High-temperature oxidation of Zircaloy in hydrogen-steam mixtures

International Nuclear Information System (INIS)

Chung, H.M.; Thomas, G.R.

1982-09-01

Oxidation rates of Zircaloy-4 cladding tubes have been measured in hydrogen-steam mixtures at 1200 to 1700 0 C. For a given isothermal oxidation temperature, the oxide layer thicknesses have been measured as a function of time, steam supply rate, and hydrogen overpressure. The oxidation rates in the mixtures were compared with similar data obtained in pure steam and helium-steam environments under otherwise identical conditions. The rates in pure steam and helium-steam mixtures were equivalent and comparable to the parabolic rates obtained under steam-saturated conditions and reported in the literature. However, when the helium was replaced with hydrogen of equivalent partial pressure, a significantly smaller oxidation rate was observed. For high steam-supply rates, the oxidation kinetics in a hydrogen-steam mixture were parabolic, but the rate was smaller than for pure steam or helium-steam mixtures. Under otherwise identical conditions, the ratio of the parabolic rate for hydrogen-steam to that for pure steam decreased with increasing temperature and decreasing steam-supply rate

Aerobic oxidation of aldehydes under ambient conditions using supported gold nanoparticle catalysts

DEFF Research Database (Denmark)

Marsden, Charlotte Clare; Taarning, Esben; Hansen, David

2008-01-01

A new, green protocol for producing simple esters by selectively oxidizing an aldehyde dissolved in a primary alcohol has been established, utilising air as the oxidant and supported gold nanoparticles as catalyst. The oxidative esterifications proceed with excellent selectivities at ambient cond...... conditions; the reactions can be performed in an open flask and at room temperature. Benzaldehyde is even oxidised at a reasonable rate below -70 degrees C. Acrolein is oxidised to methyl acrylate in high yield using the same protocol.......A new, green protocol for producing simple esters by selectively oxidizing an aldehyde dissolved in a primary alcohol has been established, utilising air as the oxidant and supported gold nanoparticles as catalyst. The oxidative esterifications proceed with excellent selectivities at ambient...

Oxidation behavior of TD-NiCr in a dynamic high temperature environment

Science.gov (United States)

Tenney, D. R.; Young, C. T.; Herring, H. W.

1974-01-01

The oxidation behavior of TD-NiCr has been studied in static and high-speed flowing air environments at 1100 and 1200 C. It has been found that the stable oxide morphologies formed on the specimens exposed to the static and dynamic environments were markedly different. The faceted crystal morphology characteristic of static oxidation was found to be unstable under high-temperature, high-speed flow conditions and was quickly replaced by a porous NiO 'mushroom' type structure. Also, it was found that the rate of formation of CrO3 from Cr2O3 was greatly enhanced by high gas velocity conditions. The stability of Cr2-O3 was found to be greatly improved by the presence of an outer NiO layer, even though the NiO layer was very porous. An oxidation model is proposed to explain the observed microstructures and overall oxidation behavior of TD-NiCr alloys.

Identification of a Catalytically Highly Active Surface Phase for CO Oxidation over PtRh Nanoparticles under Operando Reaction Conditions

Science.gov (United States)

Hejral, U.; Franz, D.; Volkov, S.; Francoual, S.; Strempfer, J.; Stierle, A.

2018-03-01

Pt-Rh alloy nanoparticles on oxide supports are widely employed in heterogeneous catalysis with applications ranging from automotive exhaust control to energy conversion. To improve catalyst performance, an atomic-scale correlation of the nanoparticle surface structure with its catalytic activity under industrially relevant operando conditions is essential. Here, we present x-ray diffraction data sensitive to the nanoparticle surface structure combined with in situ mass spectrometry during near ambient pressure CO oxidation. We identify the formation of ultrathin surface oxides by detecting x-ray diffraction signals from particular nanoparticle facets and correlate their evolution with the sample's enhanced catalytic activity. Our approach opens the door for an in-depth characterization of well-defined, oxide-supported nanoparticle based catalysts under operando conditions with unprecedented atomic-scale resolution.

Cth2 Protein Mediates Early Adaptation of Yeast Cells to Oxidative Stress Conditions.

Directory of Open Access Journals (Sweden)

Laia Castells-Roca

Full Text Available Cth2 is an mRNA-binding protein that participates in remodeling yeast cell metabolism in iron starvation conditions by promoting decay of the targeted molecules, in order to avoid excess iron consumption. This study shows that in the absence of Cth2 immediate upregulation of expression of several of the iron regulon genes (involved in high affinity iron uptake and intracellular iron redistribution upon oxidative stress by hydroperoxide is more intense than in wild type conditions where Cth2 is present. The oxidative stress provokes a temporary increase in the levels of Cth2 (itself a member of the iron regulon. In such conditions Cth2 molecules accumulate at P bodies-like structures when the constitutive mRNA decay machinery is compromised. In addition, a null Δcth2 mutant shows defects, in comparison to CTH2 wild type cells, in exit from α factor-induced arrest at the G1 stage of the cell cycle when hydroperoxide treatment is applied. The cell cycle defects are rescued in conditions that compromise uptake of external iron into the cytosol. The observations support a role of Cth2 in modulating expression of diverse iron regulon genes, excluding those specifically involved in the reductive branch of the high-affinity transport. This would result in immediate adaptation of the yeast cells to an oxidative stress, by controlling uptake of oxidant-promoting iron cations.

High temperature oxidation behavior of SiC coating in TRISO coated particles

International Nuclear Information System (INIS)

Liu, Rongzheng; Liu, Bing; Zhang, Kaihong; Liu, Malin; Shao, Youlin; Tang, Chunhe

2014-01-01

Highlights: • High temperature oxidation tests of SiC coating in TRISO particles were carried out. • The dynamic oxidation process was established. • Oxidation mechanisms were proposed. • The existence of silicon oxycarbides at the SiO 2 /SiC interface was demonstrated. • Carbon was detected at the interface at high temperatures and long oxidation time. - Abstract: High temperature oxidation behavior of SiC coatings in tristructural-isotropic (TRISO) coated particles is crucial to the in-pile safety of fuel particles for a high temperature gas cooled reactor (HTGR). The postulated accident condition of air ingress was taken into account in evaluating the reliability of the SiC layer. Oxidation tests of SiC coatings were carried out in the ranges of temperature between 800 and 1600 °C and time between 1 and 48 h in air atmosphere. Based on the microstructure evolution of the oxide layer, the mechanisms and kinetics of the oxidation process were proposed. The existence of silicon oxycarbides (SiO x C y ) at the SiO 2 /SiC interface was demonstrated by X-ray photospectroscopy (XPS) analysis. Carbon was detected by Raman spectroscopy at the interface under conditions of very high temperatures and long oxidation time. From oxidation kinetics calculation, activation energies were 145 kJ/mol and 352 kJ/mol for the temperature ranges of 1200–1500 °C and 1550–1600 °C, respectively

Radiation deterioration of several aromatic polymers under oxidative conditions

International Nuclear Information System (INIS)

Sasuga, Tsuneo; Hagiwara, Miyuki

1987-01-01

Radiation-induced oxidative irradiation effects (with γ-rays under oxygen pressure) or poly(aryl sulphones) (U-PS and PES), poly(aryl ester) (U-Polymer), poly(aryl amide) (A-Film) and poly(aryl ether ether ketone) (PEEK) have been studied based on changes in tensile properties. The deterioration dose estimated from the decrease in the elongation at break was as low as one-fifth to one-tenth of that in high-dose-rate electron-beam irradiation, but the order of radiation resistance of the polymers did not differ from that in electron-beam irradiation, i.e. PEEK > A-Film > U-Polymer > U-PS > PES. The radiation stability of aromatic units under oxidative conditions was estimated from a comparison of the radiation resistance of the polymers themselves and their chemical structures. The following order was obtained: diphenyl ether, diphenyl ketone > aromatic amide>> bisphenol A > diphenyl sulphone. The deterioration mechanism of PEEK under oxidative irradiation was studied by measuring dynamic viscoelastic properties. It was concluded that deterioration in mechanical properties under oxidative irradiation was brought about by chain scission only. (author)

Sorption of neptunium under oxidizing and reducing groundwater conditions

International Nuclear Information System (INIS)

Hakanen, M.

1991-01-01

Sorption of neptunium was studied under aerobic, anoxic and reducing groundwater conditions using solutions with initial Np concentrations of 10 -14 to 10 -8 mol/l. Under aerobic conditions the sorption was the same for all concentrations. Under anoxic conditions the same proportion of neptunium (70-80%) was removed from the water. The neptunium sorbed on rock surfaces was of mixed oxidation states. Only Np(V) was found in waters. Under reducing groundwater conditions, nearly all the neptunium was removed from water. The sorbed neptunium was at first almost completely in the form of Np(IV). The submicrogram amounts of neptunium were partly oxidized with time, but Np(V) did not dissolve in reducing water. The holding oxidant character of the tonalite to Np(V) and, the holding reductant character of rocks to small amounts of Np(IV), was demonstrated under anaerobic and reducing groundwater conditions, respectively. (orig.)

Formation conditions and prospecting criteria for sandstone uranium deposit of interlayer oxidation type

International Nuclear Information System (INIS)

Huang Shijie

1994-01-01

This paper comprehensively analyses the geotectonic setting and favourable conditions, such as structure of the basin, sedimentary facies and paleogeography, geomorphology and climate, hydrodynamics and hydrogeochemistry, the development of interlayered oxidation etc, necessary for the formation of sandstone uranium deposit of interlayered oxidation type. The following prospecting criteria is proposed, namely: abundant uranium source, arid climate, stable big basin, flat-lying sandstone bed, big alluvial fan, little change in sedimentary facies, intercalation of sandstone and mudstone beds, shallow burying of sandstone bed, well-aquiferous sandstone bed, high permeability of sandstone bed, development of interlayered oxidation, and high content of reductant in sandstone. In addition, the 6 in 1 hydrogenic genetic model is proposed

Optimization of thorium oxalate precipitation conditions relative to thorium oxide sinterability

International Nuclear Information System (INIS)

White, G.D.; Bray, L.A.; Hart, P.E.

1980-01-01

The effect of thorium oxalate precipitation conditions on derived oxide sinterability was investigated with the objective of producing ThO 2 powder that could be sintered to high density without premilling. Precipitation conditions examined were temperature, digestion time and agitation method which were employed in a two-level factorial experimental design to delineate their effects. The two levels for each of the factors, respectively, were 10 0 C and 70 0 C, 15 min and 360 min, and mechanical stirrer and a homogenizer that imparted both mechanical and ultrasonic agitation. The ThO 2 derived from each of the precipitation trials was characterized with respect to morphology, surface area, and crystallite size as well as sinterability. Only precipitation temperature had a significant effect upon all the properties of the derived oxide powders

High temperature oxidation in boiler environment of chromized steel

Science.gov (United States)

Alia, F. F.; Kurniawan, T.; Asmara, Y. P.; Ani, M. H. B.; Nandiyanto, A. B. D.

2017-10-01

The demand for increasing efficiency has led to the development and construction of higher operating temperature power plant. This condition may lead to more severe thickness losses in boiler tubes due to excessive corrosion process. Hence, the research to improve the corrosion resistance of the current operated material is needed so that it can be applied for higher temperature application. In this research, the effect of chromizing process on the oxidation behaviour of T91 steel was investigated under steam condition. In order to deposit chromium, mixture of chromium (Cr) powder as master alloy, halide salt (NH4Cl) powder as activator and alumina (Al2O3) powder as inert filler were inserted into alumina retort together with the steel sample and heated inside furnace at 1050°C for ten hours under argon gas environment. Furthermore, for the oxidation process, steels were exposed at 700°C at different oxidation time (6h-24h) under steam condition. From FESEM/EDX analysis, it was found that oxidation rate of pack cemented steel was lower than the un-packed steel. These results show that Cr from chromizing process was able to become reservoir for the formation of Cr2O3 in high temperature steam oxidation, and its existence can be used for a longer oxidation time.

Decomposition mechanism of melamine borate in pyrolytic and thermo-oxidative conditions

Energy Technology Data Exchange (ETDEWEB)

Hoffendahl, Carmen; Duquesne, Sophie; Fontaine, Gaëlle; Bourbigot, Serge, E-mail: serge.bourbigot@ensc-lille.fr

2014-08-20

Highlights: • Decomposition of melamine borate in pyrolytic and thermo-oxidative conditions was investigated. • With increasing temperature, orthoboric acid forms boron oxide releasing water. • Melamine decomposes evolving melamine, ammonia and other fragments. • Boron oxide is transformed into boron nitride and boron nitride-oxide structures through presence of ammonia. - Abstract: Decomposition mechanism of melamine borate (MB) in pyrolytic and thermo-oxidative conditions is investigated in the condensed and gas phases using solid state NMR ({sup 13}C and {sup 11}B), X-ray photoelectron spectroscopy (XPS), pyrolysis-gas chromatography–mass spectrometry (py-GCMS) and thermogravimetric analysis coupled with a Fourier transform infrared spectrometer (TGA–FTIR). It is evidenced that orthoboric acid dehydrates to metaboric and then to boron oxide. The melamine is partially sublimated. At the same time, melamine condensates, i.e., melem and melon are formed. Melon is only formed in thermo-oxidative conditions. At higher temperature, melem and melon decompose releasing ammonia which reacts with the boron oxide to form boron nitride (BN) and BNO structures.

Long-Term Cyclic Oxidation Behavior of Wrought Commercial Alloys at High Temperatures

Energy Technology Data Exchange (ETDEWEB)

Li, Bingtao [Iowa State Univ., Ames, IA (United States)

2003-01-01

The oxidation resistance of a high-temperature alloy is dependent upon sustaining the formation of a protective scale, which is strongly related to the alloying composition and the oxidation condition. The protective oxide scale only provides a finite period of oxidation resistance owing to its eventual breakdown, which is especially accelerated under thermal cycling conditions. This current study focuses on the long-term cyclic oxidation behavior of a number of commercial wrought alloys. The alloys studied were Fe- and Ni-based, containing different levels of minor elements, such as Si, Al, Mn, and Ti. Oxidation testing was conducted at 1000 and 1100 C in still air under both isothermal and thermal cycling conditions (1-day and 7-days). The specific aspects studied were the oxidation behavior of chromia-forming alloys that are used extensively in industry. The current study analyzed the effects of alloying elements, especially the effect of minor element Si, on cyclic oxidation resistance. The behavior of oxide scale growth, scale spallation, subsurface changes, and chromium interdiffusion in the alloy were analyzed in detail. A novel model was developed in the current study to predict the life-time during cyclic oxidation by simulating oxidation kinetics and chromium interdiffusion in the subsurface of chromia-forming alloys.

Determination of optimal conditions for pressure oxidative leaching of Sarcheshmeh Molybdenite concentrate using Taguchi method

Directory of Open Access Journals (Sweden)

Khoshnevisana A.

2012-01-01

Full Text Available The present research work is based on finding the optimum conditions for pressure oxidative leaching of the molybdenite concentrate to produce technical-grade molybdic oxide (MoO3 with high recovery through further treatment of the filtrate solution. The Taguchi method was used to design and minimize the number of experiments. By using Taguchi orthogonal (L25 array, five parameters (time, temperature, oxygen pressure, pulp density and acid concentration at five levels were selected for 25 experiments. The experiments were designed and carried out in a high-pressure reactor in the presence of nitric acid as solvent and oxidizing agent for the molybdenite concentrate and its ReS2 content. The optimum conditions for pressure leaching of molybdenite were obtained through using Signal to Noise analysis and modified by using Minitab software prediction tool. Furthermore, the optimum condition for an economical pressure leaching of rhenium sulfide (ReS2 was achieved with the same process. Analysis of variance (ANOVA showed that the pulp density is of paramount importance in this process.

Densification of Highly Defective Ceria by High Temperature Controlled Re-Oxidation

DEFF Research Database (Denmark)

Ni, De Wei; Glasscock, Julie; Pons, Aénor

2014-01-01

Highly enhanced densification and grain growth of Ce0.9Gd0.1O1.95-δ (CGO, gadolinium-doped ceria, with 10 mol% Gd) is achieved in low oxygen activity atmospheres. However, the material can suffer mechanical failures during cooling when the re-oxidation process is not controlled due to the large...... volume changes. In this work, the redox process of CGO is investigated using dilatometry, microscopy, electrochemical impedance spectroscopy and thermodynamic analysis. In addition, the conditions allowing controlled re-oxidation and cooling in order to preserve the mechanical integrity of the CGO...... component are defined: this can be achieved over a wide temperature range (800−1200◦C) by gradually increasing the oxygen content of the atmosphere. It is found that the electrical conductivity of the CGO, particularly at low temperature (oxidation...

Sensitivity analysis of uranium solubility under strongly oxidizing conditions

International Nuclear Information System (INIS)

Liu, L.; Neretnieks, I.

1999-01-01

To evaluate the effect of geochemical conditions in the repository on the solubility of uranium under strongly oxidizing conditions, a mathematical model has been developed to determine the solubility, by utilizing a set of nonlinear algebraic equations to describe the chemical equilibria in the groundwater environment. The model takes into account the predominant precipitation-dissolution reactions, hydrolysis reactions and complexation reactions that may occur under strongly oxidizing conditions. The model also includes the solubility-limiting solids induced by the presence of carbonate, phosphate, silicate, calcium, and sodium in the groundwater. The thermodynamic equilibrium constants used in the solubility calculations are essentially taken from the NEA Thermochemical Data Base of Uranium, with some modification and some uranium minerals added, such as soddyite, rutherfordite, uranophane, uranyl orthophosphate, and becquerelite. By applying this model, the sensitivities of uranium solubility to variations in the concentrations of various groundwater component species are systematically investigated. The results show that the total analytical concentrations of carbonate, phosphate, silicate, and calcium in deep groundwater play the most important role in determining the solubility of uranium under strongly oxidizing conditions

Oxidation of boron carbide at high temperatures

International Nuclear Information System (INIS)

Steinbrueck, Martin

2005-01-01

The oxidation kinetics of various types of boron carbides (pellets, powder) were investigated in the temperature range between 1073 and 1873 K. Oxidation rates were measured in transient and isothermal tests by means of mass spectrometric gas analysis. Oxidation of boron carbide is controlled by the formation of superficial liquid boron oxide and its loss due to the reaction with surplus steam to volatile boric acids and/or direct evaporation at temperatures above 1770 K. The overall reaction kinetics is paralinear. Linear oxidation kinetics established soon after the initiation of oxidation under the test conditions described in this report. Oxidation is strongly influenced by the thermohydraulic boundary conditions and in particular by the steam partial pressure and flow rate. On the other hand, the microstructure of the B 4 C samples has a limited influence on oxidation. Very low amounts of methane were produced in these tests

Effect of a ZrO{sub 2} coating deposited by the sol–gel method on the resistance of FeCrAl alloy in high-temperature oxidation conditions

Energy Technology Data Exchange (ETDEWEB)

Chęcmanowski, Jacek Grzegorz, E-mail: jacek.checmanowski@pwr.wroc.pl [Wrocław University of Technology, Faculty of Chemistry, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław (Poland); Szczygieł, Bogdan, E-mail: bogdan.szczygiel@pwr.wroc.pl [Wrocław University of Technology, Faculty of Chemistry, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław (Poland)

2013-05-15

One-, three- and five-layer protective ZrO{sub 2} coatings were deposited on a FeCrAl alloy base by the sol–gel method. A zirconium(IV) isopropoxide isopropanol complex was used as the zirconium precursor. It has been shown that zirconium in the amount of 0.3–0.5 wt.% improves the resistance of FeCrAl alloy in high-temperature oxidation conditions (in air at T = 1060 °C for t = 2400 h). Even a very low Zr content affects the morphology, porosity and composition of the forming scale (SEM, EDS). An analysis of the chemical composition of the material after oxidation indicated to-core Zr diffusion. The presence of zirconium prevents catastrophic corrosion of the FeCrAl alloy during oxidation. In the case of the alloy without the reactive element (Zr) this type of corrosion occurred after about 1800 h. The oxidation of the FeCrAl alloy covered with ZrO{sub 2} coatings proceeds in three stages. In the first stage, lasting about 50 h, the mass of the sample grows rapidly, then for 700 h the mass changes minimally and in the third stage the oxidation proceeds according to a parabolic dependence. The presence of Zr on the surface of the FeCrAl alloy significantly contributes to the protective effect of the coatings. - Highlights: ► Multilayer ZrO{sub 2} coatings were deposited on FeCrAl alloy by sol–gel method. ► Study of alloy composition indicates to-core Zr diffusion in high temperature. ► Even very low content affects morphology and porosity of forming scale. ► Zirconium improves the resistance of FeCrAl alloy in high temperature conditions. ► Presence of ZrO{sub 2} prevents catastrophic corrosion of FeCrAl alloy during oxidation.

Oxygen-Rich Lithium Oxide Phases Formed at High Pressure for Potential Lithium-Air Battery Electrode.

Science.gov (United States)

Yang, Wenge; Kim, Duck Young; Yang, Liuxiang; Li, Nana; Tang, Lingyun; Amine, Khalil; Mao, Ho-Kwang

2017-09-01

The lithium-air battery has great potential of achieving specific energy density comparable to that of gasoline. Several lithium oxide phases involved in the charge-discharge process greatly affect the overall performance of lithium-air batteries. One of the key issues is linked to the environmental oxygen-rich conditions during battery cycling. Here, the theoretical prediction and experimental confirmation of new stable oxygen-rich lithium oxides under high pressure conditions are reported. Three new high pressure oxide phases that form at high temperature and pressure are identified: Li 2 O 3 , LiO 2 , and LiO 4 . The LiO 2 and LiO 4 consist of a lithium layer sandwiched by an oxygen ring structure inherited from high pressure ε-O 8 phase, while Li 2 O 3 inherits the local arrangements from ambient LiO 2 and Li 2 O 2 phases. These novel lithium oxides beyond the ambient Li 2 O, Li 2 O 2 , and LiO 2 phases show great potential in improving battery design and performance in large battery applications under extreme conditions.

Assessing the cost of helping: the roles of body condition and oxidative balance in the Seychelles warbler (Acrocephalus sechellensis.

Directory of Open Access Journals (Sweden)

Janske van de Crommenacker

Full Text Available In cooperatively breeding species, helping close relatives may provide important fitness benefits. However, helping can be energetically expensive and may result in increased generation of reactive oxygen species. Consequently, an oxidant/antioxidant imbalance can lead to higher oxidative stress susceptibility. Given the potential costs of helping, it may be that only individuals with a sufficiently good body condition and/or stable oxidative balance can afford to help. Knowledge about relationships between social status and oxidative balance in cooperatively breeding systems is still limited. Studying these relationships is important for understanding the costs of helping and physiological pressures of reproduction. Here we evaluate the relationship between helping behaviour, body condition and oxidative balance in a wild population of the cooperatively breeding Seychelles warbler (Acrocephalus sechellensis. In this species, some subordinate individuals help dominant birds with the rearing of young, while others refrain from any assistance. We assessed body condition and oxidative parameters of birds of different social status caught during different breeding stages. We found that, prior to breeding, female subordinates that did not subsequently help (non-helpers had significantly lower body condition and higher ROMs (reactive oxygen metabolites than helpers and dominants. During the later stages of breeding, body condition was low in dominants and helpers, but high in non-helpers. Differences in oxidative balance between individuals of different social status were found only during nest care: Dominant males occupied with guarding behaviours tended to have relatively high oxidative stress susceptibility. Furthermore, dominant and helper females showed elevated antioxidant capacity (measured as OXY in the weeks just prior to egg-laying, possibly representing a change in their reproductive physiology. The results imply that an individuals

High temperature transient deformation of mixed oxide fuels

International Nuclear Information System (INIS)

Slagle, O.D.

1986-01-01

The purpose of this paper is to present recent experimental results on fuel creep under transient conditions at high temperatures. The effect of temperature, stress, heating rate, density and grain size were considered. An empirical formulation is derived for the relationship between strain, stress, temperature and heating rate. This relationship provides a means for incorporating stress relief into the analysis of fuel-cladding interaction during an overpower transient. The effect of sample density and initial grain size is considered by varying the sample parameters. Previously derived steady-state creep relationships for the high temperature creep of mixed oxide fuel were combined with the time dependency of creep found for UO 2 to calculate a transient creep relationship for mixed oxide fuel. These calculated results were found to be in good agreement with the measured high temperature transient creep results

Two oxidation pathways of bioactive flavonol rhamnazin under ambient conditions

International Nuclear Information System (INIS)

Ramešová, Šárka; Degano, Ilaria; Sokolová, Romana

2014-01-01

Graphical abstract: - Highlights: • The oxidation mechanism of rhamnazin has not been solved yet. • Rhamnazin decomposes in solution during minutes handled in the presence of air. • The main oxidation product of rhamnazin was identified even if it is not stable. • Two parallel oxidation mechanisms of rhamnazin in air were determined. - Abstract: Two pathways of the oxidation mechanism of rhamnazin under ambient conditions are proposed. The redox potential of rhamnazin strongly depends on the presence of dissociation forms in solution. In situ spectroelectrochemistry and identification of degradation products by HPLC-DAD and HPLC–ESI-MS/MS confirmed the presence of fast subsequent chemical reactions following the electron transfer. As demonstrated, strict anaerobic conditions have to be preserved in studies of antioxidant properties and of its pharmacological efficiency. In the absence of oxygen, 2,4-dihydroxy-2-(4′-hydroxy-3′-methoxybenzoyl) -6-methoxy-benzofuran-3(2H)-one was identified as the only oxidation product

Rate law of Fe(II) oxidation under low O2 conditions

Science.gov (United States)

Kanzaki, Yoshiki; Murakami, Takashi

2013-12-01

Despite intensive studies on Fe(II) oxidation kinetics, the oxidation rate law has not been established under low O2 conditions. The importance of Fe(II) oxidation under low O2 conditions has been recently recognized; for instance, the Fe(II)/Fe(III) compositions of paleosols, ancient soils formed by weathering, can produce a quantitative pattern of the atmospheric oxygen increase during the Paleoproterozoic. The effects of partial pressure of atmospheric oxygen (PO2) on the Fe(II) oxidation rate were investigated to establish the Fe(II) oxidation rate - PO2 relationships under low O2 conditions. All oxidation experiments were carried out in a glove box by introducing Ar gas at ∼10-5-∼10-4 atm of PO2, pH 7.57-8.09 and 22 °C. Luminol chemiluminescence was adopted to measure low Fe(II) concentrations (down to ∼2 nM). Combining previous data under higher PO2 conditions (10-3-0.2 atm) with the present data, the rate law for Fe(II) oxidation over a wide range of PO2 (10-5-0.2 atm) was found to be written as: d[Fe(II)]/dt=-k[Fe(II)][[]2 where the exponent of [O2], x, and the rate constant, k, change from x = 0.98 (±0.04) and log k = 15.46 (±0.06) at ∼6 × 10-3-0.2 atm of PO2 to x = 0.58 (±0.02) and log k = 13.41 (±0.03) at 10-5-∼6 × 10-3 atm of PO2. The most plausible mechanism that explains the change in x under low O2 conditions is that, instead of O2, oxygen-derived oxidants, H2O2 and to some extent, O2rad -, dominate the oxidation reactions at PO2. The rate law found in the present study requires us to reconsider distributions of Fe redox species at low PO2 in natural environments, especially in paleoweathering profiles, and may provide a deeper understanding of the evolution of atmospheric oxygen in the Precambrian.

