investigation.

PubMed

Sviatenko, L K; Gorb, L; Leszczynska, D; Okovytyy, S I; Shukla, M K; Leszczynski, J

2017-03-22

Alkaline hydrolysis of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), as one of the most promising methods for nitrocompound remediation, was investigated computationally at the PCM(Pauling)/M06-2X/6-311++G(d,p) level of theory. Computational simulation shows that RDX hydrolysis is a highly exothermic multistep process involving initial deprotonation and nitrite elimination, cycle cleavage, further transformation of cycle-opened intermediates to end products caused by a series of C-N bond ruptures, hydroxide attachments, and proton transfers. Computationally predicted products of RDX hydrolysis such as nitrite, nitrous oxide, formaldehyde, formate, and ammonia correspond to experimentally observed ones. Accounting of specific hydration of hydroxide is critical to create an accurate kinetic model for alkaline hydrolysis. Simulated kinetics of the hydrolysis are in good agreement with available experimental data. A period of one month is necessary for 99% RDX decomposition at pH 10. Computations predict significant increases of the reaction rate of hydrolysis at pH 11, pH 12, and pH 13.

Environmental Technology Verification: Test Report of Mobile Source Emission Control Devices--Johnson Matthey PCRT2 1000, Version 2, Filter + Diesel Oxidation Catalyst

EPA Science Inventory

The Johnson Matthey PCRT2 1000, v.2 system is a partial continuously regenerating technology (PCRT) system that consists of a flow-through partial filter combined with a DOC. The system is designed for low temperature exhaust resulting from intermittent loads from medium and heav...

Integrated Fuel Cell/Coal Gasifier

NASA Technical Reports Server (NTRS)

Ferrall, J. F.

1985-01-01

Powerplant design with low-temperature coal gasifier coupled to highly-exothermic fuel cell for efficient production of dc power eliminates need for oxygen in gasifier and achieves high fuel efficiency with recycling of waste heat from fuel cell.

Prediction and Prevention of Chemical Reaction Hazards: Learning by Simulation.

ERIC Educational Resources Information Center

Shacham, Mordechai; Brauner, Neima; Cutlip, Michael B.

2001-01-01

Points out that chemical hazards are the major cause of accidents in chemical industry and describes a safety teaching approach using a simulation. Explains a problem statement on exothermic liquid-phase reactions. (YDS)

Effect of methane partial pressure on the performance of a membrane biofilm reactor coupling methane-dependent denitrification and anammox.

PubMed

Cai, Chen; Hu, Shihu; Chen, Xueming; Ni, Bing-Jie; Pu, Jiaoyang; Yuan, Zhiguo

2018-10-15

Complete nitrogen removal has recently been demonstrated by integrating anaerobic ammonium oxidation (anammox) and denitrifying anaerobic methane oxidation (DAMO) processes. In this work, the effect of methane partial pressure on the performance of a membrane biofilm reactor (MBfR) consisting of DAMO and anammox microorganisms was evaluated. The activities of DAMO archaea and DAMO bacteria in the biofilm increased significantly with increased methane partial pressure, from 367 ± 9 and 58 ± 22 mg-N L -1 d -1 to 580 ± 12 and 222 ± 22 mg-N L -1 d -1 , respectively, while the activity of anammox bacteria only increased slightly, when the methane partial pressure was elevated from 0.24 to 1.39 atm in the short-term batch tests. The results were supported by a long-term (seven weeks) continuous test, when the methane partial pressure was dropped from 1.39 to 0.78 atm. The methane utilization efficiency was always above 96% during both short-term and long-term tests. Taken together, nitrogen removal rate (especially the nitrate reduction rate by DAMO archaea) and methane utilization efficiency could be maintained at high levels in a broad range of methane partial pressure (0.24-1.39 atm in this study). In addition, a previously established DAMO/anammox biofilm model was used to analyze the experimental data. The observed impacts of methane partial pressure on biofilm activity were well explained by the modeling results. These results suggest that methane partial pressure can potentially be used as a manipulated variable to control reaction rates, ultimately to maintain high nitrogen removal efficiency, according to nitrogen loading rate. Copyright © 2018 Elsevier B.V. All rights reserved.

Partial uncoupling of oxidative phosphorylation induces premature senescence in human fibroblasts and yeast mother cells.