Sensitizing effects of NOx on CH4 oxidation at high pressure

DEFF Research Database (Denmark)

Rasmussen, Christian Lund; Rasmussen, Anja Egede; Glarborg, Peter

2008-01-01

The CH4/O2/NOx system is investigated in a laboratory-scale high pressure laminar flow reactor with the purpose of elucidating the sensitizing effects of NOx on CH4 oxidation at high pressures and medium temperatures. Experiments are conducted at 100, 50, and 20 bar, 600-900 K, and stoichiometric...... ratios ranging from highly reducing to oxidizing conditions. The experimental results are interpreted in terms of a detailed kinetic model drawn from previous work of the authors, including an updated reaction subset for the direct interactions of NOx and C1-2 hydrocarbon species relevant...

Hydrogenation and high temperature oxidation of Zirconium claddings

International Nuclear Information System (INIS)

Novotny, T.; Perez-Feró, E.; Horváth, M.

2015-01-01

In the last few years a new series of experiments started for supporting the new LOCA criteria, considering the proposals of US NRC. The effects which can cause the embrittlement of VVER fuel claddings were reviewed and evaluated in the framework of the project. The purpose of the work was to determine how the fuel cladding’s hydrogen uptake under normal operating conditions, effect the behavior of the cladding under LOCA conditions. As a first step a gas system equipment with gas valves and pressure gauge was built, in which the zirconium alloy can absorb hydrogen under controlled conditions. In this apparatus E110 (produced by electrolytic method, currently used at Paks NPP) and E110G (produced by a new technology) alloys were hydrogenated to predetermined hydrogen contents. According the results of ring compression tests the E110G alloys lose their ductility above 3200 ppm hydrogen content. This limit can be applied to determine the ductile-brittle transition of the nuclear fuel claddings. After the hydrogenation, high temperature oxidation experiments were carried out on the E110G and E110 samples at 1000 °C and 1200 °C. 16 pieces of E110G and 8 samples of E110 with 300 ppm and 600 ppm hydrogen content were tested. The oxidation of the specimens was performed in steam, under isothermal conditions. Based on the ring compression tests load-displacement curves were recorded. The main objective of the compression tests was to determine the ductile-brittle transition. These results were compared to the results of our previous experiments where the samples did not contain hydrogen. The original claddings showed more ductile behavior than the samples with hydrogen content. The higher hydrogen content resulted in a more brittle mechanical behavior. However no significant difference was observed in the oxidation kinetics of the same cladding types with different hydrogen content. The experiments showed that the normal operating hydrogen uptake of the fuel claddings

Possibility of Localized Corrosion of PWR primary side materials in oxidative decontamination condition

Energy Technology Data Exchange (ETDEWEB)

Park, Sang Yoon; Jung, Jun Young; Won, Huijun; Kim, Seon Byeong; Choi, Wangkyu; Moon, Jeikwon [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2014-05-15

Primary circuit of a PWR (radionuclides uptake in the inner oxide layer and oxide/metal interface occurred inevitably. Therefore, it is necessary to remove the inner oxide layer as well as the outer oxide layer to achieve excellent decontamination effects. It is known that the outer oxide layers are typically composed of Fe{sub 3}O{sub 4} and NiFe{sub 2}O{sub 4}. On the other hand, the inner oxide layers are composed of Cr{sub 2}O{sub 3}, (Ni{sub 1-x}Ni{sub x})(Cr{sub 1-y}Fe{sub y}){sub 2}O{sub 4}, and FeCr{sub 2}O{sub 4}. Because of chromium in the trivalent oxidation state which is difficult to dissolve, the oxide layer has an excellent protectiveness and is hard to decontaminate. For the dissolution of chromium-rich oxide, there have been developed an alkaline permanganate (AP) or nitric permanganate (NP). A disadvantage of the AP process is the generation of a large volume of secondary waste. On the other hand, NP process is highly incompatible to the corrosion of the structure materials. In this study as a part of developing decontamination process, we investigated the corrosion behavior of the structure materials such as Inconel-600 and type 304 stainless steel in NP and AP oxidative decontamination conditions for the safe use of an oxidative phase in PWR system decontamination. The corrosion behavior was analyzed through the potential-pH equilibrium for the system of Cr-H{sub 2}O / Mn-H{sub 2}O at 90 .deg. C and potentiodynamic polarization in a typical AP and NP solution were evaluated. The AP or NP treated specimen surface was observed using an optical microscope and scanning electron microscopy (SEM) for an evaluation of the localized corrosion. The possibility of localized corrosion of PWR primary side materials under oxidative decontamination condition was evaluated using a potentiodynamic polarization technique, observation of localized corrosion morphology, and consideration of potential-pH diagrams at 90 .deg. C. From the results of these tests, we

Sclerotial biomass and carotenoid yield of Penicillium sp. PT95 under oxidative growth conditions and in the presence of antioxidant ascorbic acid.

Science.gov (United States)

Li, X L; Cui, X H; Han, J R

2006-09-01

To determine the effect of oxidative stress and exogenous ascorbic acid on sclerotial biomass and carotenoid yield of Penicillium sp. PT95. In this experiment, high oxidative stress was applied by the inclusion of FeSO(4) in the growth medium and exposure to light. Low oxidative stress was applied by omitting iron from the growth medium and by incubation in the dark. Supplementation of exogenous ascorbic acid (as antioxidant) to the basal medium caused a concentration-dependent delay of sclerotial differentiation (up to 48 h), decrease of sclerotial biomass (up to 40%) and reduction of carotenoid yield (up to 91%). On the contrary, the exogenous ascorbic acid also caused a concentration-dependent decrease of lipid peroxidation in colonies of this fungus. Under high oxidative stress growth condition, the sclerotial biomass and carotenoid yield of PT95 strain in each plate culture reached 305 mg and 32.94 microg, which were 1.23 and 3.71 times higher, respectively, than those at low oxidative stress growth condition. These data prompted us to consider that in order to attain higher sclerotial biomass and pigment yield, the strain PT95 should be grown under high oxidative stress and in the absence of antioxidants. These results suggest that strain PT95 may be used for solid-state fermentation of carotenoid production under high oxidative stress growth conditions.

High-temperature oxidation of tungsten covered by layer of glass-enamel melt

International Nuclear Information System (INIS)

Vasnetsova, V.B.; Shardakov, N.T.; Kudyakov, V.Ya.; Deryabin, V.A.

1997-01-01

Corrosion losses of tungsten covered by the layer of glass-enamel melt were determined at 800, 850, 900, 950 deg C. It is shown that the rate of high-temperature oxidation of tungsten decreases after application of glass-enamel melt on its surface. This is probably conditioned by reduction of area of metal interaction with oxidizing atmosphere

Sensitivity to grid resolution in the ability of a chemical transport model to simulate observed oxidant chemistry under high-isoprene conditions

Directory of Open Access Journals (Sweden)

K. Yu

2016-04-01

Full Text Available Formation of ozone and organic aerosol in continental atmospheres depends on whether isoprene emitted by vegetation is oxidized by the high-NOx pathway (where peroxy radicals react with NO or by low-NOx pathways (where peroxy radicals react by alternate channels, mostly with HO2. We used mixed layer observations from the SEAC4RS aircraft campaign over the Southeast US to test the ability of the GEOS-Chem chemical transport model at different grid resolutions (0.25°  ×  0.3125°, 2°  ×  2.5°, 4°  ×  5° to simulate this chemistry under high-isoprene, variable-NOx conditions. Observations of isoprene and NOx over the Southeast US show a negative correlation, reflecting the spatial segregation of emissions; this negative correlation is captured in the model at 0.25°  ×  0.3125° resolution but not at coarser resolutions. As a result, less isoprene oxidation takes place by the high-NOx pathway in the model at 0.25°  ×  0.3125° resolution (54 % than at coarser resolution (59 %. The cumulative probability distribution functions (CDFs of NOx, isoprene, and ozone concentrations show little difference across model resolutions and good agreement with observations, while formaldehyde is overestimated at coarse resolution because excessive isoprene oxidation takes place by the high-NOx pathway with high formaldehyde yield. The good agreement of simulated and observed concentration variances implies that smaller-scale non-linearities (urban and power plant plumes are not important on the regional scale. Correlations of simulated vs. observed concentrations do not improve with grid resolution because finer modes of variability are intrinsically more difficult to capture. Higher model resolution leads to decreased conversion of NOx to organic nitrates and increased conversion to nitric acid, with total reactive nitrogen oxides (NOy changing little across model resolutions. Model concentrations in the

Efficient and facile one pot carboxylation of multiwalled carbon nanotubes by using oxidation with ozone under mild conditions

International Nuclear Information System (INIS)

Naeimi, Hossein; Mohajeri, Ali; Moradi, Leila; Rashidi, Ali Morad

2009-01-01

Graphical abstract: In this work, oxidation of carbon nanotubes with ozone in the presence of hydrogen peroxide was studied. The reactions were performed under clean and mild conditions and oxidized products with high concentration of oxygenated groups were yielded. The reaction products were characterized with attenuated total reflectance (ATR), Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffractometry (XRD), back titration, X-ray photoelectron spectroscopy (XPS) and the dispersion behavior of the oxidized multiwalled carbon nanotubes (MWCNTs) was also studied. The results confirmed the presence of high concentrations of oxidative groups on the carbon nanotubes (CNTs) treated by the method of the present work.

Oxidative Stress in Early Life: Associations with Sex, Rearing Conditions, and Parental Physiological Traits in Nestling Pied Flycatchers.

Science.gov (United States)

López-Arrabé, Jimena; Cantarero, Alejandro; Pérez-Rodríguez, Lorenzo; Palma, Antonio; Moreno, Juan

2016-01-01

Conditions experienced during juvenile development can affect the fitness of an organism. During early life, oxidative stress levels can be particularly high as a result of the increased metabolism and the relatively immature antioxidant system of the individual, and this may have medium- and long-term fitness consequences. Here we explore variation in levels of oxidative stress measured during early life in relation to sex, rearing conditions (hatching date and brood size), and parental condition and levels of oxidative markers in a wild population of the pied flycatcher (Ficedula hypoleuca) followed for 2 yr. A marker of total antioxidant status (TAS) in plasma and total levels of glutathione (GSH) in red blood cells, as well as a marker of oxidative damage in plasma lipids (malondialdehyde [MDA]), were assessed simultaneously. Our results show that nestling total GSH levels were associated with parental oxidative status, correlating negatively with maternal MDA and positively with total GSH levels of both parents, with a high estimated heritability. This suggests that parental physiology and genes could be determinants for endogenous components of the antioxidant system of the offspring. Moreover, we found that total GSH levels were higher in female than in male nestlings and that hatching date was positively associated with antioxidant defenses (higher TAS and total GSH levels). These results suggest that different components of oxidative balance are related to a variety of environmental and intrinsic--including parental--influencing factors. Future experimental studies must disentangle the relative contribution of each of these on nestling oxidative status and how the resulting oxidative stress at early phases shape adult phenotype and fitness.

High-throughput technology for novel SO2 oxidation catalysts

International Nuclear Information System (INIS)

Loskyll, Jonas; Stoewe, Klaus; Maier, Wilhelm F

2011-01-01

We review the state of the art and explain the need for better SO 2 oxidation catalysts for the production of sulfuric acid. A high-throughput technology has been developed for the study of potential catalysts in the oxidation of SO 2 to SO 3 . High-throughput methods are reviewed and the problems encountered with their adaptation to the corrosive conditions of SO 2 oxidation are described. We show that while emissivity-corrected infrared thermography (ecIRT) can be used for primary screening, it is prone to errors because of the large variations in the emissivity of the catalyst surface. UV-visible (UV-Vis) spectrometry was selected instead as a reliable analysis method of monitoring the SO 2 conversion. Installing plain sugar absorbents at reactor outlets proved valuable for the detection and quantitative removal of SO 3 from the product gas before the UV-Vis analysis. We also overview some elements used for prescreening and those remaining after the screening of the first catalyst generations. (topical review)

Oxidation damage evaluation by non-destructive method for graphite components in high temperature gas-cooled reactor

International Nuclear Information System (INIS)

Shibata, Taiju; Tada, Tatsuya; Sumita, Junya; Sawa, Kazuhiro

2008-01-01

To develop non-destructive evaluation methods for oxidation damage on graphite components in High Temperature Gas-cooled Reactors (HTGRs), the applicability of ultrasonic wave and micro-indentation methods were investigated. Candidate graphites, IG-110 and IG-430, for core components of Very High Temperature Reactor (VHTR) were used in this study. These graphites were oxidized uniformly by air at 500degC. The following results were obtained from this study. (1) Ultrasonic wave velocities with 1 MHz can be expressed empirically by exponential formulas to burn-off, oxidation weight loss. (2) The porous condition of the oxidized graphite could be evaluated with wave propagation analysis with a wave-pore interaction model. It is important to consider the non-uniformity of oxidized porous condition. (3) Micro-indentation method is expected to determine the local oxidation damage. It is necessary to assess the variation of the test data. (author)

Interaction of oxides of nitrogen and aromatic hydrocarbons under simulated atmospheric conditions

International Nuclear Information System (INIS)

Obrien, R.J.; Green, P.J.; Doty, R.A.; Vanderzanden, J.W.; Easton, R.R.; Irwin, R.P.

1979-01-01

The reactions of nitrogen oxides with aromatic hydrocarbons under simulated atmospheric conditions are investigated. Gaseous reaction products formed when toluene is irradiated under simulated atmospheric conditions in the presence of nitrogen oxides were analyzed by gas chromatography. Reaction products detected include acetylene, water, acetaldehyde, acetone, toluene, benzaldehyde, ortho-, meta- and para-cresol, benzyl nitrate and meta- and para-nitrotoluene. Reaction mechanisms yielding the various products are illustrated. The assumption that all the nitrogen oxides observed to be lost from the reaction products can be accounted for by nitric acid formation in the absence of ozone formation is verified by a model in which the hydroxyl radical is assumed to be the only means of removing toluene. Under conditions in which ozone is formed, nitrogen oxide loss is accounted for by ozone formation in addition to nitric acid formation

High throughput measurement of high temperature strength of ceramics in controlled atmosphere and its use on solid oxide fuel cell anode supports

DEFF Research Database (Denmark)

Frandsen, Henrik Lund; Curran, Declan; Rasmussen, Steffen

2014-01-01

In the development of structural and functional ceramics for high temperature electrochemical conversion devices such as solid oxide fuel cells, their mechanical properties must be tested at operational conditions, i.e. at high temperature and controlled atmospheres. Furthermore, characterization...... for testing multiple samples at operational conditions providing a high throughput and thus the possibility achieve high reliability. Optical methods are used to measure deformations contactless, frictionless load measuring is achieved, and multiple samples are handled in one heat up. The methodology...... is validated at room temperature, and exemplified by measurement of the strength of solid oxide fuel cell anode supports at 800 C. © 2014 Elsevier B.V. All rights reserved....

Fuel removal from plasma-facing components by oxidation-based techniques. An overview of surface conditions after oxidation

International Nuclear Information System (INIS)

Rubel, M.J.; De Temmerman, G.; Sergienko, G.; Sundelin, P.; Emmoth, B.; Philipps, V.

2007-01-01

Oxygen-assisted fuel removal is reported for laboratory-prepared a-C:D films and for layers obtained by boronisation in a tokamak and then exposed to a helium-oxygen glow discharge in TEXTOR. Oxidation of thick mixed-material co-deposits under laboratory conditions is also presented. The essential results are following: (i) laboratory-prepared amorphous deuterated carbon (a-C:D) layers are decomposed efficiently by the He-O 2 glow: D and C contents are decreased by a factor of 45-220 and 25-60, respectively; (ii) the same treatment of the boronised films leads to the release of D but no removal of carbon is observed; (iii) the thermal oxidation (at 300 deg. C in air under laboratory conditions) of co-deposits on PFC and probes exposed to the SOL reduces the D content by a factor of 4-5 after 2 h, whereas nearly complete fuel removal (98%) occurs after 10 h at 300 deg. C. The study shows that the fuel removal efficiency is dependent on the overall composition of the mixed layer. It is high from pure a-C:D films but distinctly less efficient from real co-deposits

High temperature oxidation resistant cermet compositions

Science.gov (United States)

Phillips, W. M. (Inventor)

1976-01-01

Cermet compositions are designed to provide high temperature resistant refractory coatings on stainless steel or molybdenum substrates. A ceramic mixture of chromium oxide and aluminum oxide form a coating of chromium oxide as an oxidation barrier around the metal particles, to provide oxidation resistance for the metal particles.

Laser-Induced Reductive Sintering of Nickel Oxide Nanoparticles under Ambient Conditions

KAUST Repository

Paeng, Dongwoo; Lee, Daeho; Yeo, Junyeob; Yoo, Jae-Hyuck; Allen, Frances I.; Kim, Eunpa; So, Hongyun; Park, Hee K.; Minor, Andrew M.; Grigoropoulos, Costas P.

2015-01-01

© 2015 American Chemical Society. This work is concerned with the kinetics of laser-induced reductive sintering of nonstoichiometric crystalline nickel oxide (NiO) nanoparticles (NPs) under ambient conditions. The mechanism of photophysical reductive sintering upon irradiation using a 514.5 nm continuous-wave (CW) laser on NiO NP thin films has been studied through modulating the laser power density and illumination time. Protons produced due to high-temperature decomposition of the solvent present in the NiO NP ink, oxygen vacancies in the NiO NPs, and electronic excitation in the NiO NPs by laser irradiation all affect the early stage of the reductive sintering process. Once NiO NPs are reduced by laser irradiation to Ni, they begin to coalesce, forming a conducting material. In situ optical and electrical measurements during the reductive sintering process take advantage of the distinct differences between the oxide and the metallic phases to monitor the transient evolution of the process. We observe four regimes: oxidation, reduction, sintering, and reoxidation. A characteristic time scale is assigned to each regime.

Laser-Induced Reductive Sintering of Nickel Oxide Nanoparticles under Ambient Conditions

KAUST Repository

Paeng, Dongwoo

2015-03-19

© 2015 American Chemical Society. This work is concerned with the kinetics of laser-induced reductive sintering of nonstoichiometric crystalline nickel oxide (NiO) nanoparticles (NPs) under ambient conditions. The mechanism of photophysical reductive sintering upon irradiation using a 514.5 nm continuous-wave (CW) laser on NiO NP thin films has been studied through modulating the laser power density and illumination time. Protons produced due to high-temperature decomposition of the solvent present in the NiO NP ink, oxygen vacancies in the NiO NPs, and electronic excitation in the NiO NPs by laser irradiation all affect the early stage of the reductive sintering process. Once NiO NPs are reduced by laser irradiation to Ni, they begin to coalesce, forming a conducting material. In situ optical and electrical measurements during the reductive sintering process take advantage of the distinct differences between the oxide and the metallic phases to monitor the transient evolution of the process. We observe four regimes: oxidation, reduction, sintering, and reoxidation. A characteristic time scale is assigned to each regime.

Tungsten oxide nanowires grown on graphene oxide sheets as high-performance electrochromic material

International Nuclear Information System (INIS)

Chang, Xueting; Sun, Shibin; Dong, Lihua; Hu, Xiong; Yin, Yansheng

2014-01-01

Graphical abstract: Electrochromic mechanism of tungsten oxide nanowires-reduced graphene oxide composite. - Highlights: • A novel inorganic-nano-carbon hybrid composite was prepared. • The hybrid composite has sandwich-like structure. • The hybrid composite exhibited high-quality electrohcromic performance. - Abstract: In this work, we report the synthesis of a novel hybrid electrochromic composite through nucleation and growth of ultrathin tungsten oxide nanowires on graphene oxide sheets using a facile solvothermal route. The competition between the growth of tungsten oxide nanowires and the reduction of graphene oxide sheets leads to the formation of sandwich-structured tungsten oxide-reduced graphene oxide composite. Due to the strongly coupled effect between the ultrathin tungsten oxide nanowires and the reduced graphene oxide nanosheets, the novel electrochromic composite exhibited high-quality electrochromic performance with fast color-switching speed, good cyclic stability, and high coloration efficiency. The present tungsten oxide-reduced graphene oxide composite represents a new approach to prepare other inorganic-reduced graphene oxide hybrid materials for electrochemical applications

Selective oxidation of n-butane to maleic anhydride under oxygen-deficient conditions over V-P-O mixed oxides

NARCIS (Netherlands)

Bosch, H.; Bruggink, A.A.; Ross, J.R.H.

1987-01-01

The selective oxidation of n-butane to maleic anhydride over V-P-O mixed oxides was studied under oxygen deficient conditions. The mixed oxides were prepared with P/V atomic ratios ranging from 0.7 to 1.0. Catalysts with P/V <1.0 did not show any selectivity to maleic anhydride formation, regardless

Mathematical Modeling of Wastewater Oxidation under Microgravity Conditions

OpenAIRE

Boyun Guo; Donald W. Holder; David S. Schechter

2005-01-01

Volatile removal assembly (VRA) is a module installed in the International Space Station for removing contaminants (volatile organics) in the wastewater produced by the crew. The VRA contains a slim pack bed reactor to perform catalyst oxidation of the wastewater at elevated pressure and temperature under microgravity conditions. Optimal design of the reactor requires a thorough understanding about how the reactor performs under microgravity conditions. The objective of this study was to theo...

Evidence of highly oxidizing environment over the South Pole

International Nuclear Information System (INIS)

Davis, D.

2001-01-01

Researchers at the Georgia Institute of Technology have discovered high levels of an air purifying chemical or oxidizing agent in the near-surface atmosphere over the South Pole. This research, funded by the National Science Foundation, has implications for interpreting historical global climate records stored in Antarctic ice cores. The hydroxyl (OH) radical is higher at the South Pole than that estimated from OH measurements recorded at the equator. The OH radical is vital to scrubbing pollution and naturally occurring chemicals from the air and prevents a buildup of toxic levels of chemicals. The near surface atmospheric zone is a highly oxidizing environment at the South Pole. There is evidence that oxidizing chemistry continues to occur in the buried snow. This active chemistry could modify chemical species before they are trapped in the ice in their final chemical forms. Therefore, glaciochemists who study climate change based on analysis of trace chemicals trapped in polar ice will have to be more careful in their interpretations of Antarctic ice cores. Any significant increase of nitric oxide levels in any snow-covered area should result in high OH levels. Scientists used the selected-ion chemical ionization mass spectrometer technique to measure OH. To measure nitric oxide (NO), they used chemiluminescence with modifications to improve its sensitivity. Nitric oxide is also a radical and is a by-product of internal combustion engines. At the South Pole, it is formed when ultraviolet radiation interacts with nitrate ions. The source of NO is not clear, but it may originate from stratospheric denitrification and the long-range transport of nitric acid formed at low latitude during electrical storms. Scientists are also working to better understand the oxidation of dimethyl sulfide (DMS) under the cold conditions and high latitudes of Antarctica. This information will help glaciochemists to better interpret sulfate and methane sulfonate concentrations

Effects of Thermal Annealing Conditions on Cupric Oxide Thin Film

Energy Technology Data Exchange (ETDEWEB)

Kim, Hyo Seon; Oh, Hee-bong; Ryu, Hyukhyun [Inje University, Gimhae (Korea, Republic of); Lee, Won-Jae [Dong-Eui University, Busan (Korea, Republic of)

2015-07-15

In this study, cupric oxide (CuO) thin films were grown on fluorine doped tin oxide(FTO) substrate by using spin coating method. We investigated the effects of thermal annealing temperature and thermal annealing duration on the morphological, structural, optical and photoelectrochemical properties of the CuO film. From the results, we could find that the morphologies, grain sizes, crystallinity and photoelectrochemical properties were dependent on the annealing conditions. As a result, the maximum photocurrent density of -1.47 mA/cm{sup 2} (vs. SCE) was obtained from the sample with the thermal annealing conditions of 500 ℃ and 40 min.

High purity samarium oxide from mixed rare earth carbonates

International Nuclear Information System (INIS)

Queiroz, Carlos A. da S.; Seneda, Jose A.; Vasconcellos, Mari E. de; Pedreira Filho, Walter dos R.

2013-01-01

A simple and economical chemical process for the production of highly pure samarium oxides is discussed. The raw material, which was used in the form of rare earth carbonates was produced industrially from the chemical treatment of Brazilian monazite. Ion exchange chromatography was performed using a strong cationic resin that is typically employed in water treatment processes to fractionate rare earth elements (REE) without the use of retention ions. Under these conditions, 99.9% pure Sm 2 O 3 was eluted using the ammonium salt of ethylenediaminetetraacetic acid (EDTA) at a controlled pH. The EDTA-samarium complex was separated from EDTA and then precipitated as oxalate and fired to samarium oxide. Molecular absorption spectrophotometry was used to monitor the samarium content during the proposed process, and sector field inductively coupled plasma mass spectrometry was used to certify the purity of the samarium oxide. Typical samarium oxide obtained from the proposed procedure contained the following contaminants in micrograms per gram: Sc (20.90); Y (11.80); La (8.4); Ce (4.3); Pr (2.5); Nd (5.1); Eu (94); Gd (114); Tb (3.6); Dy (2.5), Ho (2.3); Er (3.0); Tm (2.3); Yb (38,2); Lu (25.6). The high-purity samarium oxides produced in the present study can be used as an alternative to imported products in research and development applications. (author)

High temperature oxidation test of oxide dispersion strengthened (ODS) steel claddings

International Nuclear Information System (INIS)

Narita, Takeshi; Ukai, Shigeharu; Kaito, Takeji; Ohtsuka, Satoshi; Matsuda, Yasushi

2006-07-01

In a feasibility study of ODS steel cladding, its high temperature oxidation resistance was evaluated. Although addition of Cr is effective for preventing high temperature oxidation, excessively higher amount of Cr leads to embrittlement due to the Cr-rich α' precipitate formation. In the ODS steel developed by the Japan Atomic Energy Agency (JAEA), the Cr content is controlled in 9Cr-ODS martensite and 12Cr-ODS ferrite. In this study, high temperature oxidation test was conducted for ODS steels, and their results were compared with that of conventional austenitic stainless steel and ferritic-martensitic stainless steel. Following results were obtained in this study. (1) 9Cr-ODS martensitic and 12Cr-ODS ferritic steel have superior high temperature oxidation resistance compared to 11mass%Cr PNC-FMS and even 17mass% SUS430 and equivalent to austenitic PNC316. (2) The superior oxidation resistance of ODS steel was attributed to earlier formation of the protective alpha-Cr 2 O 3 layer at the matrix and inner oxide scale interface. The grain size of ODS steel is finer than that of PNC-FMS, so the superior oxidation resistance of ODS steel can be attributed to the enhanced Cr-supplying rate throughout the accelerated grain boundary diffusion. Finely dispersed Y 2 O 3 oxide particles in the ODS steel matrix may also stabilized the adherence between the protective alpha-Cr 2 O 3 layer and the matrix. (author)

Biotic manganese oxidation coupled with methane oxidation using a continuous-flow bioreactor system under marine conditions.

Science.gov (United States)

Kato, Shingo; Miyazaki, Masayuki; Kikuchi, Sakiko; Kashiwabara, Teruhiko; Saito, Yumi; Tasumi, Eiji; Suzuki, Katsuhiko; Takai, Ken; Cao, Linh Thi Thuy; Ohashi, Akiyoshi; Imachi, Hiroyuki

2017-10-01

Biogenic manganese oxides (BioMnOx) can be applied for the effective removal and recovery of trace metals from wastewater because of their high adsorption capacity. Although a freshwater continuous-flow system for a nitrifier-based Mn-oxidizing microbial community for producing BioMnOx has been developed so far, a seawater continuous-flow bioreactor system for BioMnOx production has not been established. Here, we report BioMnOx production by a methanotroph-based microbial community by using a continuous-flow bioreactor system. The bioreactor system was operated using a deep-sea sediment sample as the inoculum with methane as the energy source for over 2 years. The BioMnOx production became evident after 370 days of reactor operation. The maximum Mn oxidation rate was 11.4 mg L -1 day -1 . An X-ray diffraction analysis showed that the accumulated BioMnOx was birnessite. 16S rRNA gene-based clone analyses indicated that methanotrophic bacterial members were relatively abundant in the system; however, none of the known Mn-oxidizing bacteria were detected. A continuous-flow bioreactor system coupled with nitrification was also run in parallel for 636 days, but no BioMnOx production was observed in this bioreactor system. The comparative experiments indicated that the methanotroph-based microbial community, rather than the nitrifier-based community, was effective for BioMnOx production under the marine environmental conditions.

Application of high-pressure techniques: stabilization and oxidation-state control of novel superconductive and related multi-layered copper oxides

International Nuclear Information System (INIS)

Yamauchi, H.; Karppinen, M.

2000-01-01

Copper oxide superconductors possess multi-layered structures with a layer sequence of -CuO 2 -(Q-CuO 2 ) n-1 -AO-(MO 1±δ ) m -AO- or -CuO 2 -B-(O 2 -B) s-1 -CuO 2 -AO-(MO 1±δ ) m -AO- along the elongated c axis. Based on this layer sequence, the known copper oxide structures are categorized as members of the homologous series, M m A r Q n-1 Cu n O m+r+2 +n ±δ (M-mr(n-1)n ; category A) or M m A 2k B s Cu 1+k O m +4k +2s±δ (M-m(2k)s (1+k ); category B). Stabilization of such structures especially in the case of high values of the n /s parameter, i.e. the higher members of the homologous series, has been demonstrated to be apparently promoted under high pressures and/or strongly oxidizing conditions. Consequently, techniques for applying both high oxygen gas pressures (10-2000 atm) and ultra-high solid-medium pressures (2-8 GPa) have been advantageously utilized in synthesizing various superconductive copper oxide phases. Especially the ultra-high solid-medium pressure synthesis carried out in the so-called cubic-anvil/belt-type apparatus has proven to be extremely successful in synthesizing novel superconductive phases. In order to achieve high partial pressures of oxygen in the solid-medium environment, 'external' oxygen-generating oxides such as KClO 4 , KClO 3 and Ag 2 O 2 are commonly added to the precursor mixtures. It is emphasized that in some cases it is possible to utilize 'internal' oxidizing agents alone, i.e. highly oxidized precursors such as BaCuO 2+δ and Ba 2 Cu 3 O 5+δ containing metal constituents common with the desired copper oxide phase only. In the present paper, the potential and applications of high-pressure techniques in synthesizing multi-layered copper oxides and related structures are reviewed and discussed with emphasis on the important 'historical' discoveries of novel phases and the present status of controlled production of high-quality samples of such phases. (author)

Stability and oxidation products of hydrolysable tannins in basic conditions detected by HPLC/DAD-ESI/QTOF/MS.

Science.gov (United States)

Tuominen, Anu; Sundman, Terhi

2013-01-01

Hydrolysable tannins occur in plants that are used for food or medicine by humans or herbivores. Basic conditions can alter the structures of tannins, that is, the oxidation of phenolic groups can lead to the formation of toxic quinones. Previously, these labile quinones and other oxidation products have been studied with colorimetric or electron paramagnetic resonance methods, which give limited information about products. To study the stability and oxidation products of hydrolysable tannins in basic conditions using HPLC with a diode-array detector (DAD) combined with electrospray ionisation (ESI) and quadrupole time-of-flight (QTOF) MS. Three galloyl glucoses, four galloyl derivatives with different polyols and three ellagitannins were purified from plants. The incubation reactions of tannins were monitored by HPLC/DAD at five pH values and in reduced oxygen conditions. Reaction products were identified based on UV spectra and mass spectral fragmentation obtained with the high-resolution HPLC/DAD-ESI/QTOF/MS. The use of a base-resistant HPLC column enabled injections without the sample pre-treatment and thus detection of short-lived products. Hydrolysable tannins were unstable in basic conditions and half-lives were mostly less than 10 min at pH 10. Degradation rates were faster at pH 11 but slower at milder pH. The HPLC analyses revealed that various products were formed and identified to be the result of hydrolysis, deprotonation and oxidation. Interestingly, the main hydrolysis product was ellagic acid; it was also formed from galloyl glucoses that do not contain oxidatively coupled galloyl groups in their initial structures. HPLD/DAD-ESI/QTOF/MS was an efficient method for the identification of polyphenol oxidation products and showed how different pH conditions determine the fate of hydrolysable tannins. Copyright © 2013 John Wiley & Sons, Ltd.

Oxidation and Reduction of Liquid SnPb (60/40) under Ambient and Vacuum Conditions

DEFF Research Database (Denmark)

Kuhmann, Jochen Friedrich; Maly, K.; Preuss, A.

1998-01-01

One of the most straightforward approaches to fluxless solder bonding is using vacuum conditions to prevent further oxidation and, where needed, to reduce solder oxides by the use of molecular hydrogen (H-2).(1-3) This study On oxidation and reduction of solder oxides on SnPb (60/40) is aimed...... to provide a better understanding for fluxless solder bonding applications under controlled atmospheric conditions; By means of scanning Auger spectroscopy it is shown, that growth of oxide films on metallic SnPb above the eutectic temperature can be significantly reduced by decreasing the O-2 partial...

Impact of oxidative stress defense on bacterial survival and morphological change in Campylobacter jejuni under aerobic conditions

Directory of Open Access Journals (Sweden)

Euna eOh

2015-04-01

Full Text Available Campylobacter jejuni, a microaerophilic foodborne pathogen, inescapably faces high oxygen tension during its transmission to humans. Thus, the ability of C. jejuni to survive under oxygen-rich conditions may significantly impact C. jejuni viability in food and food safety as well. In this study, we investigated the impact of oxidative stress resistance on the survival of C. jejuni under aerobic conditions by examining three mutants defective in key antioxidant genes, including ahpC, katA, and sodB. All the three mutants exhibited growth reduction under aerobic conditions compared to the wild type (WT, and the ahpC mutant showed the most significant growth defect. The CFU reduction in the mutants was recovered to the WT level by complementation. Higher levels of reactive oxygen species (ROS were accumulated in C. jejuni under aerobic conditions than microaerobic conditions, and supplementation of culture media with an antioxidant recovered the growth of C. jejuni. The levels of lipid peroxidation and protein oxidation were significantly increased in the mutants compared to WT. Additionally, the mutants exhibited different morphological changes under aerobic conditions. The ahpC and katA mutants developed coccoid morphology by aeration, whereas the sodB mutant established elongated cellular morphology. Compared to microaerobic conditions, interestingly, aerobic culture conditions substantially induced the formation of coccoidal cells, and antioxidant treatment reduced the emergence of coccoid forms under aerobic conditions. The ATP concentrations and PMA-qPCR analysis supported that oxidative stress is a factor that induces the development of a viable-but-non-culturable (VBNC state in C. jejuni. The findings in this study clearly demonstrated that oxidative stress resistance plays an important role in the survival and morphological changes of C. jejuni under aerobic conditions.

A model for the release of low-volatility fission products in oxidizing conditions

International Nuclear Information System (INIS)

Cox, D.S.; Hunt, C.E.L.; Liu, Z.; Keller, N.A.; Barrand, R.D.; O'Connor, R.F.

1991-07-01

A thermodynamic and kinetic model has been developed for calculating low-volatility fission-product releases from UO 2 at high temperatures in oxidizing conditions. Volatilization of the UO 2 matrix is assumed to be the rate controlling process. Oxidation kinetics of the UO 2 are modelled by either interfacial rate control, gas phase oxidant transport control, or solid-state diffusion of oxygen. The vapour pressure of UO 3 in equilibrium with the oxidizing fuel is calculated from thermodynamic data, and volatilization rates are determined using a model for forced convective mass transport. Low-volatility fission-product releases are calculated from the volume of vapourized fuel. Model calculations are conservative compared to experimental data for Zr, La, Ce and Nb fission-product releases from irradiated UO 2 exposed to air at 1973-2350 K. The implications of this conservatism are discussed in terms of possible rate control by processes other than convective mass transport of UO 3 . Coefficients for effective surface area (based on experimental data) and for heterogeneous rate controlling reaction kinetics are introduced to facilitate agreement between calculations and the experimental data.

Monomeric adiponectin modulates nitric oxide release and calcium movements in porcine aortic endothelial cells in normal/high glucose conditions.

Science.gov (United States)

Grossini, Elena; Farruggio, Serena; Qoqaiche, Fatima; Raina, Giulia; Camillo, Lara; Sigaudo, Lorenzo; Mary, David; Surico, Nicola; Surico, Daniela

2016-09-15

Perivascular adipose tissue can be involved in the process of cardiovascular pathology through the release of adipokines, namely adiponectins. Monomeric adiponectin has been shown to increase coronary blood flow in anesthetized pigs through increased nitric oxide (NO) release and the involvement of adiponectin receptor 1 (AdipoR1). The present study was therefore planned to examine the effects of monomeric adiponectin on NO release and Ca(2+) transients in porcine aortic endothelial cells (PAEs) in normal/high glucose conditions and the related mechanisms. PAEs were treated with monomeric adiponectin alone or in the presence of intracellular kinases blocker, AdipoR1 and Ca(2+)-ATPase pump inhibitors. The role of Na(+)/Ca(2+) exchanger was examined in experiments performed in zero Na(+) medium. NO release and intracellular Ca(2+) were measured through specific probes. In PAE cultured in normal glucose conditions, monomeric adiponectin elevated NO production and [Ca(2+)]c. Similar effects were observed in high glucose conditions, although the response was lower and not transient. The Ca(2+) mobilized by monomeric adiponectin originated from an intracellular pool thapsigargin- and ATP-sensitive and from the extracellular space. Moreover, the effects of monomeric adiponectin were prevented by kinase blockers and AdipoR1 inhibitor. Finally, in normal glucose condition, a role for Na(+)/Ca(2+) exchanger and Ca(2+)-ATPase pump in restoring Ca(2+) was found. Our results add new information about the control of endothelial function elicited by monomeric adiponectin, which would be achieved by modulation of NO release and Ca(2+) transients. A signalling related to Akt, ERK1/2 and p38MAPK downstream AdipoR1 would be involved. Copyright © 2016 Elsevier Inc. All rights reserved.

Short review of high-pressure crystal growth and magnetic and electrical properties of solid-state osmium oxides

Energy Technology Data Exchange (ETDEWEB)

Yamaura, Kazunari, E-mail: YAMAURA.Kazunari@nims.go.jp [Superconducting Properties Unit, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); Graduate School of Chemical Sciences and Engineering, Hokkaido University, North 10 West 8, Kita-ku, Sapporo, Hokkaido 060-0810 (Japan)

2016-04-15

High-pressure crystal growth and synthesis of selected solid-state osmium oxides, many of which are perovskite-related types, are briefly reviewed, and their magnetic and electrical properties are introduced. Crystals of the osmium oxides, including NaOsO{sub 3}, LiOsO{sub 3}, and Na{sub 2}OsO{sub 4}, were successfully grown under high-pressure and high-temperature conditions at 6 GPa in the presence of an appropriate amount of flux in a belt-type apparatus. The unexpected discovery of a magnetic metal–insulator transition in NaOsO{sub 3}, a ferroelectric-like transition in LiOsO{sub 3}, and high-temperature ferrimagnetism driven by a local structural distortion in Ca{sub 2}FeOsO{sub 6} may represent unique features of the osmium oxides. The high-pressure and high-temperature synthesis and crystal growth has played a central role in the development of solid-state osmium oxides and the elucidation of their magnetic and electronic properties toward possible use in multifunctional devices. - Graphical Abstract: Flux-grown crystals of NaOsO{sub 3} under high-pressure and high-temperature conditions in a belt-type apparatus. The crystal shows a magnetically driven metal–insulator transition at a temperature of 410 K. - Highlights: • Short review of high-pressure crystal growth of solid-state osmium oxides. • Wide variety of magnetic properties of solid-state osmium oxides. • Perovskite and related dense structures stabilized at 3–17 GPa.

Characterization of noble metals deposits and oxides in conditions of BWR reactors

International Nuclear Information System (INIS)

Arganis J, C.R.; Aguilar T, J.A.; Contreras R, A.

2008-01-01

The oxides deposited on steel 304l under normal chemistry conditions (NWC) and hydrogen chemistry (HWC) with presence of Zn, being that the first ones present hexagonal oxides of Hematite and the second bipyramidal crystals possibly Magnetite with traces of Zn. Deposits of Pt on the oxidized surfaces under NWC conditions were obtained, being glasses from 2 to 4 μm and Pt-Rh deposits were obtained on the oxidized surfaces in presence of Zn, by its size its were not possible to observe them by scanning electron microscopy. The kinetics of the surfaces of Hematite and of the deposits of Pt it was measured by means of the Tafel extrapolation technique, being proven the catalytic effect of the Pt, even in sizes of 11 μm. (Author)

Oxidative stress and the high altitude environment

Directory of Open Access Journals (Sweden)

Jakub Krzeszowiak

2013-03-01

Full Text Available In the recent years there has been considerable interest in mountain sports, including mountaineering, owing to the general availability of climbing clothing and equipment as well trainings and professional literature. This raised a new question for the environmental and mountain medicine: Is mountaineering harmful to health? Potential hazards include the conditions existing in the alpine environment, i.e. lower atmospheric pressure leading to the development of hypobaric hypoxia, extreme physical effort, increased UV radiation, lack of access to fresh food, and mental stress. A reasonable measure of harmfulness of these factors is to determine the increase in the level of oxidative stress. Alpine environment can stimulate the antioxidant enzyme system but under specific circumstances it may exceed its capabilities with simultaneous consumption of low-molecular antioxidants resulting in increased generation of reactive oxygen species (ROS. This situation is referred to as oxidative stress. Rapid and uncontrolled proliferation of reactive oxygen species leads to a number of adverse changes, resulting in the above-average damage to the lipid structures of cell membranes (peroxidation, proteins (denaturation, and nucleic acids. Such situation within the human body cannot take place without resultant systemic consequences. This explains the malaise of people returning from high altitude and a marked decrease in their physical fitness. In addition, a theory is put forward that the increase in the level of oxidative stress is one of the factors responsible for the onset of acute mountain sickness (AMS. However, such statement requires further investigation because the currently available literature is inconclusive. This article presents the causes and effects of development of oxidative stress in the high mountains.

Effect of thermal treatment conditions on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid

International Nuclear Information System (INIS)

Gorshkova, T.P.; Tarasova, D.V.; Olen'kova, I.P.; Andrushkevich, T.V.; Nikoro, T.A.

1984-01-01

The effect of thermal treatment conditions (temperature and gas medium) on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid is investigated. It is shown that active and selective catalysts are formed in the course of thermal decomposition of the drying product of ammonium metavanadate and paramolybdate under the conditions ensuring the vanadium ion reduction up to tetravalent state with conservation of molybdenum oxidation degree equal to 6. It is possible to realize it either by treatment of the catalyst calcinated in the air flow at 300 deg by the reaction mixture at the activation stage or by gas-reducer flow treatment at 280 deg. Thermal treatment in the reducing medium of the oxidized catalyst does not lead to complete regeneration of its properties

Study of the oxidation of Fe-Cr alloys at high temperatures

International Nuclear Information System (INIS)

Carneiro, J.F.; Sabioni, A.C.S.

2010-01-01

The high temperature oxidation behavior of Fe-1.5%Cr, Fe-5.0%Cr, Fe-10%Cr and Fe- 15%Cr model alloys were investigated from 700 to 850 deg C, in air atmosphere. The oxidation treatments were performed in a thermobalance with a sensitivity of 1μg. The oxide films grown by oxidation of the alloys were characterized by scanning electronic microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). The oxide films are Fe-Cr spinels with variable composition depending on the alloy composition. For all conditions studied, the oxidation kinetics of these alloys follow a parabolic law. The comparison of the oxidation rates of the four alloys, at 700 deg C, shows that the parabolic oxidation constants decrease from 1.96x10 -9 g 2 .cm -4 .s -1 , for the alloy Fe-1.5% Cr, to 1.18 x 10-14g 2 .cm -4 .s -1 for the alloy Fe-15% Cr. Comparative analysis of the oxidation behavior of the Fe-10%Cr and Fe-15%Cr alloys, between 700 and 850 deg C, shows that the oxidation rates of these alloys are comparable to 800 deg C, above this temperature the Fe-10%Cr alloy shows lower resistance to oxidation. (author)

Behavior of an improved Zr fuel cladding with oxidation resistant coating under loss-of-coolant accident conditions

Energy Technology Data Exchange (ETDEWEB)

Park, Dong Jun, E-mail: pdj@kaeri.re.kr; Kim, Hyun Gil; Jung, Yang Il; Park, Jung Hwan; Yang, Jae Ho; Koo, Yang Hyun

2016-12-15

This study investigates protective coatings for improving the high temperature oxidation resistance of Zr fuel claddings for light water nuclear reactors. FeCrAl alloy and Cr layers were deposited onto Zr plates and tubes using cold spraying. For the FeCrAl/Zr system, a Mo layer was introduced between the FeCrAl coating and the Zr matrix to prevent inter-diffusion at high temperatures. Both the FeCrAl and Cr coatings improved the oxidation resistance compared to that of the uncoated Zr alloy when exposed to a steam environment at 1200 °C. The ballooning behavior and mechanical properties of the coated cladding samples were studied under simulated loss-of-coolant accident conditions. The coated samples showed higher burst temperatures, lower circumferential strain, and smaller rupture openings compared to the uncoated Zr. Although 4-point bend tests of the coated samples showed a small increase in the maximum load, ring compression tests of a sectioned sample showed increased ductility. - Highlights: • Cr and FeCrAl were coated onto Zr fuel cladding for light water nuclear reactors. • Mo layer between FeCrAl and Zr prevented inter-diffusion at high temperatures. • Coated claddings were tested under loss-of-cooling accident conditions. • Coating improved high-temperature oxidation resistance and mechanical properties.

Investigation of the oxidation behavior of dispersion stabilized alloys when exposed to a dynamic high temperature environment

Science.gov (United States)

Tenney, D. R.

1974-01-01

The oxidation behavior of TD-NiCr and TD-NiCrAlY alloys have been studied at 2000 and 2200 F in static and high speed flowing air environments. The TD-NiCrAlY alloys preoxidized to produce an Al2O3 scale on the surface showed good oxidation resistance in both types of environments. The TD-NiCr alloy which had a Cr2O3 oxide scale after preoxidation was found to oxidize more than an order of magnitude faster under the dynamic test conditions than at comparable static test conditions. Although Cr2O3 normally provides good oxidation protection, it was rapidly lost due to formation of volatile CrO3 when exposed to the high speed air stream. The preferred oxide arrangement for the dynamic test consisted of an external layer of NiO with a porous mushroom type morphology, an intermediate duplex layer of NiO and Cr2O3, and a continuous inner layer of Cr2O3 in contact with the alloy substrate. An oxidation model has been developed to explain the observed microstructure and overall oxidation behavior of all alloys.

Influence of microorganisms on the oxidation state distribution of multivalent actinides under anoxic conditions

International Nuclear Information System (INIS)

Reed, Donald Timothy; Borkowski, Marian; Lucchini, Jean-Francois; Ams, David; Richmann, M.K.; Khaing, H.; Swanson, J.S.

2010-01-01

The fate and potential mobility of multivalent actinides in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium, uranium and neptunium are the near-surface multivalent contaminants of concern and are also key contaminants for the deep geologic disposal of nuclear waste. Their mobility is highly dependent on their redox distribution at their contamination source as well as along their potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity. Under anoxic conditions, indirect and direct bioreduction mechanisms exist that promote the prevalence of lower-valent species for multivalent actinides. Oxidation-state-specific biosorption is also an important consideration for long-term migration and can influence oxidation state distribution. Results of ongoing studies to explore and establish the oxidation-state specific interactions of soil bacteria (metal reducers and sulfate reducers) as well as halo-tolerant bacteria and Archaea for uranium, neptunium and plutonium will be presented. Enzymatic reduction is a key process in the bioreduction of plutonium and uranium, but co-enzymatic processes predominate in neptunium systems. Strong sorptive interactions can occur for most actinide oxidation states but are likely a factor in the stabilization of lower-valent species when more than one oxidation state can persist under anaerobic microbiologically-active conditions. These results for microbiologically active systems are interpreted in the context of their overall importance in defining the potential migration of multivalent actinides in the subsurface.

Nb effect on Zr-alloy oxidation under high pressure steam at high temperatures

International Nuclear Information System (INIS)

Park, Kwangheon; Yang, Sungwoo; Kim, Kyutae

2005-01-01

The high-pressure steam effects on the oxidation of Zircaloy-4 (Zry-4) and Zirlo (Zry-1%Nb) claddings at high temperature have been analyzed. Test temperature range was 700-900degC, and pressures were 1-150 bars. High pressure-steam enhances oxidation of Zry-4, and the dependency of enhancement looks exponential to steam pressure. The origin of the oxidation enhancement turned out to be the formation of cracks in oxide. The loss of tetragonal phase by high-pressure steam seems related to the crack formation. Addition of Nb as an alloying element to Zr alloy reduces significantly the steam pressure effects on oxidation. The higher compressive stresses and the smaller fraction of tetragonal oxides in Zry-1%Nb seem to be the diminished effect of high-pressure steam on oxidation. (author)

Biological iron oxidation by Gallionella spp. in drinking water production under fully aerated conditions.

Science.gov (United States)

de Vet, W W J M; Dinkla, I J T; Rietveld, L C; van Loosdrecht, M C M

2011-11-01

Iron oxidation under neutral conditions (pH 6.5-8) may be a homo- or heterogeneous chemically- or a biologically-mediated process. The chemical oxidation is supposed to outpace the biological process under slightly alkaline conditions (pH 7-8). The iron oxidation kinetics and growth of Gallionella spp. - obligatory chemolithotrophic iron oxidizers - were assessed in natural, organic carbon-containing water, in continuous lab-scale reactors and full-scale groundwater trickling filters in the Netherlands. From Gallionella cell numbers determined by qPCR, balances were made for all systems. The homogeneous chemical iron oxidation occurred in accordance with the literature, but was retarded by a low water temperature (13 °C). The contribution of the heterogeneous chemical oxidation was, despite the presence of freshly formed iron oxyhydroxides, much lower than in previous studies in ultrapure water. This could be caused by the adsorption of natural organic matter (NOM) on the iron oxide surfaces. In the oxygen-saturated natural water with a pH ranging from 6.5 to 7.7, Gallionella spp. grew uninhibited and biological iron oxidation was an important, and probably the dominant, process. Gallionella growth was not even inhibited in a full-scale filter after plate aeration. From this we conclude that Gallionella spp. can grow under neutral pH and fully aerated conditions when the chemical iron oxidation is retarded by low water temperature and inhibition of the autocatalytic iron oxidation. Copyright © 2011 Elsevier Ltd. All rights reserved.

High glucose alters retinal astrocytes phenotype through increased production of inflammatory cytokines and oxidative stress.

Directory of Open Access Journals (Sweden)

Eui Seok Shin

Full Text Available Astrocytes are macroglial cells that have a crucial role in development of the retinal vasculature and maintenance of the blood-retina-barrier (BRB. Diabetes affects the physiology and function of retinal vascular cells including astrocytes (AC leading to breakdown of BRB. However, the detailed cellular mechanisms leading to retinal AC dysfunction under high glucose conditions remain unclear. Here we show that high glucose conditions did not induce the apoptosis of retinal AC, but instead increased their rate of DNA synthesis and adhesion to extracellular matrix proteins. These alterations were associated with changes in intracellular signaling pathways involved in cell survival, migration and proliferation. High glucose conditions also affected the expression of inflammatory cytokines in retinal AC, activated NF-κB, and prevented their network formation on Matrigel. In addition, we showed that the attenuation of retinal AC migration under high glucose conditions, and capillary morphogenesis of retinal endothelial cells on Matrigel, was mediated through increased oxidative stress. Antioxidant proteins including heme oxygenase-1 and peroxiredoxin-2 levels were also increased in retinal AC under high glucose conditions through nuclear localization of transcription factor nuclear factor-erythroid 2-related factor-2. Together our results demonstrated that high glucose conditions alter the function of retinal AC by increased production of inflammatory cytokines and oxidative stress with significant impact on their proliferation, adhesion, and migration.

High pressure oxidation of C2H4/NO mixtures

DEFF Research Database (Denmark)

Giménez-López, J.; Alzueta, M.U.; Rasmussen, C.T.

2011-01-01

An experimental and kinetic modeling study of the interaction between C2H4 and NO has been performed under flow reactor conditions in the intermediate temperature range (600–900K), high pressure (60bar), and for stoichiometries ranging from reducing to oxidizing conditions. The main reaction...... pathways of the C2H4/O2/NOx conversion, the capacity of C2H4 to remove NO, and the influence of the presence of NOx on the C2H4 oxidation are analyzed. Compared to the C2H4/O2 system, the presence of NOx shifts the onset of reaction 75–150K to lower temperatures. The mechanism of sensitization involves...... the reaction HOCH2CH2OO+NO→CH2OH+CH2O+NO2, which pushes a complex system of partial equilibria towards products. This is a confirmation of the findings of Doughty et al. [3] for a similar system at atmospheric pressure. Under reducing conditions and temperatures above 700K, a significant fraction of the NOx...