PubMed

Stöckl, Petra; Zankl, Christina; Hütter, Eveline; Unterluggauer, Hermann; Laun, Peter; Heeren, Gino; Bogengruber, Edith; Herndler-Brandstetter, Dietmar; Breitenbach, Michael; Jansen-Dürr, Pidder

2007-09-15

The mitochondrial theory of aging predicts that functional alterations in mitochondria leading to reactive oxygen species (ROS) production contribute to the aging process in most if not all species. Using cellular senescence as a model for human aging, we have recently reported partial uncoupling of the respiratory chain in senescent human fibroblasts. In the present communication, we address a potential cause-effect relationship between impaired mitochondrial coupling and premature senescence. Chronic exposure of human fibroblasts to the chemical uncoupler carbonylcyanide p-trifluoromethoxyphenylhydrazone (FCCP) led to a temporary, reversible uncoupling of oxidative phosphorylation. FCCP inhibited cell proliferation in a dose-dependent manner, and a significant proportion of the cells entered premature senescence within 12 days. Unexpectedly, chronic exposure of cells to FCCP led to a significant increase in ROS production, and the inhibitory effect of FCCP on cell proliferation was eliminated by the antioxidant N-acetyl-cysteine. However, antioxidant treatment did not prevent premature senescence, suggesting that a reduction in the level of oxidative phosphorylation contributes to phenotypical changes characteristic of senescent human fibroblasts. To assess whether this mechanism might be conserved in evolution, the influence of mitochondrial uncoupling on replicative life span of yeast cells was also addressed. Similar to our findings in human fibroblasts, partial uncoupling of oxidative phsophorylation in yeast cells led to a substantial decrease in the mother-cell-specific life span and a concomitant incrase in ROS, indicating that life span shortening by mild mitochondrial uncoupling may represent a "public" mechanism of aging.

Interaction of dimethylamine with clean and partially oxidized copper surfaces

NASA Astrophysics Data System (ADS)

Kelber, J. A.; Rogers, J. W.; Banse, B. A.; Koel, B. E.

1990-05-01

The interaction of dimethylamine (DMA) with partially oxidized polycrystalline copper [Cu(poly)] and clean and partially oxidized Cu(110) between 110 and 500 K has been examined using electron stimulated desorption (ESD), high resolution electron energy loss spectroscopy (HREELS) and temperature programmed desorption (TPD). ESD mass spectra of the DMA adsorbed on O/Cu(poly) between 112 and 230 K consistently display peaks at 44 amu [(CH 3) 2N] + and 46 amu [(CH 3) 2NH-H] +, but no significant parent peak at 45 amu [(CH 3) 2NH] +, even though this last feature is prominent in the gas-phase mass spectrum. OH - is not observed at temperatures below 184 K and the yield at higher temperatures is much less than that of O +. HREELS of DMA on clean and oxygen covered Cu(110) obtained at temperatures between 100 and 320 K show characteristic vibrational spectra for molecular DMA and no OH(a) vibrational modes. TPD results show that the desorption profiles of all the major peaks in the DMA mass spectrum follow that of the parent peak with no evidence for production of H 2O. The ESD, HREELS and TPD results all indicate that DMA is molecularly and reversibly adsorbed, with no significant formation of surface hydroxyl species. The results indicate that preferential adsorption of amines from amine/epoxy mixtures onto metal oxide surfaces could passivate the surface and prevent subsequent bonding to the epoxy resin.

Barley has two peroxisomal ABC transporters with multiple functions in β-oxidation

PubMed Central

Mendiondo, Guillermina M.; Medhurst, Anne; van Roermund, Carlo W.; Zhang, Xuebin; Devonshire, Jean; Scholefield, Duncan; Fernández, José; Axcell, Barry; Ramsay, Luke; Waterham, Hans R.; Waugh, Robbie; Theodoulou, Frederica L.; Holdsworth, Michael J.

2014-01-01

In oilseed plants, peroxisomal β-oxidation functions not only in lipid catabolism but also in jasmonate biosynthesis and metabolism of pro-auxins. Subfamily D ATP-binding cassette (ABC) transporters mediate import of β-oxidation substrates into the peroxisome, and the Arabidopsis ABCD protein, COMATOSE (CTS), is essential for this function. Here, the roles of peroxisomal ABCD transporters were investigated in barley, where the main storage compound is starch. Barley has two CTS homologues, designated HvABCD1 and HvABCD2, which are widely expressed and present in embryo and aleurone tissues during germination. Suppression of both genes in barley RNA interference (RNAi) lines indicated roles in metabolism of 2,4-dichlorophenoxybutyrate (2,4-DB) and indole butyric acid (IBA), jasmonate biosynthesis, and determination of grain size. Transformation of the Arabidopsis cts-1 null mutant with HvABCD1 and HvABCD2 confirmed these findings. HvABCD2 partially or completely complemented all tested phenotypes of cts-1. In contrast, HvABCD1 failed to complement the germination and establishment phenotypes of cts-1 but increased the sensitivity of hypocotyls to 100 μM IBA and partially complemented the seed size phenotype. HvABCD1 also partially complemented the yeast pxa1/pxa2Δ mutant for fatty acid β-oxidation. It is concluded that the core biochemical functions of peroxisomal ABC transporters are largely conserved between oilseeds and cereals but that their physiological roles and importance may differ. PMID:24913629