Environmental conditions can modulate the links among oxidative stress, age, and longevity.

Science.gov (United States)

Marasco, Valeria; Stier, Antoine; Boner, Winnie; Griffiths, Kate; Heidinger, Britt; Monaghan, Pat

2017-06-01

Understanding the links between environmental conditions and longevity remains a major focus in biological research. We examined within-individual changes between early- and mid-adulthood in the circulating levels of four oxidative stress markers linked to ageing, using zebra finches (Taeniopygia guttata): a DNA damage product (8-hydroxy-2'-deoxyguanosine; 8-OHdG), protein carbonyls (PC), non-enzymatic antioxidant capacity (OXY), and superoxide dismutase activity (SOD). We further examined whether such within-individual changes differed among birds living under control (ad lib food) or more challenging environmental conditions (unpredictable food availability), having previously found that the latter increased corticosterone levels when food was absent but improved survival over a three year period. Our key findings were: (i) 8-OHdG and PC increased with age in both environments, with a higher increase in 8-OHdG in the challenging environment; (ii) SOD increased with age in the controls but not in the challenged birds, while the opposite was true for OXY; (iii) control birds with high levels of 8-OHdG died at a younger age, but this was not the case in challenged birds. Our data clearly show that while exposure to the potentially damaging effects of oxidative stress increases with age, environmental conditions can modulate the pace of this age-related change. Copyright © 2017 Elsevier B.V. All rights reserved.

Contribution to the identification of the processes kinetically limiting of the zirconium alloys oxidation; characterization of the oxide films formed at high temperature by solids electrochemistry

International Nuclear Information System (INIS)

Vermoyal, J.J.

2000-06-01

The corrosion behavior of zirconium alloys used for cladding tubes has been extensively studied under several oxidation conditions (temperature, steam, dry air, oxygen...) in order to clarify the mechanism(s) of oxide growth and breakdown. Oxidation rate is generally assumed to be controlled by oxygen diffusion inwards the oxide layer. Nevertheless, several experimental facts, such as acceleration or inhibition of corrosion rate in coupling conditions, suggest that electrochemical processes are involved as a rate determining step. This work is an attempt to shed light about the rate-limiting-mechanism of two zirconium alloys oxidation: Zircaloy-4 (Zy-4) and Zr-Nb(1%)O(0,13%). Impedance spectroscopy characterizations of oxide films formed in high temperature water and studied in gaseous atmosphere clearly show the difference of electrical properties between the two alloys. The in situ electrochemical and thermogravimetric investigations in gaseous medium, and the polarization effects on oxidation and hydridation of Zr alloys in PWRs conditions indicate that oxygen diffusion can be considered as the limiting kinetic step for Zy-4 oxidation. On the contrary, the acceleration of oxide growth on Zr-Nb(1%)O(0,13%) under anodic polarization in PWRs conditions (360 deg C) suggests that either the electronic conductivity in the oxide or an interfacial process at least partially control the oxidation rate. Catalytic effects observed in gaseous medium when noble metals increase the oxygen reduction rate would tend to corroborate the oxidation control of this alloy by an interfacial mechanism. An electrochemical description and a heterogeneous kinetics approach based on a diffusion-interfacial process as rate determining step are then proposed. (author)

Microstructure and High Temperature Oxidation Property of Fe-Cr-B Based Metal/Ceramic Composite Manufactured by Powder Injection Molding Process

Science.gov (United States)

Joo, Yeun-Ah; Kim, Young-Kyun; Yoon, Tae-Sik; Lee, Kee-Ahn

2018-03-01

This study investigated the microstructure and high temperature oxidation property of Fe-Cr-B metal/ceramic composite manufactured using powder injection molding process. Observations of initial microstructure showed a unique structure where α-Fe and (Cr, Fe)2B form a continuous three-dimensional network. High temperature oxidation tests were performed at 900, 1000 and 1100 °C, for 24 h, and the oxidation weight gain according to each temperature condition was 0.13, 0.84 and 6.4 mg/cm2, respectively. The oxidation results according to time at 900 and 1000 °C conditions represented parabolic curves, and at 1100 °C condition formed a rectilinear curve. Observation and phase analysis results of the oxides identified Cr2O3 and SiO2 at 900 and 1000 °C. In addition to Cr2O3 and SiO2, CrBO3 and FeCr2O4 formed due to phase decomposition of boride were identified at 1100 °C. Based on the findings above, this study suggested the high temperature oxidation mechanism of Fe-Cr-B metal/ceramic composite manufactured using powder injection molding, and the possibility of its application as a high temperature component material was also discussed.

Modelling of Zircaloy-steam-oxidation under severe fuel damage conditions

International Nuclear Information System (INIS)

Malang, S.; Neitzel, H.J.

1983-01-01

Small break loss-of-coolant accidents and special transients in an LWR, in combination with loss of required safety systems, may lead to an uncovered core for an extended period of time. As a consequence, the cladding temperature could rise up to the melting point due to the decay heat, resulting in severely damaged fuel rods. During heat-up the claddings oxidize due to oxygen uptake from the steam atmosphere in the core. The modeling and assessment of the Zircaloy-steam oxidation under such conditions is important, mainly for two reasons: The oxidation of the cladding influences the temperature transients due to the exothermic heat of reaction; the amount of liquified fuel depends on the oxide layer thickness and the oxygen content of the remaining Zircaloy metal when the melting point is reached. (author)

High temperature oxidation behavior of ODS steels

Science.gov (United States)

Kaito, T.; Narita, T.; Ukai, S.; Matsuda, Y.

2004-08-01

Oxide dispersion strengthened (ODS) steels are being developing for application as advanced fast reactor cladding and fusion blanket materials, in order to allow increased operation temperature. Oxidation testing of ODS steel was conducted under a controlled dry air atmosphere to evaluate the high temperature oxidation behavior. This showed that 9Cr-ODS martensitic steels and 12Cr-ODS ferritic steels have superior high temperature oxidation resistance compared to 11 mass% Cr PNC-FMS and 17 mass% Cr ferritic stainless steel. This high temperature resistance is attributed to earlier formation of the protective α-Cr 2O 3 on the outer surface of ODS steels.

Highly Conductive One-Dimensional Manganese Oxide Wires by Coating with Graphene Oxides

Science.gov (United States)

Tojo, Tomohiro; Shinohara, Masaki; Fujisawa, Kazunori; Muramatsu, Hiroyuki; Hayashi, Takuya; Ahm Kim, Yoong; Endo, Morinobu

2012-10-01

Through coating with graphene oxides, we have developed a chemical route to the bulk production of long, thin manganese oxide (MnO2) nanowires that have high electrical conductivity. The average diameter of these hybrid nanowires is about 25 nm, and their average length is about 800 nm. The high electrical conductivity of these nanowires (ca. 189.51+/-4.51 µS) is ascribed to the homogeneous coating with conductive graphene oxides as well as the presence of non-bonding manganese atoms. The growth mechanism of the nanowires is theoretically supported by the initiation of morphological conversion from graphene oxide to wrapped structures through the formation of covalent bonds between manganese and oxygen atoms at the graphene oxide edge.

Sex-specific effects of prenatal and postnatal nutritional conditions on the oxidative status of great tit nestlings.

Science.gov (United States)

Giordano, M; Costantini, D; Tschirren, B

2015-01-01

The early life period is characterized by fast growth and development, which can lead to high reactive oxygen species (ROS) production. Young animals thus have to balance their investment in growth versus ROS defence, and this balance is likely mediated by resource availability. Consequently resources transferred prenatally by the mother and nutritional conditions experienced shortly after birth may crucially determine the oxidative status of young animals. Here, we experimentally investigated the relative importance of pre- and early postnatal nutritional conditions on the oxidative status of great tit nestlings (Parus major). We show that resources transferred by the mother through the egg and nutritional conditions encountered after hatching affect the oxidative status of nestling in a sex-specific way. Daughters of non-supplemented mothers and daughters which did not receive extra food during the early postnatal period had higher oxidative damage than sons, while no differences between sons and daughters were found when extra food was provided pre- or postnatally. No effect of the food supplementations on growth, fledging mass or tarsus length was observed, indicating that female nestlings maintained their investment in growth at the expense of ROS defence mechanisms when resources were limited. The lower priority of the antioxidant defence system for female nestlings was also evidenced by lower levels of specific antioxidant components. These results highlight the important role of early parental effects in shaping oxidative stress in the offspring, and show that the sensitivity to these parental effects is sex-specific.

First-principles study on oxidation effects in uranium oxides and high-pressure high-temperature behavior of point defects in uranium dioxide

Science.gov (United States)

Geng, Hua Y.; Song, Hong X.; Jin, K.; Xiang, S. K.; Wu, Q.

2011-11-01

Formation Gibbs free energy of point defects and oxygen clusters in uranium dioxide at high-pressure high-temperature conditions are calculated from first principles, using the LSDA+U approach for the electronic structure and the Debye model for the lattice vibrations. The phonon contribution on Frenkel pairs is found to be notable, whereas it is negligible for the Schottky defect. Hydrostatic compression changes the formation energies drastically, making defect concentrations depend more sensitively on pressure. Calculations show that, if no oxygen clusters are considered, uranium vacancy becomes predominant in overstoichiometric UO2 with the aid of the contribution from lattice vibrations, while compression favors oxygen defects and suppresses uranium vacancy greatly. At ambient pressure, however, the experimental observation of predominant oxygen defects in this regime can be reproduced only in a form of cuboctahedral clusters, underlining the importance of defect clustering in UO2+x. Making use of the point defect model, an equation of state for nonstoichiometric oxides is established, which is then applied to describe the shock Hugoniot of UO2+x. Furthermore, the oxidization and compression behavior of uranium monoxide, triuranium octoxide, uranium trioxide, and a series of defective UO2 at 0 K are investigated. The evolution of mechanical properties and electronic structures with an increase of the oxidation degree are analyzed, revealing the transition of the ground state of uranium oxides from metallic to Mott insulator and then to charge-transfer insulator due to the interplay of strongly correlated effects of 5f orbitals and the shift of electrons from uranium to oxygen atoms.

High-Temperature, Dual-Atmosphere Corrosion of Solid-Oxide Fuel Cell Interconnects

Science.gov (United States)

Gannon, Paul; Amendola, Roberta

2012-12-01

High-temperature corrosion of ferritic stainless steel (FSS) surfaces can be accelerated and anomalous when it is simultaneously subjected to different gaseous environments, e.g., when separating fuel (hydrogen) and oxidant (air) streams, in comparison with single-atmosphere exposures, e.g., air only. This so-called "dual-atmosphere" exposure is realized in many energy-conversion systems including turbines, boilers, gasifiers, heat exchangers, and particularly in intermediate temperature (600-800°C) planar solid-oxide fuel cell (SOFC) stacks. It is generally accepted that hydrogen transport through the FSS (plate or tube) and its subsequent integration into the growing air-side surface oxide layer can promote accelerated and anomalous corrosion—relative to single-atmosphere exposure—via defect chemistry changes, such as increased cation vacancy concentrations, decreased oxygen activity, and steam formation within the growing surface oxide layers. Establishment of a continuous and dense surface oxide layer on the fuel side of the FSS can inhibit hydrogen transport and the associated effects on the air side. Minor differences in FSS composition, microstructure, and surface conditions can all have dramatic influences on dual-atmosphere corrosion behaviors. This article reviews high-temperature, dual-atmosphere corrosion phenomena and discusses implications for SOFC stacks, related applications, and future research.

Oxidation behaviour of titanium in high temperature steam

International Nuclear Information System (INIS)

Moroishi, Taishi; Shida, Yoshiaki

1978-01-01

The oxidation of pure titanium was studied in superheated steam at 400 -- 550 0 C. The effects of prior cold working and several heat treatment conditions on the oxidation were examined and also the effects of the addition of small amounts of iron and oxygen were investigated. The oxidation mechanism of pure titanium is discussed in relation to the scale structure and the oxidation kinetics. Hydrogen absorption rate was also measured. As a result, the following conclusions were drawn: (1) The oxidation of pure titanium in steam was faster than in air and breakaway oxidation was observed above 500 0 C after the specimen had gained a certain weight. Prior cold working and heat treatment conditions scarcely affected the oxidation rate, whereas the specimen containing small amounts of iron and oxygen showed a little more rapid oxidation. (2) At 500 and 550 0 C a dark grey inner scale and a yellow-brown outer scale were formed. The outer scale was apt to exfoliate after the occurrence of breakaway oxidation. At 400 and 450 0 C only a dark grey scale was observed. All of these oxides were identified as the rutile type, TiO 2 . Furthermore, the presence of a thin and uniform oxygen rich layer beneath the external scale was confirmed at all test temperatures. (3) The measured weight gain approximately followed the cubic rate law; this would be expected for the following reason; one component of the weight gain is due to the dissolved oxygen, the amount of which remains constant after the early stages of oxidation. The second component is due to the parabolic growth of the external TiO 2 scale. When these contributions are added a pseudo-cubic weight gain curve results. (4) It was shown that 50 percent of the hydrogen generated during the oxidation was absorbed into the metal. (auth.)

High formation of secondary organic aerosol from the photo-oxidation of toluene

Directory of Open Access Journals (Sweden)

L. Hildebrandt

2009-05-01

Full Text Available Toluene and other aromatics have long been viewed as the dominant anthropogenic secondary organic aerosol (SOA precursors, but the SOA mass yields from toluene reported in previous studies vary widely. Experiments conducted in the Carnegie Mellon University environmental chamber to study SOA formation from the photo-oxidation of toluene show significantly larger SOA production than parameterizations employed in current air-quality models. Aerosol mass yields depend on experimental conditions: yields are higher under higher UV intensity, under low-NO_x conditions and at lower temperatures. The extent of oxidation of the aerosol also varies with experimental conditions, consistent with ongoing, progressive photochemical aging of the toluene SOA. Measurements using a thermodenuder system suggest that the aerosol formed under high- and low-NO_x conditions is semi-volatile. These results suggest that SOA formation from toluene depends strongly on ambient conditions. An approximate parameterization is proposed for use in air-quality models until a more thorough treatment accounting for the dynamic nature of this system becomes available.

Storage conditions affect oxidative stability and nutritional composition of freeze-dried Nannochloropsis salina

DEFF Research Database (Denmark)

Safafar, Hamed; Langvad, Sten; Møller, Peter

2017-01-01

composition of microalgae biomass. In order to investigate the worsening of the nutritional quality of freeze dried biomass, a multifactorial storage experiment was conducted on a high EPA (eicosapentaenoic acid) Nannochloropsis salina biomass. The storage time (0–56 days), storage temperature (5, 20,and 40...... °C and packaging conditions (under vacuum and ambient pressure)used as main factors. During the 56 days of storage, both time and temperature strongly influenced the oxidation reactions which result in deterioration of bioactive compounds such as carotenoids, tocopherols, and EPA. Lipid deterioration......, or cosmetics requires the knowledge of the optimum storage conditions to prevent the value-added compounds from deterioration. Results of this study improve our understanding of the chemical deterioration under different storage conditions and can help the producers/customers to extend the shelf life...

FoxO3a Serves as a Biomarker of Oxidative Stress in Human Lens Epithelial Cells under Conditions of Hyperglycemia.

Directory of Open Access Journals (Sweden)

Ilangovan Raju

Full Text Available Forkhead box 'O' transcription factors (FoxOs are implicated in the pathogenesis of type2 diabetes and other metabolic diseases. Abnormal activity of FoxOs was reported in the glucose and insulin metabolism. Expression of FoxO proteins was reported in ocular tissues; however their function under hyperglycemic conditions was not examined.Human lens epithelial cell line was used to study the function of FoxO proteins. Immunofluorescence, flow cytometry and Western blotting were employed to detect the FoxO proteins under the conditions of hyperglycemia.In this study we examined the role of FoxO3a in hyperglycemia-induced oxidative stress in human lens epithelial cells. FoxO3a protein expression was elevated in a dose- and time-dependent fashion after high glucose treatment. Anti-oxidant defense mechanisms of the lens epithelial cells were diminished as evidenced from loss of mitochondrial membrane integrity and lowered MnSOD after 72 h treatment with high glucose. Taken together, FoxO3a acts as a sensitive indicator of oxidative stress and cell homeostasis in human lens epithelial cells during diabetic conditions.FoxO3a is an early stress response protein to glucose toxicity in diabetic conditions.

Zirconium metal-water oxidation kinetics. V. Oxidation of Zircaloy in high pressure steam

International Nuclear Information System (INIS)

Pawel, R.E.; Cathcart, J.V.; Campbell, J.J.; Jury, S.H.

1977-12-01

A series of scoping tests to determine the influence of steam pressure on the isothermal oxidation kinetics of Zircaloy-4 PWR tubing was undertaken. The oxidation experiments were conducted in flowing steam at 3.45, 6.90, and 10.34 MPa (500, 1000, and 1500 psi) at 905 0 C (1661 0 F), and at 3.45 and 6.90 MPa at 1101 0 C (2014 0 F). A comparison of the results of these experiments with those obtained for oxidation in steam at atmospheric pressure under similar conditions indicated that measurable enhancement of the oxidation rate occurred with increasing pressure at 905 0 C, but not at 1100 0 C

In vivo oxidation in remelted highly cross-linked retrievals.

Science.gov (United States)

Currier, B H; Van Citters, D W; Currier, J H; Collier, J P

2010-10-20

Elimination of free radicals to prevent oxidation has played a major role in the development and product differentiation of the latest generation of highly cross-linked ultra-high molecular weight polyethylene bearing materials. In the current study, we (1) examined oxidation in a series of retrieved remelted highly cross-linked ultra-high molecular weight polyethylene bearings from a number of device manufacturers and (2) compared the retrieval results with findings for shelf-stored control specimens. The hypothesis was that radiation-cross-linked remelted ultra-high molecular weight polyethylene would maintain oxidative stability in vivo comparable with the stability during shelf storage and in published laboratory aging tests. Fifty remelted highly cross-linked ultra-high molecular weight polyethylene acetabular liners and nineteen remelted highly cross-linked ultra-high molecular weight polyethylene tibial inserts were received after retrieval from twenty-one surgeons from across the U.S. Thirty-two of the retrievals had been in vivo for two years or more. Each was measured for oxidation with use of Fourier transform infrared spectroscopy. A control series of remelted highly cross-linked ultra-high molecular weight polyethylene acetabular liners from three manufacturers was analyzed with electron paramagnetic resonance spectroscopy to measure free radical content and with Fourier transform infrared spectroscopy to measure oxidation initially and after eight to nine years of shelf storage in air. The never-implanted, shelf-aged controls had no measurable free-radical content initially or after eight to nine years of shelf storage. The never-implanted controls showed no increase in oxidation during shelf storage. Oxidation measurements showed measurable oxidation in 22% of the retrieved remelted highly cross-linked liners and inserts after an average of two years in vivo. Because never-implanted remelted highly cross-linked ultra-high molecular weight

A thermodynamic approach for selecting operating conditions in the design of reversible solid oxide cell energy systems

Science.gov (United States)

Wendel, Christopher H.; Kazempoor, Pejman; Braun, Robert J.

2016-01-01

Reversible solid oxide cell (ReSOC) systems are being increasingly considered for electrical energy storage, although much work remains before they can be realized, including cell materials development and system design optimization. These systems store electricity by generating a synthetic fuel in electrolysis mode and subsequently recover electricity by electrochemically oxidizing the stored fuel in fuel cell mode. System thermal management is improved by promoting methane synthesis internal to the ReSOC stack. Within this strategy, the cell-stack operating conditions are highly impactful on system performance and optimizing these parameters to suit both operating modes is critical to achieving high roundtrip efficiency. Preliminary analysis shows the thermoneutral voltage to be a useful parameter for analyzing ReSOC systems and the focus of this study is to quantitatively examine how it is affected by ReSOC operating conditions. The results reveal that the thermoneutral voltage is generally reduced by increased pressure, and reductions in temperature, fuel utilization, and hydrogen-to-carbon ratio. Based on the thermodynamic analysis, many different combinations of these operating conditions are expected to promote efficient energy storage. Pressurized systems can achieve high efficiency at higher temperature and fuel utilization, while non-pressurized systems may require lower stack temperature and suffer from reduced energy density.

Comprehensive Study of Lanthanum Aluminate High-Dielectric-Constant Gate Oxides for Advanced CMOS Devices

Directory of Open Access Journals (Sweden)

Masamichi Suzuki

2012-03-01

Full Text Available A comprehensive study of the electrical and physical characteristics of Lanthanum Aluminate (LaAlO3 high-dielectric-constant gate oxides for advanced CMOS devices was performed. The most distinctive feature of LaAlO3 as compared with Hf-based high-k materials is the thermal stability at the interface with Si, which suppresses the formation of a low-permittivity Si oxide interfacial layer. Careful selection of the film deposition conditions has enabled successful deposition of an LaAlO3 gate dielectric film with an equivalent oxide thickness (EOT of 0.31 nm. Direct contact with Si has been revealed to cause significant tensile strain to the Si in the interface region. The high stability of the effective work function with respect to the annealing conditions has been demonstrated through comparison with Hf-based dielectrics. It has also been shown that the effective work function can be tuned over a wide range by controlling the La/(La + Al atomic ratio. In addition, gate-first n-MOSFETs with ultrathin EOT that use sulfur-implanted Schottky source/drain technology have been fabricated using a low-temperature process.

Studies of high coverage oxidation of the Cu(100) surface using low energy positrons

Science.gov (United States)

Fazleev, N. G.; Maddox, W. B.; Weiss, A. H.

2012-02-01

The study of oxidation of single crystal metal surfaces is important in understanding the corrosive and catalytic processes associated with thin film metal oxides. The structures formed on oxidized transition metal surfaces vary from simple adlayers of chemisorbed oxygen to more complex structures which result from the diffusion of oxygen into subsurface regions. In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Calculations are performed for various high coverage missing row structures ranging between 0.50 and 1.50 ML oxygen coverage. The results of calculations of positron binding energy, positron work function, and annihilation characteristics of surface trapped positrons with relevant core electrons as function of oxygen coverage are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES).

Effect of decontamination on oxidation of austenitic stainless steel in reactor conditions

International Nuclear Information System (INIS)

Starkman, T.

1984-07-01

Austenitic stainless steels were oxidized in static autoclaves in light water reactor conditions. After the autoclave treatments the specimens were decontaminated with the aid of alkaline potassium permanganate (AP) and oxalic and citric acid (CITROX) as well as electrochemically in H 3 PO 4 . Alternating oxidation and decontamination tests were performed. An elemental analysis of the surfaces of the specimens was carried out by electron spectroscopy. Changes in structures and thicknesses of the oxide layers were observed. (author)

High pressure Moessbauer spectroscopy of perovskite iron oxide

International Nuclear Information System (INIS)

Nasu, Saburo; Suenaga, Tomoya; Morimoto, Shotaro; Kawakami, Takateru; Kuzushita, Kaori; Takano, Mikio

2003-01-01

High-pressure 57 Fe Moessbauer spectroscopy using a diamond anvil cell has been performed for perovskite iron oxides SrFeO 3 , CaFeO 3 and La 1/3 Sr 2/3 O 3 . The charge states and the magnetic dependency to pressure were determined. Pressure magnetic phase diagrams of these perovskite iron oxides are determined up to about 70 GPa. To be clear the magnetic ordered state, they are measured up to 7.8 T external magnetic fields at 4.5K. The phase transition of these perovskite oxides to ferromagnetisms with high magnetic ordered temperature is observed. In higher pressure, high spin-low spin transition of oxides besides CaFeO 3 is generated. The feature of Moessbauer spectroscopy, perovskite iron oxide and Moessbauer spectroscopy under high pressure are explained. (S.Y.)

Measurement of oxide-layer thickness of internal granules in high-purity aluminium

International Nuclear Information System (INIS)

Takacs, S.; Ditroi, F.; Mahunka, I.

1989-01-01

Charged-particle activation analysis was used for the determination of bulk oxygen concentration in aluminium. High-purity aluminium samples and mixtures containing different amounts of alumina were irradiated by 13 MeV 3 He particles. The aim of the investigation was to determine the oxide-layer thickness on the surface of internal aluminium granules. The measurement was carried out by determining the bulk oxygen concentration in the samples, and calculating the oxide-layer thickness, by using model conditions about the microstructure of the aluminium samples. (author) 5 refs

Development of Ultra-high Purity (UHP) Fe-Based Alloys with High Creep and Oxidation Resistance for A-USC Technology

Science.gov (United States)

Hamdani, Fethi; Das, Nishith K.; Shoji, Tetsuo

2018-06-01

The design of ultra-high purity (UHP) Fe-based model alloys for advanced ultra-supercritical (A-USC) technology is attempted in this work. Creep testing has been performed in air at 700 °C and a stress level of 150 MPa. Analysis of the fracture surface and cross section of the crept specimen was performed. To evaluate the oxidation resistance in A-USC conditions, oxidation testing was performed in supercritical water (SCW) at 700 °C and 25 MPa. Weight gain (WG) measurements and meticulous characterization of the oxide scale were carried out. Based on thermodynamics and density functional theory calculations, some reactive elements in the Fe-Cr-Ni system were designated to promote precipitation strengthening and to improve the hydrogen-accelerated oxidation resistance. The addition of a 2 wt pct Mo into Fe-22Cr-22Ni-0.6Nb wt pct-based matrix did not significantly improve the creep resistance. The addition of 0.26 wt pct Zr coupled with cold working was effective for improving creep properties. The Mo-modified model alloy showed almost the same WG value as SUS310, while the Zr-modified alloy showed a higher WG value. Meanwhile, a Cr-enriched continuous oxide layer was formed at the oxidation front of the Zr-modified alloy and SUS310S after exposure to SCW conditions.

Development of Ultra-high Purity (UHP) Fe-Based Alloys with High Creep and Oxidation Resistance for A-USC Technology

Science.gov (United States)

Hamdani, Fethi; Das, Nishith K.; Shoji, Tetsuo

2018-03-01

The design of ultra-high purity (UHP) Fe-based model alloys for advanced ultra-supercritical (A-USC) technology is attempted in this work. Creep testing has been performed in air at 700 °C and a stress level of 150 MPa. Analysis of the fracture surface and cross section of the crept specimen was performed. To evaluate the oxidation resistance in A-USC conditions, oxidation testing was performed in supercritical water (SCW) at 700 °C and 25 MPa. Weight gain (WG) measurements and meticulous characterization of the oxide scale were carried out. Based on thermodynamics and density functional theory calculations, some reactive elements in the Fe-Cr-Ni system were designated to promote precipitation strengthening and to improve the hydrogen-accelerated oxidation resistance. The addition of a 2 wt pct Mo into Fe-22Cr-22Ni-0.6Nb wt pct-based matrix did not significantly improve the creep resistance. The addition of 0.26 wt pct Zr coupled with cold working was effective for improving creep properties. The Mo-modified model alloy showed almost the same WG value as SUS310, while the Zr-modified alloy showed a higher WG value. Meanwhile, a Cr-enriched continuous oxide layer was formed at the oxidation front of the Zr-modified alloy and SUS310S after exposure to SCW conditions.