High Temperature Oxidation and Electrochemical Studies Related to Hot Corrosion

DTIC Science & Technology

1992-05-01

sulfidation. In sulfidation, NaCI reacts with sulfur found in the fuel to form Na2SO4. The sodium sulfate reacts with the protective oxide scale resulting...fluxing or acid -base reaction model. In sufidation, 4 Bornstein explains that the oxide scales are insoluble in stoichiometric sodium sulfate , but due to...oxygen partial pressures an electron hopping mechanism dominates. Reduced cerium ions and Ce3+- oxygen vacancy associates generate these conducting

Membrane-micelle model for humus in soils and sediments and its relation to humification

USGS Publications Warehouse

Wershaw, Robert L.

1994-01-01

Humification, the process whereby biomass consisting of dead plant and animal remains is converted into soil organic matter (humus), is one of the basic processes of the carbon cycle. The organic compounds that make up plant and animal tissue are thermodynamically unstable in the oxidizing atmosphere at the surface of the Earth. After the organisms in which they are incorporated die, the compounds are converted back to carbon dioxide and water by degradation reactions catalyzed by enzymes secreted by micro-organisms. However, not all the organic compounds in the dead biomass are immediately converted; some of the material is only partially oxidized. The residue left after partial oxidative degradation of the dead biomass is the source of the organic compounds that accumulate in soils and sediments as humus. Previously, humification was thought to involve a conversion of degradation products by a series of polymerization reactions into new types of polymeric species that are different from the precursor molecular species in the original biomass. However, it is proposed here that the depolymerization and oxidation reactions that take place during the enzymatic degradation of biopolymers produce amphiphiles--molecules that have a polar (hydrophilic) part and a nonpolar (hydrophobic) part. These amphiphiles that result from the partial oxidative degradation of dead biomass assemble spontaneously into ordered aggregates in which the hydrophobic parts of the molecules form the interiors and the hydrophilic parts of the molecules make up the exterior surfaces of the aggregates. These ordered aggregates constitute the humus in soils and sediments. Humus ordered aggregates most likely exist as bilayer membranes coating mineral grains and as micelles in solution.

Catalysis by Atomic-Sized Centers: Methane Activation for Partial Oxidation and Combustion

DTIC Science & Technology

2015-07-21

example, H adsorbed alone on an oxide surface will bind to oxygen to form a hydroxide . However, if a Lewis base (e.g. any electron donor) is...that on a gold surface, which is not surprising considering the bonding character between the cluster and metal surfaces. The high mobility verifies

Corrosion protection for silver reflectors

DOEpatents

Arendt, Paul N.; Scott, Marion L.

1991-12-31

A method of protecting silver reflectors from damage caused by contact with gaseous substances which are often present in the atmosphere and a silver reflector which is so protected. The inventive method comprises at least partially coating a reflector with a metal oxide such as aluminum oxide to a thickness of 15 .ANG. or less.

Application of Response Surface Methodology on Leaching of Iron from Partially Laterised Khondalite Rocks: A Bauxite Mining Waste

NASA Astrophysics Data System (ADS)

Swain, Ranjita; Bhima Rao, R.

2018-04-01

In the present investigation, response surface methodology (RSM) is used for a quadratic model that continuously controls the process parameters. This model is used to optimize the removal of iron oxide from Partially Laterised Khondalite (PLK) rocks which is influenced by several independent variables namely acid concentration, time and temperature. Second order response functions are produced for leaching of iron oxide from PLK rocks-a bauxite mining waste. In RSM, Box-Behnken design is used for the process optimization to achieve maximum removal of iron oxide. The influence of the process variables of leaching of iron oxide is presented in the form of 3-D response graphs. The results of this investigation reveals that 3 M hydrochloric acid concentration, 240 min time and 373 K temperature are found to be the best conditions for removal of 99% Fe2O3. The product obtain at this condition contain 80% brightness which is suitable for ceramic and filler industry applications. The novelity of the work is that the waste can be a value added product after suitable physical beneficiation and chemical treatment.

The PEMFC-integrated CO oxidation — a novel method of simplifying the fuel cell plant

NASA Astrophysics Data System (ADS)

Rohland, Bernd; Plzak, Vojtech

Natural gas and methanol are the most economical fuels for residential fuel cell power generators as well as for mobile PEM-fuel cells. However, they have to be reformed with steam into hydrogen, which is to be cleaned from CO by shift-reaction and by partial oxidation to a level of no more than 30 ppm CO. This level is set by the Pt/Ru-C-anode of the PEMFC. A higher partial oxidation reaction rate for CO than those of Pt/Ru-C can be achieved in an oxidic Au-catalyst system. In the Fe 2O 3-Au system, a reaction rate of 2·10 -3 mol CO/s g Au at 1000 ppm CO and 5% "air bleed" at 80°C is achieved. This high rate allows to construct a catalyst-sheet for each cell within a PEMFC-stack. Practical and theoretical current/voltage characteristics of PEMFCs with catalyst-sheet are presented at 1000 ppm CO in hydrogen with 5% "air bleed". This gives the possibility of simplifying the gas processor of the plant.