Oxidation behaviour of titanium in high temperature steam

Energy Technology Data Exchange (ETDEWEB)

Moroishi, T; Shida, Y [Sumitomo Metal Industries Ltd., Amagasaki, Hyogo (Japan). Central Research Labs.

1978-03-01

The oxidation of pure titanium was studied in superheated steam at 400 -- 550/sup 0/C. The effects of prior cold working and several heat treatment conditions on the oxidation were examined and also the effects of the addition of small amounts of iron and oxygen were investigated. The oxidation mechanism of pure titanium is discussed in relation to the scale structure and the oxidation kinetics. Hydrogen absorption rate was also measured. As a result, the following conclusions were drawn: (1) The oxidation of pure titanium in steam was faster than in air and breakaway oxidation was observed above 500/sup 0/C after the specimen had gained a certain weight. Prior cold working and heat treatment conditions scarcely affected the oxidation rate, whereas the specimen containing small amounts of iron and oxygen showed a little more rapid oxidation. (2) At 500 and 550/sup 0/C a dark grey inner scale and a yellow-brown outer scale were formed. The outer scale was apt to exfoliate after the occurrence of breakaway oxidation. At 400 and 450/sup 0/C only a dark grey scale was observed. All of these oxides were identified as the rutile type, TiO/sub 2/. Furthermore, the presence of a thin and uniform oxygen rich layer beneath the external scale was confirmed at all test temperatures. (3) The measured weight gain approximately followed the cubic rate law; this would be expected for the following reason; one component of the weight gain is due to the dissolved oxygen, the amount of which remains constant after the early stages of oxidation. The second component is due to the parabolic growth of the external TiO/sub 2/ scale. When these contributions are added a pseudo-cubic weight gain curve results. (4) It was shown that 50 percent of the hydrogen generated during the oxidation was absorbed into the metal.

High rate flame synthesis of highly crystalline iron oxide nanorods

International Nuclear Information System (INIS)

Merchan-Merchan, W; Taylor, A M; Saveliev, A V

2008-01-01

Single-step flame synthesis of iron oxide nanorods is performed using iron probes inserted into an opposed-flow methane oxy-flame. The high temperature reacting environment of the flame tends to convert elemental iron into a high density layer of iron oxide nanorods. The diameters of the iron oxide nanorods vary from 10 to 100 nm with a typical length of a few microns. The structural characterization performed shows that nanorods possess a highly ordered crystalline structure with parameters corresponding to cubic magnetite (Fe 3 O 4 ) with the [100] direction oriented along the nanorod axis. Structural variations of straight nanorods such as bends, and T-branched and Y-branched shapes are frequently observed within the nanomaterials formed, opening pathways for synthesis of multidimensional, interconnected networks

Osteocalcin protects pancreatic beta cell function and survival under high glucose conditions

Energy Technology Data Exchange (ETDEWEB)

Kover, Karen, E-mail: kkover@cmh.edu [Division of Endocrine/Diabetes, Children' s Mercy Hospital & Clinics, Kansas City, MO 64108 (United States); University of Missouri-Kansas City School of Medicine, Kansas City, MO 64108 (United States); Yan, Yun; Tong, Pei Ying; Watkins, Dara; Li, Xiaoyu [Division of Endocrine/Diabetes, Children' s Mercy Hospital & Clinics, Kansas City, MO 64108 (United States); University of Missouri-Kansas City School of Medicine, Kansas City, MO 64108 (United States); Tasch, James; Hager, Melissa [Kansas City University Medical Biosciences, Kansas City, MO (United States); Clements, Mark; Moore, Wayne V. [Division of Endocrine/Diabetes, Children' s Mercy Hospital & Clinics, Kansas City, MO 64108 (United States); University of Missouri-Kansas City School of Medicine, Kansas City, MO 64108 (United States)

2015-06-19

Diabetes is characterized by progressive beta cell dysfunction and loss due in part to oxidative stress that occurs from gluco/lipotoxicity. Treatments that directly protect beta cell function and survival in the diabetic milieu are of particular interest. A growing body of evidence suggests that osteocalcin, an abundant non-collagenous protein of bone, supports beta cell function and proliferation. Based on previous gene expression data by microarray, we hypothesized that osteocalcin protects beta cells from glucose-induced oxidative stress. To test our hypothesis we cultured isolated rat islets and INS-1E cells in the presence of normal, high, or high glucose ± osteocalcin for up to 72 h. Oxidative stress and viability/mitochondrial function were measured by H{sub 2}O{sub 2} assay and Alamar Blue assay, respectively. Caspase 3/7 activity was also measured as a marker of apoptosis. A functional test, glucose stimulated insulin release, was conducted and expression of genes/protein was measured by qRT-PCR/western blot/ELISA. Osteocalcin treatment significantly reduced high glucose-induced H{sub 2}O{sub 2} levels while maintaining viability/mitochondrial function. Osteocalcin also significantly improved glucose stimulated insulin secretion and insulin content in rat islets after 48 h of high glucose exposure compared to untreated islets. As expected sustained high glucose down-regulated gene/protein expression of INS1 and BCL2 while increasing TXNIP expression. Interestingly, osteocalcin treatment reversed the effects of high glucose on gene/protein expression. We conclude that osteocalcin can protect beta cells from the negative effects of glucose-induced oxidative stress, in part, by reducing TXNIP expression, thereby preserving beta cell function and survival. - Highlights: • Osteocalcin reduces glucose-induced oxidative stress in beta cells. • Osteocalcin preserves beta cell function and survival under stress conditions. • Osteocalcin reduces glucose

Osteocalcin protects pancreatic beta cell function and survival under high glucose conditions

International Nuclear Information System (INIS)

Kover, Karen; Yan, Yun; Tong, Pei Ying; Watkins, Dara; Li, Xiaoyu; Tasch, James; Hager, Melissa; Clements, Mark; Moore, Wayne V.

2015-01-01

Diabetes is characterized by progressive beta cell dysfunction and loss due in part to oxidative stress that occurs from gluco/lipotoxicity. Treatments that directly protect beta cell function and survival in the diabetic milieu are of particular interest. A growing body of evidence suggests that osteocalcin, an abundant non-collagenous protein of bone, supports beta cell function and proliferation. Based on previous gene expression data by microarray, we hypothesized that osteocalcin protects beta cells from glucose-induced oxidative stress. To test our hypothesis we cultured isolated rat islets and INS-1E cells in the presence of normal, high, or high glucose ± osteocalcin for up to 72 h. Oxidative stress and viability/mitochondrial function were measured by H 2 O 2 assay and Alamar Blue assay, respectively. Caspase 3/7 activity was also measured as a marker of apoptosis. A functional test, glucose stimulated insulin release, was conducted and expression of genes/protein was measured by qRT-PCR/western blot/ELISA. Osteocalcin treatment significantly reduced high glucose-induced H 2 O 2 levels while maintaining viability/mitochondrial function. Osteocalcin also significantly improved glucose stimulated insulin secretion and insulin content in rat islets after 48 h of high glucose exposure compared to untreated islets. As expected sustained high glucose down-regulated gene/protein expression of INS1 and BCL2 while increasing TXNIP expression. Interestingly, osteocalcin treatment reversed the effects of high glucose on gene/protein expression. We conclude that osteocalcin can protect beta cells from the negative effects of glucose-induced oxidative stress, in part, by reducing TXNIP expression, thereby preserving beta cell function and survival. - Highlights: • Osteocalcin reduces glucose-induced oxidative stress in beta cells. • Osteocalcin preserves beta cell function and survival under stress conditions. • Osteocalcin reduces glucose-induced TXNIP

Trace methane oxidation studied in several Euryarchaeota under diverse conditions

Directory of Open Access Journals (Sweden)

James J. Moran

2005-01-01

Full Text Available We used 13C-labeled methane to document the extent of trace methane oxidation by Archaeoglobus fulgidus, Archaeoglobus lithotrophicus, Archaeoglobus profundus, Methanobacterium thermoautotrophicum, Methanosarcina barkeri and Methanosarcina acetivorans. The results indicate trace methane oxidation during growth varied among different species and among methanogen cultures grown on different substrates. The extent of trace methane oxidation by Mb. thermoautotrophicum (0.05 ± 0.04%, ± 2 standard deviations of the methane produced during growth was less than that by M. barkeri (0.15 ± 0.04%, grown under similar conditions with H2 and CO2. Methanosarcina acetivorans oxidized more methane during growth on trimethylamine (0.36 ± 0.05% than during growth on methanol (0.07 ± 0.03%. This may indicate that, in M. acetivorans, either a methyltransferase related to growth on trimethylamine plays a role in methane oxidation, or that methanol is an intermediate of methane oxidation. Addition of possible electron acceptors (O2, NO3–, SO22–, SO32– or H2 to the headspace did not substantially enhance or diminish methane oxidation in M. acetivorans cultures. Separate growth experiments with FAD and NAD+ showed that inclusion of these electron carriers also did not enhance methane oxidation. Our results suggest trace methane oxidized during methanogenesis cannot be coupled to the reduction of these electron acceptors in pure cultures, and that the mechanism by which methane is oxidized in methanogens is independent of H2 concentration. In contrast to the methanogens, species of the sulfate-reducing genus Archaeoglobus did not significantly oxidize methane during growth (oxidizing 0.003 ± 0.01% of the methane provided to A. fulgidus, 0.002 ± 0.009% to A. lithotrophicus and 0.003 ± 0.02% to A. profundus. Lack of observable methane oxidation in the three Archaeoglobus species examined may indicate that methyl-coenzyme M reductase, which is not present in

Opposing effects of oxidative challenge and carotenoids on antioxidant status and condition-dependent sexual signalling.

Science.gov (United States)

Tomášek, Oldřich; Gabrielová, Barbora; Kačer, Petr; Maršík, Petr; Svobodová, Jana; Syslová, Kamila; Vinkler, Michal; Albrecht, Tomáš

2016-03-22

Several recent hypotheses consider oxidative stress to be a primary constraint ensuring honesty of condition-dependent carotenoid-based signalling. The key testable difference between these hypotheses is the assumed importance of carotenoids for redox homeostasis, with carotenoids being either antioxidant, pro-oxidant or unimportant. We tested the role of carotenoids in redox balance and sexual signalling by exposing adult male zebra finches (Taeniopygia guttata) to oxidative challenge (diquat dibromide) and manipulating carotenoid intake. As the current controversy over the importance of carotenoids as antioxidants could stem from the hydrophilic basis of commonly-used antioxidant assays, we used the novel measure of in vivo lipophilic antioxidant capacity. Oxidative challenge reduced beak pigmentation but elicited an increase in antioxidant capacity suggesting resource reallocation from signalling to redox homeostasis. Carotenoids counteracted the effect of oxidative challenge on lipophilic (but not hydrophilic) antioxidant capacity, thereby supporting carotenoid antioxidant function in vivo. This is inconsistent with hypotheses proposing that signalling honesty is maintained through either ROS-induced carotenoid degradation or the pro-oxidant effect of high levels of carotenoid-cleavage products acting as a physiological handicap. Our data further suggest that assessment of lipophilic antioxidant capacity is necessary to fully understand the role of redox processes in ecology and evolution.

Relationships among oxidation-reduction and acid-base properties of the actinides in high oxidation states

International Nuclear Information System (INIS)

Morss, L.R.

1992-01-01

The first chemical identification of plutonium, its subsequent isolation on the macroscopic scale, and more recent chemical separation schemes were achieved by taking advantage of the differences among the oxidation states of uranium, neptunium, and plutonium. Many acid-base properties modify the relative stabilities of oxidation states of the actinides. In the solid state, strongly basic compounds such as Cs 2 O yield complex oxides with oxidation states of Np(VII), Pu(VI), and Am(VI) whereas more acidic compounds such as CsF yield complex fluorides with lower oxidation states. In aqueous solution, high basicity and strongly covalent complexes favor high oxidation states. In nonaqueous solvent systems, high acidity generally favors low oxidation states. This paper elucidates and attempts to interpret the effects of these acid-base properties in a systematic fashion

Oxide vapor distribution from a high-frequency sweep e-beam system

Science.gov (United States)

Chow, R.; Tassano, P. L.; Tsujimoto, N.

1995-03-01

Oxide vapor distributions have been determined as a function of operating parameters of a high frequency sweep e-beam source combined with a programmable sweep controller. We will show which parameters are significant, the parameters that yield the broadest oxide deposition distribution, and the procedure used to arrive at these conclusions. A design-of-experimental strategy was used with five operating parameters: evaporation rate, sweep speed, sweep pattern (pre-programmed), phase speed (azimuthal rotation of the pattern), profile (dwell time as a function of radial position). A design was chosen that would show which of the parameters and parameter pairs have a statistically significant effect on the vapor distribution. Witness flats were placed symmetrically across a 25 inches diameter platen. The stationary platen was centered 24 inches above the e-gun crucible. An oxide material was evaporated under 27 different conditions. Thickness measurements were made with a stylus profilometer. The information will enable users of the high frequency e-gun systems to optimally locate the source in a vacuum system and understand which parameters have a major effect on the vapor distribution.

Luteolin and fisetin suppress oxidative stress by modulating sirtuins and forkhead box O3a expression under in vitro diabetic conditions.

Science.gov (United States)

Kim, Arang; Lee, Wooje; Yun, Jung-Mi

2017-10-01

Chronic hyperglycemia induces oxidative stress via accumulation of reactive oxygen species (ROS) and contributes to diabetic complications. Hyperglycemia induces mitochondrial superoxide anion production through the increased activity of nicotinamide adenine dinucleotide phosphate (NADPH) oxidase. This study aimed to determine whether fisetin and luteolin treatments suppress the oxidative stress by modulating the expression of sirtuins (SIRTs) and forkhead box O3a (FOXO3a) under hyperglycemic conditions in human monocytes. Human monocytic cells (THP-1) were cultured under osmotic control (14.5 mmol/L mannitol), normoglycemic (NG, 5.5 mmol/L glucose), or hyperglycemic (HG, 20 mmol/L glucose) conditions, in the absence or presence of fisetin and luteolin for 48 h. To determine the effect of fisetin and luteolin treatments on high glucose-induced oxidative stress, western blotting and intracellular staining were performed. Hyperglycemic conditions increased the ROS production, as compared to normoglycemic condition. However, fisetin and luteolin treatments inhibited ROS production under hyperglycemia. To obtain further insight into ROS production in hyperglycemic conditions, evaluation of p47phox expression revealed that fisetin and luteolin treatments inhibited p47phox expression under hyperglycemic conditions. Conversely, the expression levels of SIRT1, SIRT3, SIRT6, and FOXO3a were decreased under high glucose conditions compared to normal glucose conditions, but exposure to fisetin and luteolin induced the expression of SIRT1, SIRT3, SIRT6, and FOXO3a. The above findings suggest that fisetin and luteolin inhibited high glucose-induced ROS production in monocytes through the activation of SIRTs and FOXO3a. The results of our study supports current researches that state fisetin and luteolin as potential agents for the development of novel strategies for diabetes.

High pressure Moessbauer spectroscopy of perovskite iron oxide

CERN Document Server

Nasu, S; Morimoto, S; Kawakami, T; Kuzushita, K; Takano, M

2003-01-01

High-pressure sup 5 sup 7 Fe Moessbauer spectroscopy using a diamond anvil cell has been performed for perovskite iron oxides SrFeO sub 3 , CaFeO sub 3 and La sub 1 sub / sub 3 Sr sub 2 sub / sub 3 O sub 3. The charge states and the magnetic dependency to pressure were determined. Pressure magnetic phase diagrams of these perovskite iron oxides are determined up to about 70 GPa. To be clear the magnetic ordered state, they are measured up to 7.8 T external magnetic fields at 4.5K. The phase transition of these perovskite oxides to ferromagnetisms with high magnetic ordered temperature is observed. In higher pressure, high spin-low spin transition of oxides besides CaFeO sub 3 is generated. The feature of Moessbauer spectroscopy, perovskite iron oxide and Moessbauer spectroscopy under high pressure are explained. (S.Y.)

Combination of microbial oxidation and biogenic schwertmannite immobilization: A potential remediation for highly arsenic-contaminated soil.

Science.gov (United States)

Yang, Zhihui; Wu, Zijian; Liao, Yingping; Liao, Qi; Yang, Weichun; Chai, Liyuan

2017-08-01

Here, a novel strategy that combines microbial oxidation by As(III)-oxidizing bacterium and biogenic schwertmannite (Bio-SCH) immobilization was first proposed and applied for treating the highly arsenic-contaminated soil. Brevibacterium sp. YZ-1 isolated from a highly As-contaminated soil was used to oxidize As(III) in contaminated soils. Under optimum culture condition for microbial oxidation, 92.3% of water-soluble As(III) and 84.4% of NaHCO 3 -extractable As(III) in soils were removed. Bio-SCH synthesized through the oxidation of ferrous sulfate by Acidithiobacillus ferrooxidans immobilize As(V) in the contaminated soil effectively. Consequently, the combination of microbial oxidation and Bio-SCH immobilization performed better in treating the highly As-contaminated soil with immobilization efficiencies of 99.3% and 82.6% for water-soluble and NaHCO 3 -extractable total As, respectively. Thus, the combination can be considered as a green remediation strategy for developing a novel and valuable solution for As-contaminated soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

Low temperature spent fuel oxidation under tuff repository conditions

International Nuclear Information System (INIS)

Einziger, R.E.; Woodley, R.E.

1985-01-01

The Nevada Nuclear Waste Storage Investigations Project is studying the suitability of tuffaceous rocks at Yucca Mountain, Nye County, Nevada, for high level waste disposal. The oxidation state of LWR spent fuel in a tuff repository may be a significant factor in determining its ability to inhibit radionuclide migration. Long term exposure at low temperatures to the moist air expected in a tuff repository is expected to increase the oxidation state of the fuel. A program is underway to determine the spent fuel oxidation mechanisms which might be active in a tuff repository. Initial work involves a series of TGA experiments to determine the effectiveness of the technique and to obtain preliminary oxidation data. Tests were run at 200 0 C and 225 0 C for as long as 720 hours. Grain boundary diffusion appears to open up a greater surface area for oxidation prior to onset of bulk diffusion. Temperature strongly influences the oxidation rates. The effect of moisture is small but readily measurable. 25 refs., 7 figs., 4 tabs

The sensitivity of particle pH to NH3: Can high NH3 cause London Fog conditions?

Science.gov (United States)

Weber, R. J.; Guo, H.; Nenes, A.

2017-12-01

High ammonia emissions from agriculture or other sources have been suggested to elevate ambient particle pH levels to near neutral acidity (pH=7), a condition that promotes rapid SO2 oxidation by NO2 to form aerosol sulfate concentration consistent with "London fog" levels. This mechanism has been used to explain pollution haze events in China. Predicted pH for locations in the US and Europe show fine particles are highly acidic with pH typically less than 2. The results are consistent with measured ammonia and nitric acid gas-particle partitioning, validating predicted pH levels. Using these data sets from representative sites around the world we conduct a thermodynamic analysis of aerosol pH and its sensitivity to ammonia levels. We find that particle pH, regardless of ammonia levels, is always acidic even for the unusually high ammonia levels found in highly polluted Asian cities, Beijing (pH=4.5) and Xi'an (pH=5), locations where sulfate production from NOx is proposed. These results indicate that sulfur dioxide oxidation through a NO2-mediated pathway is not likely in China, nor any other region of the world (e.g., US, Mediterranean) since the fine aerosol is consistently acidic. The mildly acidic conditions would, however, permit rapid oxidation of sulfur dioxide through transition metal chemistry. The limited alkalinity from the carbonate buffer in dust and seasalt can provide the only likely set of conditions where NO2-mediated oxidation of SO2 outcompetes with other well-established pathways.

Evaporative light scattering detector in normal-phase high-performance liquid chromatography determination of FAME oxidation products.

Science.gov (United States)

Morales, Arturo; Marmesat, Susana; Dobarganes, M Carmen; Márquez-Ruiz, Gloria; Velasco, Joaquín

2012-09-07

The use of an ELS detector in NP-HPLC for quantitative analysis of oxidation products in FAME obtained from oils is evaluated in this study. The results obtained have shown that the ELS detector enables the quantitative determination of the hydroperoxides of oleic and linoleic acid methyl esters as a whole, and connected in series with a UV detector makes it possible to determine both groups of compounds by difference, providing useful complementary information. The limits of detection (LOD) and quantification (LOQ) found for hydroperoxides were respectively 2.5 and 5.7 μg mL⁻¹ and precision of quantitation expressed as coefficient of variation was lower than 10%. Due to a low sensitivity the ELS detector shows limitations to determine the low contents of secondary oxidation products in the direct analysis of FAME oxidized at low or moderate temperature. Analysis of FAME samples obtained either from high linoleic sunflower oil (HLSO) or high oleic sunflower oil (HOSO) and oxidized at 80 °C showed that only ketodienes formed from methyl linoleate can be determined in samples with relatively high oxidation, being the LOD and LOQ 0.2 and 0.4 mg/g FAME, respectively, at the analytical conditions applied. The ELS detector also enabled the determination of methyl cis-9,10-epoxystearate and methyl trans-9,10-epoxystearate, which were resolved at the chromatographic conditions applied. Results showed that these compounds, which are formed from methyl oleate, were not detected in the high-linoleic sample, but occurred at non-negligible levels in the oxidized FAME obtained from HOSO. Copyright © 2012 Elsevier B.V. All rights reserved.

Initial stages of high temperature metal oxidation

International Nuclear Information System (INIS)

Yang, C.Y.; O'Grady, W.E.

1981-01-01

The application of XPS and UPS to the study of the initial stages of high temperature (> 350 0 C) electrochemical oxidation of iron and nickel is discussed. In the high temperature experiments, iron and nickel electrodes were electrochemically oxidized in contact with a solid oxide electrolyte in the uhv system. The great advantages of this technique are that the oxygen activity at the interface may be precisely controlled and the ability to run the reactions in uhv allows the simultaneous observation of the reactions by XPS

Experimental investigation into the surface oxidation of lignite high temperature coke

Energy Technology Data Exchange (ETDEWEB)

Schaefer, H G; Dallmann, W [Technische Hochschule Aachen (Germany, F.R.). Lehrgebiet Kokerei und Brikettierung

1979-11-01

It was intended to produce lignite high temperature coke (BHFK) in the laboratory comparable to that produced with the Salem-Lurgi-open hearth process and quench them according to the prescribed condition. By this means, the surface oxide formation could be continually recorded gravimetrically. The self-sustaining reaction of the physical and chemical adsorption on the loose material were observed under consideration that the adsorption or surface oxide can exist in a gaseous as well as in a liquid aggregate. The established steam isotherms and electron-microscope photos identified the product BFHK as a material which shows in the range of high-humidity capillary condensation. The continuous gravimetric adsorption leads to 1,9 per cent by weight on dry surface oxides. On the other hand, oxidized coke in the presence of water builds up on the surface to 2,3 per cent by weight. It became apparent that the finest capillary water is not involved in the formation of the oxide. For the dry accumulation, which is a reaction of the first degree, the equation for the accumulation of the oxygen is given. From the BET surface, made up from the graphite-like ring structure of the carbon surface, as well as the dposited quantity of oxide, the surface density of the oxygen atoms is indicated in relation to the quantity of carbon atoms, or alternatively the six-ring. The dry deposition leads to a proportion of 1,5 oxygen atoms to 10 carbon atoms. In a wet reaction, the ratio is 1,8 to 10. With increasing quantities of oxide, the content of volatile matter, the sparking point and reactivity increase, while the porosity diminishes as a consequence.

Facet-Dependent Oxidative Goethite Growth As a Function of Aqueous Solution Conditions.

Science.gov (United States)

Strehlau, Jennifer H; Stemig, Melissa S; Penn, R Lee; Arnold, William A

2016-10-04

Nitroaromatic compounds are groundwater pollutants that can be degraded through reactions with Fe(II) adsorbed on iron oxide nanoparticles, although little is known about the evolving reactivity of the minerals with continuous pollutant exposure. In this work, Fe(II)/goethite reactivity toward 4-chloronitrobenzene (4-ClNB) as a function of pH, organic matter presence, and reactant concentrations was explored using sequential-spike batch reactors. Reaction rate constants were smaller with lower pH, introduction of organic matter, and diluted reactant concentrations as compared to a reference condition. Reaction rate constants did not change with the number of 4-ClNB spikes for all reaction conditions. Under all conditions, oxidative goethite growth was demonstrated through X-ray diffraction, magnetic characterization, and transmission electron microscopy. Nonparametric statistics were applied to compare histograms of lengths and widths of goethite nanoparticles as a function of varied solution conditions. The conditions that slowed the reaction also resulted in statistically shorter and wider particles than for the faster reactions. Additionally, added organic matter interfered with particle growth on the favorable {021} faces to a greater extent, with statistically reduced rate of growth on the tip facets and increased rate of growth on the side facets. These data demonstrate that oxidative growth of goethite in aqueous systems is dependent on major groundwater variables, such as pH and the presence of organic matter, which could lead to the evolving reactivity of goethite particles in natural environments.

Interface and oxide traps in high-κ hafnium oxide films

International Nuclear Information System (INIS)

Wong, H.; Zhan, N.; Ng, K.L.; Poon, M.C.; Kok, C.W.

2004-01-01

The origins of the interface trap generation and the effects of thermal annealing on the interface and bulk trap distributions are studied in detail. We found that oxidation of the HfO 2 /Si interface, removal of deep trap centers, and crystallization of the as-deposited film will take place during the post-deposition annealing (PDA). These processes will result in the removal of interface traps and deep oxide traps and introduce a large amount of shallow oxide traps at the grain boundaries of the polycrystalline film. Thus, trade-off has to be made in considering the interface trap density and oxide trap density when conducting PDA. In addition, the high interface trap and oxide trap densities of the HfO 2 films suggest that we may have to use the SiO 2 /HfO 2 stack or hafnium silicate structure for better device performance

Modeling of High Temperature Oxidation Behavior of FeCrAl Alloy by using Artificial Neural Network

Energy Technology Data Exchange (ETDEWEB)

Kim, Jae Joon; Ryu, Ho Jin [KAIST, Daejeon (Korea, Republic of)

2016-10-15

Refractory alloys are candidate materials for replacing current zirconium-base cladding of light water reactors and they retain significant creep resistance and mechanical strength at high temperatures up to 1500 ℃ due to their high melting temperature. Thermal neutron cross sections of refractory metals are higher than that of zirconium, however the loss of neutron can be overcome by reducing cladding thickness which can be facilitated with enhanced mechanical properties. However, most refractory metals show the poor oxidation resistance at a high temperature. Oxidation behaviors of the various compositions of FeCrAl alloys in high temperature conditions were modeled by using Bayesian neural network. The automatic relevance determination (ARD) technique represented the influence of the composition of alloying elements on the oxidation resistance of FeCrAl alloys. This model can be utilized to understand the tendency of oxidation behavior along the composition of each element and prove the applicability of neural network modeling for the development of new cladding material of light water reactors.