Development of a simultaneous partial nitrification, anaerobic ammonia oxidation and denitrification (SNAD) bench scale process for removal of ammonia from effluent of a fertilizer industry.

PubMed

Keluskar, Radhika; Nerurkar, Anuradha; Desai, Anjana

2013-02-01

A simultaneous partial nitrification, anammox and denitrification (SNAD) process was developed for the treatment of ammonia laden effluent of a fertilizer industry. Autotrophic aerobic and anaerobic ammonia oxidizing biomass was enriched and their ammonia removal ability was confirmed in synthetic effluent system. Seed consortium developed from these was applied in the treatment of effluent in an oxygen limited bench scale SNAD type (1L) reactor run at ambient temperature (∼30°C). Around 98.9% ammonia removal was achieved with ammonia loading rate 0.35kgNH(4)(+)-N/m(3)day in the presence of 46.6mg/L COD at 2.31days hydraulic retention time. Qualitative and quantitative analysis of the biomass from upper and lower zone of the reactor revealed presence of autotrophic ammonia oxidizing bacteria (AOB), Planctomycetes and denitrifiers as the dominant bacteria carrying out anoxic oxidation of ammonia in the reactor. Physiological and molecular studies strongly indicate presence of anammox bacteria in the anoxic zone of the SNAD reactor. Copyright © 2012 Elsevier Ltd. All rights reserved.

Process for production desulfurized of synthesis gas

DOEpatents

Wolfenbarger, James K.; Najjar, Mitri S.

1993-01-01

A process for the partial oxidation of a sulfur- and silicate-containing carbonaceous fuel to produce a synthesis gas with reduced sulfur content which comprises partially oxidizing said fuel at a temperature in the range of 1900.degree.-2600.degree. F. in the presence of a temperature moderator, an oxygen-containing gas and a sulfur capture additive which comprises a calcium-containing compound portion, a sodium-containing compound portion, and a fluoride-containing compound portion to produce a synthesis gas comprising H.sub.2 and CO with a reduced sulfur content and a molten slag which comprises (1) a sulfur-containing sodium-calcium-fluoride silicate phase; and (2) a sodium-calcium sulfide phase.

Sulfation of ceria-zirconia model automotive emissions control catalysts

NASA Astrophysics Data System (ADS)

Nelson, Alan Edwin

Cerium-zirconium mixed metal oxides are used in automotive emissions control catalysts to regulate the partial pressure of oxygen near the catalyst surface. The near surface oxygen partial pressure is regulated through transfer of atomic oxygen from the ceria-zirconia solid matrix to the platinum group metals to form metal oxides capable of oxidizing carbon monoxide and unburned hydrocarbons. Although the addition of zirconium in the cubic lattice of ceria increases the oxygen storage capacity and thermal stability of the ceria matrix, the cerium-zirconium oxide system remains particularly susceptible to deactivation from sulfur compounds. While the overall effect of sulfur on these systems is understood (partially irreversible deactivation), the fundamental and molecular interaction of sulfur with ceria-zirconia remains a challenging problem. Ceria-zirconia metal oxide solid solutions have been prepared through co-precipitation with nitrate precursors. The prepared powders were calcined and subsequently formed into planer wafers and characterized for chemical and physical attributes. The prepared samples were subsequently exposed to a sulfur dioxide based environment and characterized with spectroscopic techniques to characterize the extent of sulfation and the nature of surface sulfur species. The extent of sulfation of the model ceria-zirconia systems was characterized with Auger electron spectroscopy (AES) prior to and after treatment in a microreactor. Strong dependencies were observed between the atomic ratio of ceria to zirconia and the extent of sulfation. In addition, the partial pressure of sulfur dioxide during treatments also correlated to the extent of sulfation, while temperature only slightly effected the extent of sulfation. The AES data suggests the gas phase sulfur dioxide preferentially chemisorbs on surface ceria atoms and the extent of sulfation is heavily dependent on sulfur dioxide concentrations and only slightly dependent on catalyst temperatures, as confirmed by thermal programmed desorption (TPD). While hydrogen exposure indicated slight sulfur removal, exposure to a redox environment or atmosphere nearly eliminated the quantity of chemisorbed surface sulfur. The nature of sulfur removal is attributed to the inherent redox properties of ceria-zirconia systems. The complete analysis provides mechanistic insight into sulfation dependencies and fundamental information regarding sulfur adsorption on ceria-zirconia model automotive emissions control systems.