Structure Annotation and Quantification of Wheat Seed Oxidized Lipids by High-Resolution LC-MS/MS.

Science.gov (United States)

Riewe, David; Wiebach, Janine; Altmann, Thomas

2017-10-01

Lipid oxidation is a process ubiquitous in life, but the direct and comprehensive analysis of oxidized lipids has been limited by available analytical methods. We applied high-resolution liquid chromatography-mass spectrometry (LC-MS) and tandem mass spectrometry (MS/MS) to quantify oxidized lipids (glycerides, fatty acids, phospholipids, lysophospholipids, and galactolipids) and implemented a platform-independent high-throughput-amenable analysis pipeline for the high-confidence annotation and acyl composition analysis of oxidized lipids. Lipid contents of 90 different naturally aged wheat ( Triticum aestivum ) seed stocks were quantified in an untargeted high-resolution LC-MS experiment, resulting in 18,556 quantitative mass-to-charge ratio features. In a posthoc liquid chromatography-tandem mass spectrometry experiment, high-resolution MS/MS spectra (5 mD accuracy) were recorded for 8,957 out of 12,080 putatively monoisotopic features of the LC-MS data set. A total of 353 nonoxidized and 559 oxidized lipids with up to four additional oxygen atoms were annotated based on the accurate mass recordings (1.5 ppm tolerance) of the LC-MS data set and filtering procedures. MS/MS spectra available for 828 of these annotations were analyzed by translating experimentally known fragmentation rules of lipids into the fragmentation of oxidized lipids. This led to the identification of 259 nonoxidized and 365 oxidized lipids by both accurate mass and MS/MS spectra and to the determination of acyl compositions for 221 nonoxidized and 295 oxidized lipids. Analysis of 15-year aged wheat seeds revealed increased lipid oxidation and hydrolysis in seeds stored in ambient versus cold conditions. © 2017 The author(s). All Rights Reserved.

CO oxidation on PtSn nanoparticle catalysts occurs at the interface of Pt and Sn oxide domains formed under reaction conditions

KAUST Repository

Michalak, William D.

2014-04-01

The barrier to CO oxidation on Pt catalysts is the strongly bound adsorbed CO, which inhibits O2 adsorption and hinders CO2 formation. Using reaction studies and in situ X-ray spectroscopy with colloidally prepared, monodisperse ∼2 nm Pt and PtSn nanoparticle catalysts, we show that the addition of Sn to Pt provides distinctly different reaction sites and a more efficient reaction mechanism for CO oxidation compared to pure Pt catalysts. To probe the influence of Sn, we intentionally poisoned the Pt component of the nanoparticle catalysts using a CO-rich atmosphere. With a reaction environment comprised of 100 Torr CO and 40 Torr O2 and a temperature range between 200 and 300 C, Pt and PtSn catalysts exhibited activation barriers for CO2 formation of 133 kJ/mol and 35 kJ/mol, respectively. While pure Sn is readily oxidized and is not active for CO oxidation, the addition of Sn to Pt provides an active site for O2 adsorption that is important when Pt is covered with CO. Sn oxide was identified as the active Sn species under reaction conditions by in situ ambient pressure X-ray photoelectron spectroscopy measurements. While chemical signatures of Pt and Sn indicated intermixed metallic components under reducing conditions, Pt and Sn were found to reversibly separate into isolated domains of Pt and oxidic Sn on the nanoparticle surface under reaction conditions of 100 mTorr CO and 40 mTorr O2 between temperatures of 200-275 C. Under these conditions, PtSn catalysts exhibited apparent reaction orders in O2 for CO 2 production that were 0.5 and lower with increasing partial pressures. These reaction orders contrast the first-order dependence in O 2 known for pure Pt. The differences in activation barriers, non-first-order dependence in O2, and the presence of a partially oxidized Sn indicate that the enhanced activity is due to a reaction mechanism that occurs at a Pt/Sn oxide interface present at the nanoparticle surface. © 2014 Published by Elsevier Inc.

High temperature oxidation behavior of AISI 304L stainless steel—Effect of surface working operations

International Nuclear Information System (INIS)

Ghosh, Swati; Kumar, M. Kiran; Kain, Vivekanand

2013-01-01

Highlights: ► Surface working resulted in thinner oxide on the surface. ► Oxides on machined/ground surfaces richer in Cr, higher in specific resistivity. ► Additional ionic transport process at the metal-oxide for ground sample established. ► Presence of fragmented grains and martensite influenced oxide nature/morphology. - Abstract: The oxidation behavior of grade 304L stainless steel (SS) subjected to different surface finishing (machining and grinding) operations was followed in situ by contact electric resistance (CER) and electrochemical impedance spectroscopy (EIS) measurements using controlled distance electrochemistry (CDE) technique in high purity water (conductivity −1 ) at 300 °C and 10 MPa in an autoclave connected to a recirculation loop system. The results highlight the distinct differences in the oxidation behavior of surface worked material as compared to solution annealed material in terms of specific resistivity and low frequency Warburg impedance. The resultant oxide layer was characterized for (a) elemental analyses by glow discharge optical emission spectroscopy (GDOES) and (b) morphology by scanning electron microscopy (SEM). Oxide layers with higher specific resistivity and chromium content were formed in case of machined and ground conditions. Presence of an additional ionic transport process has also been identified for the ground condition at the metal/oxide interface. These differences in electrochemical properties and distinct morphological features of the oxide layer as a result of surface working were attributed to the prevalence of heavily fragmented grain structure and presence of martensite.

Depleted Nanocrystal-Oxide Heterojunctions for High-Sensitivity Infrared Detection

Science.gov (United States)

2015-08-28

Approved for Public Release; Distribution Unlimited Final Report: 4.3 Electronic Sensing - Depleted Nanocrystal- Oxide Heterojunctions for High...reviewed journals: Final Report: 4.3 Electronic Sensing - Depleted Nanocrystal- Oxide Heterojunctions for High-Sensitivity Infrared Detection Report Title...PERCENT_SUPPORTEDNAME FTE Equivalent: Total Number: 1 1 Final Progress Report Project title: Depleted Nanocrystal- Oxide Heterojunctions for High

Low nitrous oxide production through nitrifier-denitrification in intermittent-feed high-rate nitritation reactors.

Science.gov (United States)

Su, Qingxian; Ma, Chun; Domingo-Félez, Carlos; Kiil, Anne Sofie; Thamdrup, Bo; Jensen, Marlene Mark; Smets, Barth F

2017-10-15

Nitrous oxide (N 2 O) production from autotrophic nitrogen conversion processes, especially nitritation systems, can be significant, requires understanding and calls for mitigation. In this study, the rates and pathways of N 2 O production were quantified in two lab-scale sequencing batch reactors operated with intermittent feeding and demonstrating long-term and high-rate nitritation. The resulting reactor biomass was highly enriched in ammonia-oxidizing bacteria, and converted ∼93 ± 14% of the oxidized ammonium to nitrite. The low DO set-point combined with intermittent feeding was sufficient to maintain high nitritation efficiency and high nitritation rates at 20-26 °C over a period of ∼300 days. Even at the high nitritation efficiencies, net N 2 O production was low (∼2% of the oxidized ammonium). Net N 2 O production rates transiently increased with a rise in pH after each feeding, suggesting a potential effect of pH on N 2 O production. In situ application of 15 N labeled substrates revealed nitrifier denitrification as the dominant pathway of N 2 O production. Our study highlights operational conditions that minimize N 2 O emission from two-stage autotrophic nitrogen removal systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Experimental and Kinetic Modeling Study of Methanol Ignition and Oxidation at High Pressure

DEFF Research Database (Denmark)

Aranda, V.; Christensen, J. M.; Alzueta, Maria

2013-01-01

A detailed chemical kinetic model for oxidation of CH3OH at high pressure and intermediate temperatures has been developed and validated experimentally. Ab initio calculations and Rice–Ramsperger–Kassel–Marcus/transition state theory (RRKM/TST) analysis were used to obtain rate coefficients for CH...... the conditions studied, the onset temperature for methanol oxidation was not dependent on the stoichiometry, whereas increasing pressure shifted the ignition temperature toward lower values. Model predictions of the present experimental results, as well as rapid compression machine data from the literature, were...

High temperature oxidation behavior of TiAl-based intermetallics

International Nuclear Information System (INIS)

Stroosnijder, M.F.; Sunderkoetter, J.D.; Haanappel, V.A.C.

1996-01-01

TiAl-based intermetallic compounds have attracted considerable interest as structural materials for high-temperature applications due to their low density and substantial mechanical strength at high temperatures. However, one major drawback hindering industrial application arises from the insufficient oxidation resistance at temperatures beyond 700 C. In the present contribution some general aspects of high temperature oxidation of TiAl-based intermetallics will be presented. This will be followed by a discussion of the influence of alloying elements, in particular niobium, and of the effect of nitrogen in the oxidizing environment on the high temperature oxidation behavior of such materials

Oxidation of SiC cladding under Loss of Coolant Accident (LOCA) conditions in LWRs

International Nuclear Information System (INIS)

Lee, Y.; Yue, C.; Arnold, R. P.; McKrell, T. J.; Kazimi, M. S.

2012-01-01

An experimental assessment of Silicon Carbide (SiC) cladding oxidation rate in steam under conditions representative of Loss of Coolant Accidents (LOCA) in light water reactors (LWRs) was conducted. SiC oxidation tests were performed with monolithic alpha phase tubular samples in a vertical quartz tube at a steam temperature of 1140 deg. C and steam velocity range of 1 to 10 m/sec, at atmospheric pressure. Linear weight loss of SiC samples due to boundary layer controlled reaction of silica scale (SiO 2 volatilization) was experimentally observed. The weight loss rate increased with increasing steam flow rate. Over the range of test conditions, SiC oxidation rates were shown to be about 3 orders of magnitude lower than the oxidation rates of zircaloy 4. A SiC volatilization correlation for developing laminar flow in a vertical channel is formulated. (authors)

Oxidative dissolution of unirradiated Mimas MOX fuel (U/Pu oxides) in carbonated water under oxic and anoxic conditions

Energy Technology Data Exchange (ETDEWEB)

Odorowski, Mélina [CEA/DEN/DTCD/SECM/LMPA, BP 17171, 30207 Bagnols-sur-Cèze Cedex (France); MINES ParisTech, PSL Research University, Centre de Géosciences, 35 rue St Honoré, 77305 Fontainebleau (France); Jégou, Christophe, E-mail: christophe.jegou@cea.fr [CEA/DEN/DTCD/SECM/LMPA, BP 17171, 30207 Bagnols-sur-Cèze Cedex (France); De Windt, Laurent [MINES ParisTech, PSL Research University, Centre de Géosciences, 35 rue St Honoré, 77305 Fontainebleau (France); Broudic, Véronique; Peuget, Sylvain; Magnin, Magali; Tribet, Magaly [CEA/DEN/DTCD/SECM/LMPA, BP 17171, 30207 Bagnols-sur-Cèze Cedex (France); Martin, Christelle [Agence nationale pour la gestion des déchets radioactifs (Andra), DRD/CM, 1-7 rue Jean-Monnet, 92298 Châtenay-Malabry Cedex (France)

2016-01-15

Few studies exist concerning the alteration of Mimas Mixed-OXide (MOX) fuel, a mixed plutonium and uranium oxide, and data is needed to better understand its behavior under leaching, especially for radioactive waste disposal. In this study, two leaching experiments were conducted on unirradiated MOX fuel with a strong alpha activity (1.3 × 10{sup 9} Bq.g{sub MOX}{sup −1} reproducing the alpha activity of spent MOX fuel with a burnup of 47 GWd·t{sub HM}{sup −1} after 60 years of decay), one under air (oxic conditions) for 5 months and the other under argon (anoxic conditions with [O{sub 2}] < 1 ppm) for one year in carbonated water (10{sup −2} mol L{sup −1}). For each experiment, solution samples were taken over time and Eh and pH were monitored. The uranium in solution was assayed using a kinetic phosphorescence analyzer (KPA), plutonium and americium were analyzed by a radiochemical route, and H{sub 2}O{sub 2} generated by the water radiolysis was quantified by chemiluminescence. Surface characterizations were performed before and after leaching using Scanning Electron Microscopy (SEM), Electron Probe Microanalyzer (EPMA) and Raman spectroscopy. Solubility diagrams were calculated to support data discussion. The uranium releases from MOX pellets under both oxic and anoxic conditions were similar, demonstrating the predominant effect of alpha radiolysis on the oxidative dissolution of the pellets. The uranium released was found to be mostly in solution as carbonate species according to modeling, whereas the Am and Pu released were significantly sorbed or precipitated onto the TiO{sub 2} reactor. An intermediate fraction of Am (12%) was also present as colloids. SEM and EPMA results indicated a preferential dissolution of the UO{sub 2} matrix compared to the Pu-enriched agglomerates, and Raman spectroscopy showed the Pu-enriched agglomerates were slightly oxidized during leaching. Unlike Pu-enriched zones, the UO{sub 2} grains were much more

Biochemical basis of the high resistance to oxidative stress in ...

Indian Academy of Sciences (India)

Unknown

581. Keywords. Apoptosis; D. discoideum; oxidative stress; antioxidant enzymes; lipid peroxidation ..... multiple toxic effects of oxidative stress that is related to several pathological conditions ... culture. This work was supported by a grant to RB.

Evolution of Near-Surface Internal and External Oxide Morphology During High-Temperature Selective Oxidation of Steels

Science.gov (United States)

Story, Mary E.; Webler, Bryan A.

2018-05-01

In this work we examine some observations made using high-temperature confocal scanning laser microscopy (HT-CSLM) during selective oxidation experiments. A plain carbon steel and advanced high-strength steel (AHSS) were selectively oxidized at high temperature (850-900°C) in either low oxygen or water vapor atmospheres. Surface evolution, including thermal grooving along grain boundaries and oxide growth, was viewed in situ during heating. Experiments investigated the influence of the microstructure and oxidizing atmosphere on selective oxidation behavior. Sequences of CSLM still frames collected during the experiment were processed with ImageJ to obtain histograms that showed a general darkening trend indicative of oxidation over time with all samples. Additional ex situ scanning electron microscopy and energy dispersive spectroscopy analysis supported in situ observations. Distinct oxidation behavior was observed for each case. Segregation, grain orientation, and extent of internal oxidation were all found to strongly influence surface evolution.

Atomically Monodisperse Nickel Nanoclusters as Highly Active Electrocatalysts for Water Oxidation

KAUST Repository

Joya, Khurram

2016-04-08

Achieving water splitting at low overpotential with high oxygen evolution efficiency and stability is important for realizing solar to chemical energy conversion devices. Herein we report the synthesis, characterization and electrochemical evaluation of highly active nickel nanoclusters (Ni NCs) for water oxidation at low overpotential. These atomically precise and monodisperse Ni NCs are characterized by using UV-visible absorption spectroscopy, single crystal X-ray diffraction and mass spectrometry. The molecular formulae of these Ni NCs are found to be Ni4(PET)8 and Ni6(PET)12 and are highly active electrocatalysts for oxygen evolution without any pre-conditioning. Ni4(PET)8 are slightly better catalysts than Ni6(PET)12 and initiate the oxygen evolution at an amazingly low overpotential of ~1.51 V (vs RHE; η ≈ 280 mV). The peak oxygen evolution current density (J) of ~150 mA cm–2 at 2.0 V (vs. RHE) with a Tafel slope of 38 mV dec–1 is observed using Ni4(PET)8. These results are comparable to the state-of-the art RuO2 electrocatalyst, which is highly expensive and rare compared to Ni-based materials. Sustained oxygen generation for several hours with an applied current density of 20 mA cm–2 demonstrates the long-term stability and activity of these Ni NCs towards electrocatalytic water oxidation. This unique approach provides a facile method to prepare cost-effective, nanoscale and highly efficient electrocatalysts for water oxidation.

Isothermal Oxidation of Magnetite to Hematite in Air and Cyclic Reduction/Oxidation Under Carbon Looping Combustion Conditions

Science.gov (United States)

Simmonds, Tegan; Hayes, Peter C.

2017-12-01

In the carbon looping combustion process the oxygen carrier is regenerated through oxidation in air; this process has been simulated by the oxidation of dense synthetic magnetite for selected temperatures and times. The oxidation of magnetite in air is shown to occur through the formation of dense hematite layers on the particle surface. This dense hematite forms through lath type shear transformations or solid-state diffusion through the product layer. Cyclic reduction in CO-CO2/oxidation in air of hematite single crystals has been carried out under controlled laboratory conditions at 1173 K (900 °C). It has been shown that the initial reduction step is critical to determining the product microstructure, which consists of gas pore dendrites in the magnetite matrix with blocky hematite formed on the pore surfaces. The progressive growth of the magnetite layer with the application of subsequent cycles appears to continue until no original hematite remains, after which physical disintegration of the particles takes place.

High-density oxidized porous silicon

International Nuclear Information System (INIS)

Gharbi, Ahmed; Souifi, Abdelkader; Remaki, Boudjemaa; Halimaoui, Aomar; Bensahel, Daniel

2012-01-01

We have studied oxidized porous silicon (OPS) properties using Fourier transform infraRed (FTIR) spectroscopy and capacitance–voltage C–V measurements. We report the first experimental determination of the optimum porosity allowing the elaboration of high-density OPS insulators. This is an important contribution to the research of thick integrated electrical insulators on porous silicon based on an optimized process ensuring dielectric quality (complete oxidation) and mechanical and chemical reliability (no residual pores or silicon crystallites). Through the measurement of the refractive indexes of the porous silicon (PS) layer before and after oxidation, one can determine the structural composition of the OPS material in silicon, air and silica. We have experimentally demonstrated that a porosity approaching 56% of the as-prepared PS layer is required to ensure a complete oxidation of PS without residual silicon crystallites and with minimum porosity. The effective dielectric constant values of OPS materials determined from capacitance–voltage C–V measurements are discussed and compared to FTIR results predictions. (paper)

Effect of substrate availability on nitrous oxide production by deammonification processes under anoxic conditions.

Science.gov (United States)

Schneider, Yvonne; Beier, Maike; Rosenwinkel, Karl-Heinz

2012-05-01

Due to its high global warming potential, nitrous oxide (N(2)O) emissions from wastewater treatment processes have recently received a high degree of attention. Nevertheless, there is still a lack of information regarding the microbiological processes leading to N(2)O production. In this study, two lab-scale sequencing batch reactors were operated with deammonification biomass to investigate the role of denitrification and the influence of substrate availability regarding N(2)O formation during the anoxic phase of deammonification. Three different operational phases were established: within the first phase conversion by anammox was favoured and after a transition phase, denitrification activity was promoted. Low nitrous oxide production was observed during stable operation aiming for anammox conversion. Pulsed inflow of the wastewater containing ammonium (NH(4)(+)) and nitrite (NO(2)(-)) led to increased N(2)O production rates. Within the period of denitrification as dominating nitrogen conversion process, the nitrous oxide concentration level was higher during continuous inflow conditions, but the reaction to pulsed inflow was less pronounced. The results indicated that denitrification was responsible for N(2)O formation from the deammonification biomass. Operational settings to achieve suppression of denitrification processes to a large extend were deducted from the results of the experiments. © 2012 The Authors. Microbial Biotechnology © 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.

Relationship between oxide film structures and corrosion resistance of SUS 304 L stainless steel in high temperature pure water

International Nuclear Information System (INIS)

Yamanaka, Kazuo; Matsuda, Yasushi.

1990-01-01

The effect of various oxidation conditions on metal release of SUS304L stainless steels in deaerated pure water at 488 K was investigated. The behavior of metal release was also discussed in relation to the surface films which were formed by various oxidation treatments. The results obtained are as follows: (1) The oxidation treatment in high purity argon gas at high temperatures for short time such as 1273 K - 2 min (120S) was effective to decrease the metal dissolution, and the oxide films primarily consisted of spinel type double oxide layer containing high concentration of Mn and Cr. (2) The oxidation treatments in non-deaerated pure water at 561 K for 24∼336 h (86.4∼1209.6 ks) were furthermore effective to decrease the metal dissolution. (3) It may be concluded that the key factors controlling the metal release are thickness, structure and compactness together with compositions of surface oxide films. (author)

Highly efficient aerobic oxidation of alcohols by using less-hindered nitroxyl-radical/copper catalysis: optimum catalyst combinations and their substrate scope.

Science.gov (United States)

Sasano, Yusuke; Kogure, Naoki; Nishiyama, Tomohiro; Nagasawa, Shota; Iwabuchi, Yoshiharu

2015-04-01

The oxidation of alcohols into their corresponding carbonyl compounds is one of the most fundamental transformations in organic chemistry. In our recent report, 2-azaadamantane N-oxyl (AZADO)/copper catalysis promoted the highly chemoselective aerobic oxidation of unprotected amino alcohols into amino carbonyl compounds. Herein, we investigated the extension of the promising AZADO/copper-catalyzed aerobic oxidation of alcohols to other types of alcohol. During close optimization of the reaction conditions by using various alcohols, we found that the optimum combination of nitroxyl radical, copper salt, and solution concentration was dependent on the type of substrate. Various alcohols, including highly hindered and heteroatom-rich ones, were efficiently oxidized into their corresponding carbonyl compounds under mild conditions with lower amounts of the catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphite Oxidation Simulation in HTR Accident Conditions

Energy Technology Data Exchange (ETDEWEB)

El-Genk, Mohamed

2012-10-19

Massive air and water ingress, following a pipe break or leak in steam-generator tubes, is a design-basis accident for high-temperature reactors (HTRs). Analysis of these accidents in both prismatic and pebble bed HTRs requires state-of-the-art capability for predictions of: 1) oxidation kinetics, 2) air helium gas mixture stratification and diffusion into the core following the depressurization, 3) transport of multi-species gas mixture, and 4) graphite corrosion. This project will develop a multi-dimensional, comprehensive oxidation kinetics model of graphite in HTRs, with diverse capabilities for handling different flow regimes. The chemical kinetics/multi-species transport model for graphite burning and oxidation will account for temperature-related changes in the properties of graphite, oxidants (O2, H2O, CO), reaction products (CO, CO2, H2, CH4) and other gases in the mixture (He and N2). The model will treat the oxidation and corrosion of graphite in geometries representative of HTR core component at temperatures of 900°C or higher. The developed chemical reaction kinetics model will be user-friendly for coupling to full core analysis codes such as MELCOR and RELAP, as well as computational fluid dynamics (CFD) codes such as CD-adapco. The research team will solve governing equations for the multi-dimensional flow and the chemical reactions and kinetics using Simulink, an extension of the MATLAB solver, and will validate and benchmark the model's predictions using reported experimental data. Researchers will develop an interface to couple the validated model to a commercially available CFD fluid flow and thermal-hydraulic model of the reactor , and will perform a simulation of a pipe break in a prismatic core HTR, with the potential for future application to a pebble-bed type HTR.

High-pressure oxidation of methane

NARCIS (Netherlands)

Hashemi, Hamid; Christensen, Jakob M.; Gersen, Sander; Levinsky, Howard; Klippenstein, Stephen J.; Glarborg, Peter

2016-01-01

Methane oxidation at high pressures and intermediate temperatures was investigated in a laminar flow reactor and in a rapid compression machine (RCM). The flow-reactor experiments were conducted at 700–900 K and 100 bar for fuel-air equivalence ratios (Φ) ranging from 0.06 to 19.7, all highly

Oxide layers of Zr-1% Nb under PWR primary circuit conditions

International Nuclear Information System (INIS)

Nagy, Gabor; Kerner, Zsolt; Battistig, Gabor; Pinter-Csordas, Anna; Balogh, Janos; Pajkossy, Tamas

2001-01-01

Oxide layers were grown on Zr-1% Nb under conditions simulating those in VVER-type pressurised water reactors (PWRs), viz. in borate solutions in an autoclave at 290 deg. C. The layers were characterised by various methods: their respective thickness values were determined by weight gain measurements, Rutherford backscattering (RBS), nuclear reaction analysis (NRA) and scanning electron microscopy (SEM); the electrical properties were tested by electrochemical impedance spectroscopy. The results show that the oxide layer on Zr-1% Nb is homogeneous and somewhat thicker than that on Zircaloy-4

Anti-oxidant effect of gold nanoparticles restrains hyperglycemic conditions in diabetic mice

Directory of Open Access Journals (Sweden)

Eom SooHyun

2010-07-01

Full Text Available Abstract Background Oxidative stress is imperative for its morbidity towards diabetic complications, where abnormal metabolic milieu as a result of hyperglycemia, leads to the onset of several complications. A biological antioxidant capable of inhibiting oxidative stress mediated diabetic progressions; during hyperglycemia is still the need of the era. The current study was performed to study the effect of biologically synthesized gold nanoparticles (AuNPs to control the hyperglycemic conditions in streptozotocin induced diabetic mice. Results The profound control of AuNPs over the anti oxidant enzymes such as GSH, SOD, Catalase and GPx in diabetic mice to normal, by inhibition of lipid peroxidation and ROS generation during hyperglycemia evidence their anti-oxidant effect during hyperglycemia. The AuNPs exhibited an insistent control over the blood glucose level, lipids and serum biochemical profiles in diabetic mice near to the control mice provokes their effective role in controlling and increasing the organ functions for better utilization of blood glucose. Histopathological and hematological studies revealed the non-toxic and protective effect of the gold nanoparticles over the vital organs when administered at dosage of 2.5 mg/kilogram.body.weight/day. ICP-MS analysis revealed the biodistribution of gold nanoparticles in the vital organs showing accumulation of AuNPs in the spleen comparatively greater than other organs. Conclusion The results obtained disclose the effectual role of AuNPs as an anti-oxidative agent, by inhibiting the formation of ROS, scavenging free radicals; thus increasing the anti-oxidant defense enzymes and creating a sustained control over hyperglycemic conditions which consequently evoke the potential of AuNPs as an economic therapeutic remedy in diabetic treatments and its complications.

Water oxidation catalysis with nonheme iron complexes under acidic and basic conditions: homogeneous or heterogeneous?

Science.gov (United States)

Hong, Dachao; Mandal, Sukanta; Yamada, Yusuke; Lee, Yong-Min; Nam, Wonwoo; Llobet, Antoni; Fukuzumi, Shunichi

2013-08-19

Thermal water oxidation by cerium(IV) ammonium nitrate (CAN) was catalyzed by nonheme iron complexes, such as Fe(BQEN)(OTf)2 (1) and Fe(BQCN)(OTf)2 (2) (BQEN = N,N'-dimethyl-N,N'-bis(8-quinolyl)ethane-1,2-diamine, BQCN = N,N'-dimethyl-N,N'-bis(8-quinolyl)cyclohexanediamine, OTf = CF3SO3(-)) in a nonbuffered aqueous solution; turnover numbers of 80 ± 10 and 20 ± 5 were obtained in the O2 evolution reaction by 1 and 2, respectively. The ligand dissociation of the iron complexes was observed under acidic conditions, and the dissociated ligands were oxidized by CAN to yield CO2. We also observed that 1 was converted to an iron(IV)-oxo complex during the water oxidation in competition with the ligand oxidation. In addition, oxygen exchange between the iron(IV)-oxo complex and H2(18)O was found to occur at a much faster rate than the oxygen evolution. These results indicate that the iron complexes act as the true homogeneous catalyst for water oxidation by CAN at low pHs. In contrast, light-driven water oxidation using [Ru(bpy)3](2+) (bpy = 2,2'-bipyridine) as a photosensitizer and S2O8(2-) as a sacrificial electron acceptor was catalyzed by iron hydroxide nanoparticles derived from the iron complexes under basic conditions as the result of the ligand dissociation. In a buffer solution (initial pH 9.0) formation of the iron hydroxide nanoparticles with a size of around 100 nm at the end of the reaction was monitored by dynamic light scattering (DLS) in situ and characterized by X-ray photoelectron spectra (XPS) and transmission electron microscope (TEM) measurements. We thus conclude that the water oxidation by CAN was catalyzed by short-lived homogeneous iron complexes under acidic conditions, whereas iron hydroxide nanoparticles derived from iron complexes act as a heterogeneous catalyst in the light-driven water oxidation reaction under basic conditions.

Corrosion Behavior and Oxide Film Formation of T91 Steel under Different Water Chemistry Operation Conditions

Energy Technology Data Exchange (ETDEWEB)

Zhang, D. Q.; Shi, C.; Li, J.; Gao, L. X. [Shanghai University of Electric Power, Shanghai (China); Lee, K. Y. [Dalian University of Technology, Dalian (China)

2017-02-15

The corrosion behavior of a ferritic/martensitic steel T91 exposed to an aqueous solution containing chloride and sulfate ions is investigated depending on the stimulated all-volatile treatment (AVT) and under oxygenated treatment (OT) conditions. The corrosion of T91 steel under OT condition is severe, while the corrosion under AVT condition is not. The co-existence of chloride and sulfate ions has antagonistic effect on the corrosion of T91 steel in both AVT and OT conditions. Unlike to corrosion resistance in the aqueous solution, OT pretreatment provides T91 steel lower oxidation-resistance than VAT pretreatment. From scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS) and X-ray diffraction (XRD) analysis, the lower corrosion resistance in the aqueous solution by VAT conditions possibly is due to the formation of pits. In addition, the lower oxidation resistance of T91 steel pretreated by OT conditions is explained as follows: the cracks formed during the immersion under OT conditions accelerated peeling-off rate of the oxide film.

Nitrate reductase and nitrous oxide production by Fusarium oxysporum 11dn1 under aerobic and anaerobic conditions.

Science.gov (United States)

Kurakov, A V; Nosikov, A N; Skrynnikova, E V; L'vov, N P

2000-08-01

The fungus Fusarium oxysporum 11dn1 was found to be able to grow and produce nitrous oxide on nitrate-containing medium in anaerobic conditions. The rate of nitrous oxide formation was three to six orders of magnitude lower than the rates of molecular nitrogen production by common denitrifying bacteria. Acetylene and ammonia did not affect the release of nitrous oxide release. It was shown that under anaerobic conditions fast increase of nitrate reductase activity occurred, caused by the synthesis of enzyme de novo and protein dephosphorylation. Reverse transfer of the mycelium to aerobic conditions led to a decline in nitrate reductase activity and stopped nitrous oxide production. The presence of two nitrate reductases was shown, which differed in molecular mass, location, temperature optima, and activity in nitrate- and ammonium-containing media. Two enzymes represent assimilatory and dissimilatory nitrate reductases, which are active in aerobic and anaerobic conditions, respectively.

Zircaloy-4 and M5 high temperature oxidation and nitriding in air

Energy Technology Data Exchange (ETDEWEB)

Duriez, C. [Institut de Radioprotection et Surete Nucleaire, Direction de Prevention des Accidents Majeurs, Centre de Cadarache, 13115 St Paul Lez Durance (France)], E-mail: christian.duriez@irsn.fr; Dupont, T.; Schmet, B.; Enoch, F. [Universite Technologique de Troyes, BP 2060, 10010 Troyes (France)

2008-10-15

For the purpose of nuclear power plant severe accident analysis, degradation of Zircaloy-4 and M5 cladding tubes in air at high temperature was investigated by thermo-gravimetric analysis, in isothermal conditions, in a 600-1200 deg. C temperature range. Alloys were investigated either in a 'as received' bare state, or after steam pre-oxidation at 500 {sup o}C to simulate in-reactor corrosion. At the beginning of air exposure, the oxidation rate obeys a parabolic law, characteristic of solid-state diffusion limited regime. Parabolic rate constants compare, for Zircaloy-4 as well as for M5, with recently assessed correlations for high temperature Zircaloy-4 steam-oxidation. A thick layer of dense protective zirconia having a columnar structure forms during this diffusion-limited regime. Then, a kinetic transition (breakaway type) occurs, due to radial cracking along the columnar grain boundaries of this protective dense oxide scale. The breakaway is observed for a scale thickness that strongly increases with temperature. At the lowest temperatures, the M5 alloy appears to be breakaway-resistant, showing a delayed transition compared to Zircaloy-4. However, for both alloys, a pre-existing corrosion scale favours the transition, which occurs much earlier. The post transition kinetic regime is linear only for the lowest temperatures investigated. From 800 deg. C, a continuously accelerated regime is observed and is associated with formation of a strongly porous non-protective oxide. A mechanism of nitrogen-assisted oxide growth, involving formation and re-oxidation of ZrN particles, as well as nitrogen associated zirconia phase transformations, is proposed to be responsible for this accelerated degradation.

Capacitive behavior of highly-oxidized graphite

Science.gov (United States)

Ciszewski, Mateusz; Mianowski, Andrzej

2014-09-01

Capacitive behavior of a highly-oxidized graphite is presented in this paper. The graphite oxide was synthesized using an oxidizing mixture of potassium chlorate and concentrated fuming nitric acid. As-oxidized graphite was quantitatively and qualitatively analyzed with respect to the oxygen content and the species of oxygen-containing groups. Electrochemical measurements were performed in a two-electrode symmetric cell using KOH electrolyte. It was shown that prolonged oxidation causes an increase in the oxygen content while the interlayer distance remains constant. Specific capacitance increased with oxygen content in the electrode as a result of pseudo-capacitive effects, from 0.47 to 0.54 F/g for a scan rate of 20 mV/s and 0.67 to 1.15 F/g for a scan rate of 5 mV/s. Better cyclability was observed for the electrode with a higher oxygen amount.

The Influence of Aluminizing Process on the Surface Condition and Oxidation Resistance of Ti–45Al–8Nb–0.5(B, C Alloy

Directory of Open Access Journals (Sweden)

Wojciech Szkliniarz

2018-03-01

Full Text Available One of the major barriers limiting the suitability of TiAl intermetallic alloys for use in the demanding aircraft and automotive industries is their susceptibility to degradation as a result of oxidation at temperatures exceeding 760 °C. Paper presents the characteristics of resistance to cyclic oxidation at 950 °C for Ti–45Al–8Nb–0.5(B, C alloy with and without protective coating obtained as a result of aluminizing using out of pack method. The characteristics of surface condition were determined by scanning electron microscope with EDS system, transmission electron microscope, and X-ray diffractometer. The favorable behavior of the Ti–45Al–8Nb–0.5(B, C alloy with a protective coating under cyclic oxidation conditions is a result of a higher content of Al2O3 in the microstructure of the scale and the presence of Al and Nb-rich phases at the substrate interface, which probably constitue a barrier for oxidation process. The high temperature oxidation test revealed that aluminide coating was responsible for a remarkable improvement in the oxidation resistance.

High Temperature Oxidation of Superalloys and Intermetallic Compounds

Science.gov (United States)

2010-02-28

Oxid. Met. Vol.14, pp. 217-234. 1980. 20. T.A. Rannanarayanan, M. Raghavan and R. Petrovic-Luton. Metallic Yttrium Additions to High Temperatura ... Temperatura Alloys: Influence of AI2O3 Scale Properties. Oxid. Met. Vol.22, pp. 83-100. 1984. 21. High-temperature characterization of reactively

Translucency and Strength of High-Translucency Monolithic Zirconium-Oxide Materials

Science.gov (United States)

2016-05-12

Capt Todd D. Church APPROVED: Translucency and Strength of High-Translucency Monolithic Zirconium -Oxide Materials C~t) Kraig/[ Vandewalle Date...copyrighted material in the thesis/dissertation manuscript entitled: "Translucency arid Strength of High-Translucency Monolithic Zirconium -Oxide...Translucency Monolithic Zirconium -Oxide Materials Abstract Dental materials manufacturers have developed more translucent monolithic zirconium oxide

Computational prediction of the refinement of oxide agglomerates in a physical conditioning process for molten aluminium alloy

International Nuclear Information System (INIS)

Tong, M; Jagarlapudi, S C; Browne, D J; Patel, J B; Stone, I C; Fan, Z

2015-01-01

Physically conditioning molten scrap aluminium alloys using high shear processing (HSP) was recently found to be a promising technology for purification of contaminated alloys. HSP refines the solid oxide agglomerates in molten alloys, so that they can act as sites for the nucleation of Fe-rich intermetallic phases which can subsequently be removed by the downstream de-drossing process. In this paper, a computational modelling for predicting the evolution of size of oxide clusters during HSP is presented. We used CFD to predict the macroscopic flow features of the melt, and the resultant field predictions of temperature and melt shear rate were transferred to a population balance model (PBM) as its key inputs. The PBM is a macroscopic model that formulates the microscopic agglomeration and breakage of a population of a dispersed phase. Although it has been widely used to study conventional deoxidation of liquid metal, this is the first time that PBM has been used to simulate the melt conditioning process within a rotor/stator HSP device. We employed a method which discretizes the continuous profile of size of the dispersed phase into a collection of discrete bins of size, to solve the governing population balance equation for the size of agglomerates. A finite volume method was used to solve the continuity equation, the energy equation and the momentum equation. The overall computation was implemented mainly using the FLUENT module of ANSYS. The simulations showed that there is a relatively high melt shear rate between the stator and sweeping tips of the rotor blades. This high shear rate leads directly to significant fragmentation of the initially large oxide aggregates. Because the process of agglomeration is significantly slower than the breakage processes at the beginning of HSP, the mean size of oxide clusters decreases very rapidly. As the process of agglomeration gradually balances the process of breakage, the mean size of oxide clusters converges to a

Computational prediction of the refinement of oxide agglomerates in a physical conditioning process for molten aluminium alloy

Science.gov (United States)

Tong, M.; Jagarlapudi, S. C.; Patel, J. B.; Stone, I. C.; Fan, Z.; Browne, D. J.

2015-06-01

Physically conditioning molten scrap aluminium alloys using high shear processing (HSP) was recently found to be a promising technology for purification of contaminated alloys. HSP refines the solid oxide agglomerates in molten alloys, so that they can act as sites for the nucleation of Fe-rich intermetallic phases which can subsequently be removed by the downstream de-drossing process. In this paper, a computational modelling for predicting the evolution of size of oxide clusters during HSP is presented. We used CFD to predict the macroscopic flow features of the melt, and the resultant field predictions of temperature and melt shear rate were transferred to a population balance model (PBM) as its key inputs. The PBM is a macroscopic model that formulates the microscopic agglomeration and breakage of a population of a dispersed phase. Although it has been widely used to study conventional deoxidation of liquid metal, this is the first time that PBM has been used to simulate the melt conditioning process within a rotor/stator HSP device. We employed a method which discretizes the continuous profile of size of the dispersed phase into a collection of discrete bins of size, to solve the governing population balance equation for the size of agglomerates. A finite volume method was used to solve the continuity equation, the energy equation and the momentum equation. The overall computation was implemented mainly using the FLUENT module of ANSYS. The simulations showed that there is a relatively high melt shear rate between the stator and sweeping tips of the rotor blades. This high shear rate leads directly to significant fragmentation of the initially large oxide aggregates. Because the process of agglomeration is significantly slower than the breakage processes at the beginning of HSP, the mean size of oxide clusters decreases very rapidly. As the process of agglomeration gradually balances the process of breakage, the mean size of oxide clusters converges to a

The inhibitory effects of free ammonia on ammonia oxidizing bacteria and nitrite oxidizing bacteria under anaerobic condition.

Science.gov (United States)

Qian, Wenting; Peng, Yongzhen; Li, Xiyao; Zhang, Qiong; Ma, Bin

2017-11-01

The free ammonia (FA) inhibition on ammonia oxidizing bacteria (AOB) and nitrite oxidizing bacteria (NOB) under anaerobic condition was investigated in this study. The results indicated that NOB was more sensitive to the FA anaerobic treatment than AOB. The FA anaerobic inhibition on nitrifier gradually heightened with the increase of FA concentration. Accompanied with FA concentration increase from 0 to 16.82mgNH 3 -N·L -1 (the highest concentration adopted in this study), the activity of AOB reduced by 15.9%, while NOB decreased by 29.2%. After FA anaerobic treatment, nitrite was accumulated during nitrification. However, the nitrite accumulation disappeared on the sixth cycle of activity recovery tests with excessive aeration. Based on this result, a novel strategy for achieving nitritation is proposed, which involves recirculating a portion of the activated sludge through a side-line sludge treatment unit, where the sludge is subjected to treatment with FA under anaerobic condition. Copyright © 2017 Elsevier Ltd. All rights reserved.

High-resolution characterization of oxidation mechanism of zirconium nuclear fuel cladding alloys

International Nuclear Information System (INIS)

Hu, J.; Lozano-Perez, S.; Grovenor, C.

2015-01-01

Full text of publication follows. Zirconium alloys are used extensively as cladding materials in modern light water reactors to separate the uranium dioxide (UO 2 ) fuel rods and the coolant water in order to prevent the escape of radioactive fission products whilst maintaining heat transfer to the coolant. With increasing demand for high burn-up in modern nuclear reactors, environmental degradation of these alloys is now the life limiting factor for fuel assemblies. As part of the MUZIC-2 collaboration studying oxidation and hydrogen pickup in Zr alloys, several high resolution analysis techniques have been used to study the microstructure of a range of commercial and developmental Zr alloys. The sample used for this investigation was prepared from a Westinghouse TM developmental alloy with composition of Zr-0.9Nb-0.01Sn-0.08Fe (wt %) in the recrystallized condition. The sample was oxidised in an autoclave at EDF Energy under simulated PWR water conditions at 360 C. degrees for 360 days. Using Transmission Electron Microscope (TEM), we have studied the development of the equiaxed-columnar-equiaxed grain structure, and observe that the columnar grains are both longer and show a stronger preferred texture in more corrosion-resistant alloys. Fresnel imaging revealed the existence of both parallel interconnected pores and some vertically interconnected pores along the columnar oxide grain boundaries, which become more disconnected near the metal-oxide interface. Electron Energy Loss Spectroscopy (EELS) provided accurate quantitative analysis of the oxygen concentration across the interface, identifying the existence of local regions of stoichiometric ZrO and Zr 3 O 2 with varying thickness. These observations will be discussed in the context of current models for oxidation in zirconium alloys. (authors)

Oxidation-reduction conditions of the plants with reference to their gas resistance

Energy Technology Data Exchange (ETDEWEB)

Krasinskii, N P

1944-01-01

The object of this work was to see if there is any relation between the oxidation-reduction conditions existing in a plant, and its ability to grow successfully in the cities where air contains H/sub 2/S. Oxidation-reduction potential, capacity for its water-soluble and insoluble matter to be oxidized with KMnO/sub 4/ before and after treatment with H/sub 2/S, and finally the effect of the age of the plant were determined for different spp. of several common families of plants. In the majority of the families it was found that in various spp. of the same family these characteristics vary within a narrow and different range. Oxidation with KMnO/sub 4/ of the water-insoluble matter was found to be the best criterion of the sensitivity of a plant to H/sub 2/S.

New insight of high temperature oxidation on self-exfoliation capability of graphene oxide

Science.gov (United States)

Liu, Yuhang; Zeng, Jie; Han, Di; Wu, Kai; Yu, Bowen; Chai, Songgang; Chen, Feng; Fu, Qiang

2018-05-01

The preparation of graphene oxide (GO) via Hummers method is usually divided into two steps: low temperature oxidation at 35 °C (step I oxidation) and high temperature oxidation at 98 °C (step II oxidation). However, the effects of these two steps on the exfoliation capability and chemical structure of graphite oxide remain unclear. In this study, both the functional group content of graphite oxide and the entire evolution of interlayer spacing were investigated during the two steps. Step I oxidation is a slowly inhomogeneous oxidation step to remove unoxidized graphite flakes. The prepared graphite oxide can be easily self-exfoliated but contains a lot of organic sulfur. During the first 20 min of step II oxidation, the majority of organic sulfur can be efficiently removed and graphite oxide still remains a good exfoliation capability due to sharp increasing of carboxyl groups. However, with a longer oxidation time at step II oxidation, the decrease of organic sulfur content is slowed down apparently but without any carboxyl groups forming, then graphite oxide finally loses self-exfoliation capability. It is concluded that a short time of step II oxidation can produce purer and ultralarge GO sheets via self-exfoliation. The pure GO is possessed with better thermal stability and liquid crystal behavior. Besides, reduced GO films prepared from step II oxidation show better mechanical and electric properties after reducing compared with that obtained only via step I oxidation.

Vacuum-arc chromium coatings for Zr-1%Nb alloy protection against high-temperature oxidation in air

International Nuclear Information System (INIS)

Kuprin, A.S.; Belous, V.A.; Bryk, V.V.; Vasilenko, R.L.; Voevodin, V.N.; Ovcharenko, V.D.; Tolmacheva, G.N.; Kolodij, I.V.; Lunev, V.M.; Klimenko, I.O.

2015-01-01

The effect of vacuum-arc Cr coatings on the alloy E110 resistance to the oxidation in air at temperatures 1020 and 1100 deg C for 3600 s has been investigated. The methods of scanning electron microscope, X-ray analysis and nanoindentation were used to determine the thickness, phase, mechanical properties of coatings and oxide layers. The results show that the chromium coating can effectively protect fuel tubes against high-temperature oxidation in air for one hour. In the coating during oxidation at T = 1100 deg C a Cr 2 O 3 oxide layer of 5 μm thickness is formed preventing further oxygen penetration into the coating, and thus the tube shape is conserved. Under similar test conditions the oxidation of uncoated tubes with formation of a porous monocline oxide of ZrO 2 of a thickness more than ≥ 250 μm is observed, then the deformation and cracking of samples occur and the oxide layer breaks away

Influence of metformin and insulin on myocardial substrate oxidation under conditions encountered during cardiac surgery.

Science.gov (United States)

Holmes, Cyonna; Powell, LaShondra; Clarke, Nicholas S; Jessen, Michael E; Peltz, Matthias

2018-02-01

The influence of diabetic therapies on myocardial substrate selection during cardiac surgery is unknown but may be important to ensure optimal surgical outcomes. We hypothesized that metformin and insulin alter myocardial substrate selection during cardiac surgery and may affect reperfusion cardiac function. Rat hearts (n = 8 per group) were evaluated under 3 metabolic conditions: normokalemia, cardioplegia, or bypass. Groups were perfused with Krebs-Henseleit buffer in the presence of no additives, metformin, insulin, or both insulin and metformin. Perfusion buffer containing physiologic concentrations of energetic substrates with different carbon-13 ( 13 C) labeling patterns were used to determine substrate oxidation preferences using 13 C magnetic resonance spectroscopy and glutamate isotopomer analysis. Rate pressure product and oxygen consumption were measured. Myocardial function was not different between groups. For normokalemia, ketone oxidation was reduced in the presence of insulin and the combination of metformin and insulin reduced fatty acid oxidation. Metformin reduced fatty acid and ketone oxidation during cardioplegia. Fatty acid oxidation was increased in the bypass group compared with all other conditions. Metformin and insulin affect substrate utilization and reduce fatty acid oxidation before reperfusion. These alterations in substrate oxidation did not affect myocardial function in otherwise normal hearts. Copyright © 2017 Elsevier Inc. All rights reserved.

Steam oxidation of TP 347H FG. Laboratory exposures versus service conditions at the power plant

Energy Technology Data Exchange (ETDEWEB)

Hansson, Anette N. [DONG Energy A/S, Copenhagen (Denmark); Montgomery, Melanie [DONG Energy A/S, Copenhagen (Denmark); Technical Univ. of Denmark, Lyngby (Denmark). Dept. of Mechanical Engineering; Vattenfall Heat Nordic, Copenhagen (Denmark)

2010-07-01

TP347H FG is often used as final superheater tubing at Danish Power Plants. The oxidation behaviour of TP347H FG in steam was investigated both in laboratory conditions and field conditions. Short time exposures (336 hours) were performed in the laboratory at 500, 600 and 700 C in gasses with 8 or 46% H{sub 2}O and varying oxygen partial pressures. The shortest exposure time at the power plant was 7720 h, the temperature varied between 500 and 650 C. Surprisingly, thicker oxide layers formed within the laboratory facility at 600 and 700 C than during the long time exposures at the power plant. This could not be explained by spallation. Double-layered oxides developed during oxidation. The outer layer consist of Fe-oxides and the inner oxide contained Fe and the remaining alloy elements. Investigations with scanning electron microscopy (SEM) revealed that the morphology of the inner oxide was different for the two types of exposures. However, investigation using transmission electron microscopy (TEM) showed that the inner oxide in both cases consisted of particles of Fe-Mn-Cr spinel embedded in a metallic Fe-Ni matrix in the bulk of the (former) alloy grains and Cr-rich oxide layer along the (former) alloy grain boundaries. The main difference between the layers formed at the two locations is that the Cr-rich oxide layer is thicker for the samples exposed at the power plant than that for the samples exposed at the laboratory conditions. Furthermore, the depth of Cr depletion in the alloy adjacent the oxide layer is greater for the samples exposed at the power plant compared to those exposed in the laboratory. The microstructure investigation suggests that the slower oxidation rate of TP347H FG at the power plant as compared to the laboratory is due to a larger reservoir of Cr for the samples exposed at the power plant probably combined with a higher mobility of Cr within the alloy. (orig.)

Oxidative conditions prevail in severe IUGR with vascular disease and Doppler anomalies.

Science.gov (United States)

Maisonneuve, Emeline; Delvin, Edgard; Edgard, Annie; Morin, Lucie; Dubé, Johanne; Boucoiran, Isabelle; Moutquin, Jean-Marie; Fouron, Jean-Claude; Klam, Stephanie; Levy, Emile; Leduc, Line

2015-08-01

Intrauterine growth restriction (IUGR) and prenatal exposure to oxidative stress are thought to lead to increased risks of cardiovascular disease later in life. The objective of the present study was to document whether cord blood oxidative stress biomarkers vary with the severity of IUGR and of vascular disease in the twin pregnancy model in which both fetuses share the same maternal environment. This prospective cohort study involved dichorionic twin pairs, with one co-twin with IUGR. Oxidative stress biomarkers were measured in venous cord blood samples from each neonate of 32 twin pairs, and compared, according to severity of IUGR (IUGR <5th percentile), Doppler anomalies of the umbilical artery and early onset IUGR (in the second trimester) of the growth restricted twin. Oxidized Low-Density Lipoproteins (oxLDL) and Malondialdehyde (MDA) concentrations were increased proportionally in cases of severe IUGR. OxLDL concentrations were also increased in cases of IUGR with Doppler anomaly. Our data indicate that severe IUGR, is related to a derangement in redox balance, illustrated by increased venous cord blood oxidative stress biomarkers concentrations. Severe IUGR and IUGR with abnormal Doppler can be translated into conditions with intense oxidative stress.

Development of High Heat Input Welding Offshore Steel as Normalized Condition

Science.gov (United States)

Deng, Wei; Qin, Xiaomei

The heavy plate used for offshore structure is one of the important strategic products. In recent years, there is an increasing demand for heavy shipbuilding steel plate with excellent weldability in high heat input welding. During the thermal cycle, the microstructure of the heat affected zone (HAZ) of plates was damaged, and this markedly reduced toughness of HAZ. So, how to improve the toughness of HAZ has been a key subject in the fields of steel research. Oxide metallurgy is considered as an effective way to improve toughness of HAZ, because it could be used to retard grain growth by fine particles, which are stable at the high temperature.The high strength steel plate, which satisfies the low temperature specification, has been applied to offshore structure. Excellent properties of the plates and welded joints were obtained by oxide metallurgy technology, latest controlled rolling and accelerated cooling technology using Ultra-Fast Cooling (an on-line accelerated cooling system). The 355MPa-grade high strength steel plates with normalizing condition were obtained, and the steels have excellent weldability with heat input energy of 79 287kJ/cm, and the nil ductility transition (NDT) temperature was -70°C, which can satisfy the construction of offshore structure in cold regions.

Review Of Plutonium Oxidation Literature

International Nuclear Information System (INIS)

Korinko, P.

2009-01-01

A brief review of plutonium oxidation literature was conducted. The purpose of the review was to ascertain the effect of oxidation conditions on oxide morphology to support the design and operation of the PDCF direct metal oxidation (DMO) furnace. The interest in the review was due to a new furnace design that resulted in oxide characteristics that are different than those of the original furnace. Very little of the published literature is directly relevant to the DMO furnace operation, which makes assimilation of the literature data with operating conditions and data a convoluted task. The oxidation behavior can be distilled into three regimes, a low temperature regime (RT to 350 C) with a relatively slow oxidation rate that is influenced by moisture, a moderate temperature regime (350-450 C) that is temperature dependent and relies on more or less conventional oxidation growth of a partially protective oxide scale, and high temperature oxidation (> 500 C) where the metal autocatalytically combusts and oxidizes. The particle sizes obtained from these three regimes vary with the finest being from the lowest temperature. It is surmised that the slow growth rate permits significant stress levels to be achieved that help break up the oxides. The intermediate temperatures result in a fairly compact scale that is partially protective and that grows to critical thickness prior to fracturing. The growth rate in this regime may be parabolic or paralinear, depending on the oxidation time and consequently the oxide thickness. The high temperature oxidation is invariant in quiescent or nearly quiescent conditions due to gas blanketing while it accelerates with temperature under flowing conditions. The oxide morphology will generally consist of fine particles ( 250 (micro)m). The particle size ratio is expected to be < 5%, 25%, and 70% for fine, medium and large particles, respectively, for metal temperatures in the 500-600 C range.

Oxidative Uranium Release from Anoxic Sediments under Diffusion-Limited Conditions.

Science.gov (United States)

Bone, Sharon E; Cahill, Melanie R; Jones, Morris E; Fendorf, Scott; Davis, James; Williams, Kenneth H; Bargar, John R

2017-10-03

Uranium (U) contamination occurs as a result of mining and ore processing; often in alluvial aquifers that contain organic-rich, reduced sediments that accumulate tetravalent U, U(IV). Uranium(IV) is sparingly soluble, but may be mobilized upon exposure to nitrate (NO 3 - ) and oxygen (O 2 ), which become elevated in groundwater due to seasonal fluctuations in the water table. The extent to which oxidative U mobilization can occur depends upon the transport properties of the sediments, the rate of U(IV) oxidation, and the availability of inorganic reductants and organic electron donors that consume oxidants. We investigated the processes governing U release upon exposure of reduced sediments to artificial groundwater containing O 2 or NO 3 - under diffusion-limited conditions. Little U was mobilized during the 85-day reaction, despite rapid diffusion of groundwater within the sediments and the presence of nonuraninite U(IV) species. The production of ferrous iron and sulfide in conjunction with rapid oxidant consumption suggested that the sediments harbored large concentrations of bioavailable organic carbon that fueled anaerobic microbial respiration and stabilized U(IV). Our results suggest that seasonal influxes of O 2 and NO 3 - may cause only localized mobilization of U without leading to export of U from the reducing sediments when ample organic carbon is present.

Sulphate chemistry under pressurized oxidizing, reducing and fluctuating conditions; Sulfatkemi under trycksatta oxiderande, reducerande och fluktuerande foerhaallanden

Energy Technology Data Exchange (ETDEWEB)

Hupa, M.; Yrjas, P.; Backman, P. [Aabo Akademi, Turku (Finland). Combustion Chemistry Research Group

1997-10-01

In the literature it has been reported that sulfur capture with limestone (CaCO{sub 3}) under atmospheric fluidized bed combustion conditions reaches a maximum at about 850 deg C. Previously, the maximum has been attributed to the sintering of sorbent particles which decreases the reactive surface area. Lately, also another explanation has been reported. In this case the sulfur capture decrease at higher temperatures was concluded to be due to fluctuating oxidizing/reducing conditions in the atmospheric combustor. In this work the influence of alternating oxidizing/reducing conditions on SO{sub 2} capture at atmospheric and elevated pressure (15 bar) has been studied. In the pressurized case, the CO{sub 2} partial pressure was kept high enough to prevent CaCO{sub 3} from calcining and therefore the CaSO{sub 4} would not form CaO but CaCO{sub 3} under reducing conditions. The experiments were done with a pressurized TGA by periodically changing the gas environment between oxidizing (O{sub 2}. SO{sub 2}, CO{sub 2} and N{sub 2}) and slightly reducing (CO, SO{sub 2}, CO{sub 2} and N{sub 2}) gas mixtures at different temperatures. The results from the experiments showed that under normal pressure and slightly reducing conditions CaO formation from CaSO{sub 4} increased with temperature as expected. However, no significant amounts of CaCO{sub 3} were formed from CaSO{sub 4} at elevated pressure. It was also concluded that since the formation of CaO from CaSO{sub 4} was relatively slow it could not explain the sharp sulfur capture maximum at about 850 deg C. Therefore, it was assumed that the strongly reducing zones, where CaS thermodynamically is the stable compound, play a more important role concerning the sulfur capture in fluidized bed combustors. (orig.)

Heat treatable indium tin oxide films deposited with high power pulse magnetron sputtering

International Nuclear Information System (INIS)

Horstmann, F.; Sittinger, V.; Szyszka, B.

2009-01-01

In this study, indium tin oxide (ITO) films were prepared by high power pulse magnetron sputtering [D. J. Christie, F. Tomasel, W. D. Sproul, D. C. Carter, J. Vac. Sci. Technol. A, 22 (2004) 1415. ] without substrate heating. The ITO films were deposited from a ceramic target at a deposition rate of approx. 5.5 nm*m/min kW. Afterwards, the ITO films were covered with a siliconoxynitride film sputtered from a silicon alloy target in order to prevent oxidation of the ITO film during annealing at 650 deg. C for 10 min in air. The optical and electrical properties as well as the texture and morphology of these films were investigated before and after annealing. Mechanical durability of the annealed films was evaluated at different test conditions. The results were compared with state-of-the art ITO films which were obtained at optimized direct current magnetron sputtering conditions

Amorphous carbon nanofibres inducing high specific capacitance of deposited hydrous ruthenium oxide

International Nuclear Information System (INIS)

Barranco, V.; Pico, F.; Ibanez, J.; Lillo-Rodenas, M.A.; Linares-Solano, A.; Kimura, M.; Oya, A.; Rojas, R.M.; Amarilla, J.M.; Rojo, J.M.

2009-01-01

Composites consisting of ruthenium oxide particles deposited on amorphous carbon nanofibres are prepared by a repetitive impregnation procedure. The choice of amorphous carbon nanofibres as support of amorphous ruthenium oxide leads to composites in which the deposited oxide consists of aggregates of extremely small primary particles (1-1.5 nm-size) and showing high porosity (specific surface area of 450 m 2 g -1 ). This special deposition of the oxide seems to favour: (i) high oxide capacitance (1000 Fg -1 ) at high oxide loadings (up to 20 wt%) and (ii) high capacitance retention (ca. 80% from the initial oxide capacitance) at high current densities (200 mA cm -2 ). Amorphous carbon nanofibres are suitable supports for amorphous ruthenium oxide and perhaps for other amorphous oxides acting as active electrode materials.

Translucency and Strength of High Translucency Monolithic Zirconium Oxide Materials

Science.gov (United States)

2016-05-17

Zirconium -Oxide Materials presented at/published to the Journal of General Dentistry with MDWI 41-108, and has been assigned local file #16208. 2...Zirconia-Oxide Materials 6. TITLE OF MATERIAL TO BE PUBLISHED OR PRESENTED: Translucency and Strength of High-Translucency Monolithic Zirconium -Oxide...OBSOLETE 48. DATE Page 3 of 3 Pages Translucency and Strength of High-Translucency Monolithic Zirconium -Oxide Materials Abstract Dental materials

Radio-Oxidation in Polyolefins: Non-Stationary Kinetic Conditions

International Nuclear Information System (INIS)

Dely, N.

2006-01-01

In the last fifty years, many authors have been interested in the radio-oxidation processes occurring in polymers. The polymer degradation under ionising radiations in presence of dioxygen is well described by a radical chemistry. The radio-oxidation process occurs in three steps: the first one is the production of radicals P degree by interaction between the polymer and the ionising radiations; then radicals P degree react spontaneously with O 2 solved in the polymer giving a peroxy radical POO degree which attacks the polymer forming a hydroperoxide POOH and a new radical P degree (propagation). The third step corresponds to the termination step, that is bimolecular reactions between radicals. It is generally assumed that the stationary state is rapidly reached and consequently that the oxidation induced during the built-up period of the radical concentration can be neglected. However, to our best knowledge, the temporal evolution of radical concentrations before reaching the steady state regime has never been studied in details. We recently performed a complete study of oxygen consumption under electron irradiation for an EPDM elastomer. An analysis, as function of dose rate and oxygen pressure, and assuming steady state conditions, allowed extracting all the kinetic constants. Starting for these experimental data, we calculated the build-up of the radical concentration by solving numerically the differential equations with help of the Minichem code. We conclude that, in fact, the oxidation induced during the built-up period is negligible. In this paper we show that [P degree] could present a quasi-stationary plateau before reaching its stationary level. Consequently, the full radical time evolution is essentially determined by two characteristic times for reaching the quasi and stationary levels and three concentrations: [P degree] and [POO degree] at the stationary level and [P degree] at the quasi-stationary plateau. We show that realistic approximations can

Synthesis and analysis of Mo-Si-B based coatings for high temperature oxidation protection of ceramic materials

Science.gov (United States)

Ritt, Patrick J.

The use of Ni-based superalloys in turbine engines has all but been exhausted, with operating temperatures nearing the melting point of these materials. The use of ceramics in turbine engines, particularly ceramic matrix composites such as SiC/C and SiC/SiC, is of interest due to their low density and attractive mechanical properties at elevated temperatures. The same materials are also in consideration for leading edges on hypersonic vehicles. However, SiC-based composites degrade in high temperature environments with low partial pressures of oxygen due to active oxidation, as well as high temperature environments containing water or sand. The need for a protective external coating for SiC-based composites in service is obvious. To date, no coating investigated for SiC/C or SiC/SiC has been proven to be resistant to oxidation and corrosion at intermediate and high temperatures, as well as in environments deficient in oxygen. The Mo-Si-B coating shows great promise in this area, having been proven resistant to attack from oxidation at extreme temperatures, from water vapor and from calcia-magnesia-aluminosilicate (CMAS). The adaptation of the Mo-Si-B coating for ceramic materials is presented in detail here. Evaluation of the coating under a range of oxidation conditions as well as simulated re-entry conditions confirms the efficacy of the Mo-Si-B based coating as protection from catastrophic failure. The key to the oxidation and corrosion resistance is a robust external aluminoborosilica glass layer that forms and flows quickly to cover the substrate, even under the extreme simulated re-entry conditions. Suppression of active oxidation of SiC, which may occur during atmospheric re-entry and hypersonic flight trajectories, has also been examined. In order to adapt the Mo-Si-B based coating to low partial pressures of oxygen and elevated temperatures, controlled amounts of Al were added to the Mo-Si-B based coating. The resulting coating decreased the inward

High-pressure oxidation of ethane

DEFF Research Database (Denmark)

Hashemi, Hamid; G. Jacobsen, Jon; Rasmussen, Christian T.

2017-01-01

Ethane oxidation at intermediate temperatures and high pressures has been investigated in both a laminar flow reactor and a rapid compression machine (RCM). The flow-reactor measurements at 600–900 K and 20–100 bar showed an onset temperature for oxidation of ethane between 700 and 825 K, depending...... on pressure, stoichiometry, and residence time. Measured ignition delay times in the RCM at pressures of 10–80 bar and temperatures of 900–1025 K decreased with increasing pressure and/or temperature. A detailed chemical kinetic model was developed with particular attention to the peroxide chemistry. Rate...

Early development conditions and the oxidative cost of social context in adulthood: an experimental study in birds

Directory of Open Access Journals (Sweden)

Ana eRomero-Haro

2015-04-01

Full Text Available Environmental conditions during early life may shape phenotype in adulthood. Early adverse conditions may increase the oxidative stress in adults, which could affect their reproductive output and survival. It has also been hypothesized that the larger the reproductive investment, the higher the oxidative stress. We tested this and the potential influence of early oxidative stress on how individuals respond to a reproductive stimulation. The synthesis of the antioxidant glutathione was inhibited in captive zebra finches (Taeniopygia guttata during growth. In adulthood, the expression of a carotenoid-based sexual signal, bill redness, increased in both sexes, with females also being heavier than controls. The social context of control and glutathione-inhibited males was then manipulated to stimulate precopulatory reproductive investments. Males were individually caged in front of a female or another male. We predicted that males enduring lower early antioxidant levels and placed close to a female should pay the highest cost of a hypothetical increase in bill redness in terms of oxidative damage. However, early conditions only influenced the male’s phenotype via their partners. Males caged with females showed increases in circulating pigment (carotenoid levels, but only when females endured early low antioxidant values. This was probably related to the higher attractiveness of these females. Nevertheless, the bill redness of males did not differ during the social manipulation. Moreover, males facing females from any early condition group showed lower oxidative damage levels in plasma lipids. This result agrees with some findings in rodents, also in captivity. However, the effect may be due to increased triglyceride levels and body mass in males not facing females, as variation in these traits explained oxidative damage variability. The importance of considering housing conditions and life history when interpreting oxidative stress-related trade

Impact of SO2 and NO on CO Oxidation under Post-Flame Conditions

DEFF Research Database (Denmark)

Glarborg, Peter; Kubel, Dorte; Dam-Johansen, Kim

1996-01-01

An experimental and theoretical study of the effect of SO2 on moist CO oxidation with and without NO present was carried out under plug-flow conditions. The H/S/O thermochemistry and reaction subset was revised and a chemical kinetic model established that provide a good description of the effect...... of SO2 and NO on CO oxidation as well as the SO2/SO3 ratio in the products....

In situ Raman Spectroscopy of Oxide Films on Zirconium Alloy in Simulated PWR Primary Water Condition

Energy Technology Data Exchange (ETDEWEB)

Kim, Tae Ho; Choi, Kyoung Joon; Yoo, Seung Chang; Kim, Ji Hyun [UNIST, Ulsan (Korea, Republic of)

2016-05-15

The two layered oxide structure is formed in pre-transition oxide for the zirconium alloy in high temperature water environment. It is known that the corrosion rate is related to the volume fraction of zirconium oxide and the pores in the oxides; therefore, the aim of this paper is to investigate the oxidation behavior in the pretransition zirconium oxide in high-temperature water chemistry. In this work, Raman spectroscopy was used for in situ investigations for characterizing the phase of zirconium oxide. In situ Raman spectroscopy is a well-suited technique for investigating in detail the characteristics of oxide films in a high-temperature corrosion environment. In previous studies, an in situ Raman system was developed for investigating the oxides on nickel-based alloys and low alloy steels in high-temperature water environment. Also, the early stage oxidation behavior of zirconium alloy with different dissolved hydrogen concentration environments in high temperature water was treated in the authors' previous study. In this study, a specific zirconium alloy was oxidized and investigated with in situ Raman spectroscopy for 100 d oxidation, which is close to the first transition time of the zirconium alloy oxidation. The ex situ investigation methods such as transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) were used to further characterize the zirconium oxide structure. As oxidation time increased, the Raman peaks of tetragonal zirconium oxide were merged or became weaker. However, the monoclinic zirconium oxide peaks became distinct. The tetragonal zirconium oxide was just found near the O/M interface and this could explain the Raman spectra difference between the 30 d result and others.

High Performance Nano-Crystalline Oxide Fuel Cell Materials. Defects, Structures, Interfaces, Transport, and Electrochemistry

Energy Technology Data Exchange (ETDEWEB)

Barnett, Scott [Northwestern Univ., Evanston, IL (United States); Poeppelmeier, Ken [Northwestern Univ., Evanston, IL (United States); Mason, Tom [Northwestern Univ., Evanston, IL (United States); Marks, Lawrence [Northwestern Univ., Evanston, IL (United States); Voorhees, Peter [Northwestern Univ., Evanston, IL (United States)

2016-09-07

This project addresses fundamental materials challenges in solid oxide electrochemical cells, devices that have a broad range of important energy applications. Although nano-scale mixed ionically and electronically conducting (MIEC) materials provide an important opportunity to improve performance and reduce device operating temperature, durability issues threaten to limit their utility and have remained largely unexplored. Our work has focused on both (1) understanding the fundamental processes related to oxygen transport and surface-vapor reactions in nano-scale MIEC materials, and (2) determining and understanding the key factors that control their long-term stability. Furthermore, materials stability has been explored under the “extreme” conditions encountered in many solid oxide cell applications, i.e, very high or very low effective oxygen pressures, and high current density.

Some observations on the high temperature oxidation behaviour of plasma sprayed Ni3Al coatings

International Nuclear Information System (INIS)

Singh, H.; Prakash, S.; Puri, D.

2007-01-01

High temperature oxidation resistance of the superalloys can be greatly enhanced by plasma sprayed coatings and this is a growing industry of considerable economic importance. The purpose of these coatings is to form long-lasting oxidation protective scales. In the current investigation, Ni 3 Al powder was prepared by mechanical mixing of pure nickel and aluminium powders in a ball mill. Subsequently Ni 3 Al powder was deposited on three Ni-base superalloys: Superni 600, Superni 601 and Superni 718 and, one Fe-base superalloy, Superfer 800H by shrouded plasma spray process. Oxidation studies were conducted on the coated superalloys in air at 900 deg. C under cyclic conditions for 50 cycles. Each cycle consisted of 1 h heating followed by 20 min of cooling in air. The thermogravimetric technique was used to approximate the kinetics of oxidation. All the coated superalloys nearly followed parabolic rate law of oxidation. X-ray diffraction, SEM/EDAX and EPMA techniques were used to analyse the oxidation products. The Ni 3 Al coating was found to be successful in maintaining its adherence to the superalloy substrates in all the cases. The oxide scales formed on the oxidised coated superalloys were found to be intact and spallation-free. XRD analysis revealed the presence of phases like NiO, Al 2 O 3 and NiAl 2 O 4 in the oxide scales, which are reported as protective oxides against high temperature oxidation. The XRD results were further supported by SEM/EDAX and EPMA

Oxidation of zircaloy-2 in high temperature steam

International Nuclear Information System (INIS)

Ikeda, Seiichi; Ito, Goro; Ohashi, Shigeo

1975-01-01

Oxidation tests were conducted for zircaloy-2 in steam at temperature ranging from 900 to 1300 0 C to clarify its oxidation kinetics as a nuclear fuel cladding materials in case of a loss-of-coolant accident. The influence of maximum temperature and heating rate of the specimen on its oxidation rate in steam was investigated. The changes in mechanical properties of the specimens after oxidation tests are also studied. The results obtained were summarized as follows: (1) The weight of the specimen after oxidation in steam increased two times as the time required to reach the maximum temperature increased from 1 to 10 mins. (2) The kinetics of oxidation of zircaloy-2 in steam were not affected by the difference in the surface condition before test such as chemical polishing or pre-oxidation in steam. (3) The dominant growth of oxide film on the surface of zircaloy-2 was observed at the initial stage of oxidation in steam. However, the thickness of oxygen-rich solid solution layer under the film increased gradually with the progress of oxidation and the ratio of oxygen in oxide to that in solid solution has a constant value of 8:2. (4) The breakaway took place only in the specimen subjected to 900 0 C repeated heating. This penomenon was caused by the local growth of the oxide below a crack of the oxide film resulting from the reheating of the specimen. (5) The results of bending tests showed that the deflection until fracture of the specimen was smaller for the one heated at a higher temperature even if the weight increase was of the same order of magnitude for both specimens. (6) It was concluded that the ductility of zircaloy-2 decreased remarkably at a heating temperature in excess of 1100 0 C for more than 5 min. (auth.)

Redox conditions and protein oxidation in plant mitochondria

DEFF Research Database (Denmark)

Møller, Ian Max; Kasimova, Marina R.; Krab, Klaas

2005-01-01

Redox conditions and protein oxidation in plant mitochondria NAD(P)H has a central position in respiratory metabolism. It is produced by a large number of enzymes, e.g. the Krebs cycle dehydrogenases, in the mitochondrial matrix and is oxidised by, amongst others, the respiratory chain. Most...... of this NAD(P)H appears to be bound to proteins, in fact free NAD(P)H – an important parameter in metabolic regulation - has never been observed in mitochondria. We have estimated free and bound NAD(P)H in isolated plant mitochondria under different metabolic conditions. The fluorescence spectra of free...... and bound NADH was determined and used to deconvolute fluorescence spectra of actively respiring mitochondria. Most of the mitochondrial NADH is bound in states 2 and 4. The amount of free NADH is lower but relatively constant even increasing a little in state 3 where it is about equal to bound NADH...

High Efficient Reduction of Graphene Oxide via Nascent Hydrogen at Room Temperature

Directory of Open Access Journals (Sweden)

Qiqi Zhuo

2018-02-01

Full Text Available To develop a green and efficient method to synthesize graphene in relative milder conditions is prerequisite for graphene applications. A chemical reducing method has been developed to high efficiently reduce graphene oxide (GO using Fe2O3 and NH3BH3 as catalyst and reductants, respectively. During the process, environmental and strong reductive nascent hydrogen were generated surrounding the surface of GO sheets by catalyst hydrolysis reaction of NH3BH3 and were used for reduction of GO. The reduction process was studied by ultraviolet absorption spectroscopy, Raman spectroscopy, and Fourier transform infrared spectrum. The structure and morphology of the reduced GO were characterized with scanning electron microscopy and transmission electron microscopy. Compared to metal (Mg/Fe/Zn/Al particles and acid system which also use nascent hydrogen to reduce GO, this method exhibited higher reduction efficiency (43.6%. Also the reduction was carried out at room temperature condition, which is environmentally friendly. As a supercapacitor electrode, the reversible capacity of reduced graphene oxide was 113.8 F g−1 at 1 A g−1 and the capacitance retention still remained at 90% after 200 cycles. This approach provides a new method to reduce GO with high reduction efficiency by green reductant.

Modeling of the chemistry in oxidation flow reactors with high initial NO

Science.gov (United States)

Peng, Zhe; Jimenez, Jose L.

2017-10-01

Oxidation flow reactors (OFRs) are increasingly employed in atmospheric chemistry research because of their high efficiency of OH radical production from low-pressure Hg lamp emissions at both 185 and 254 nm (OFR185) or 254 nm only (OFR254). OFRs have been thought to be limited to studying low-NO chemistry (in which peroxy radicals (RO2) react preferentially with HO2) because NO is very rapidly oxidized by the high concentrations of O3, HO2, and OH in OFRs. However, many groups are performing experiments by aging combustion exhaust with high NO levels or adding NO in the hopes of simulating high-NO chemistry (in which RO2 + NO dominates). This work systematically explores the chemistry in OFRs with high initial NO. Using box modeling, we investigate the interconversion of N-containing species and the uncertainties due to kinetic parameters. Simple initial injection of NO in OFR185 can result in more RO2 reacted with NO than with HO2 and minor non-tropospheric photolysis, but only under a very narrow set of conditions (high water mixing ratio, low UV intensity, low external OH reactivity (OHRext), and initial NO concentration (NOin) of tens to hundreds of ppb) that account for a very small fraction of the input parameter space. These conditions are generally far away from experimental conditions of published OFR studies with high initial NO. In particular, studies of aerosol formation from vehicle emissions in OFRs often used OHRext and NOin several orders of magnitude higher. Due to extremely high OHRext and NOin, some studies may have resulted in substantial non-tropospheric photolysis, strong delay to RO2 chemistry due to peroxynitrate formation, VOC reactions with NO3 dominating over those with OH, and faster reactions of OH-aromatic adducts with NO2 than those with O2, all of which are irrelevant to ambient VOC photooxidation chemistry. Some of the negative effects are the worst for alkene and aromatic precursors. To avoid undesired chemistry, vehicle emissions

High-temperature oxidation of ion-implanted tantalum

International Nuclear Information System (INIS)

Kaufmann, E.N.; Musket, R.G.; Truhan, J.J.; Grabowski, K.S.; Singer, I.L.; Gossett, C.R.

1982-01-01

The oxidation of ion-implanted Ta in two different high temperature regimes has been studied. Oxidations were carried out at 500 0 C in Ar/O 2 mixtures, where oxide growth is known to follow a parabolic rate law in initial stages, and at 1000 0 C in pure O 2 , where a linear-rate behavior obtains. Implanted species include Al, Ce, Cr, Li, Si and Zr at fluences of the order of 10 17 /cm 2 . Oxidized samples were studied using Rutherford backscattering, nuclear reaction analysis, Auger spectroscopy, secondary-ion mass spectroscopy, x-ray diffraction and optical microscopy. Significant differences among the specimens were noted after the milder 500 0 C treatment, specifically, in the amount of oxide formed, the degree of oxygen dissolution in the metal beneath the oxide, and in the redistribution behavior of the implanted solutes. Under the severe 1000 0 C treatment, indications of different solute distributions and of different optical features were found, whereas overall oxidation rate appeared to be unaffected by the presence of the solute. 7 figures

The Effect Of The Reactive Element On The CHROMOXIDE And Aluminide Layers In The High Temperature Condition

International Nuclear Information System (INIS)

Dani, Mohammad; Effendi, Nurdin

2000-01-01

Oxide layers at high temperature condition, as Cr 2 O 3 , AI 2 O 3 , growing act not only as corrosion barrier, but also as a diffusion barrier of agressive components. MA956 and Ni75Cr25 alloy were studied to observe the elIect of Yttrium coating on their oxidation behavior. The influence ofthese coatings on the oxidation behaviour of the alloy was studied, Thin coatings of Yttrium have been applied to the surface of those alloys by vacuum coating The growth of the oxide layers under controlled has been investigated in this work by Analytical Transmission Electron Microscope (ATEM) and Scanning Electron Microscopy (SEM), It was found that addition of small amounts of elements such as Yttrium to these alloys greatly increase their oxidation resistance,

Oxidation of adsorbed ferrous iron: kinetics and influence of process conditions.

Science.gov (United States)

Buamah, R; Petrusevski, B; Schippers, J C

2009-01-01

For the removal of iron from groundwater, aeration followed with rapid (sand) filtration is frequently applied. Iron removal in this process is achieved through oxidation of Fe(2 + ) in aqueous solution followed by floc formation as well as adsorption of Fe(2 + ) onto the filter media. The rate of oxidation of the adsorbed Fe(2 + ) on the filter media plays an important role in this removal process. This study focuses on investigating the effect of pH on the rate of oxidation of adsorbed Fe(2 + ). Fe(2 + ) has been adsorbed, under anoxic conditions, on iron oxide coated sand (IOCS) in a short filter column and subsequently oxidized by feeding the column with aerated water. Ferrous ions adsorbed at pH 5, 6, 7 and 8 demonstrated consumption of oxygen, when aerated water was fed into the column. The oxygen uptake at pH 7 and 8 was faster than at pH 5 and 6. However the difference was less pronounced than expected. The difference is attributed to the pH buffering effect of the IOCS. At feedwater pH 5, 6 and 7 the pH in the effluent was higher than in the influent, while a pH drop should occur because of oxidation of adsorbed Fe(2 + ). At pH 8, the pH dropped. These phenomena are attributed to the presence of calcium and /or ferrous carbonate in IOCS.

Pressure effects on high temperature steam oxidation of Zircaloy-4

International Nuclear Information System (INIS)

Park, Kwangheon; Kim, Kwangpyo; Ryu, Taegeun

2000-01-01

The pressure effects on Zircaloy-4 (Zry-4) cladding in high temperature steam have been analyzed. A double layer autoclave was made for the high pressure, high temperature oxidation tests. The experimental test temperature range was 700 - 900 deg C, and pressures were 0.1 - 15 MPa. Steam partial pressure turns out to be an important one rather than total pressure. Steam pressure enhances the oxidation rate of Zry-4 exponentially. The enhancement depends on the temperature, and the maximum exists between 750 - 800 deg C. Pre-existing oxide layer decreases the enhancement about 40 - 60%. The acceleration of oxidation rate by high pressure team seems to be originated from the formation of cracks by abrupt transformation of tetragonal phase in oxide, where the un-stability of tetragonal phase comes from the reduction of surface energy by steam. (author)

Effect of fabrication conditions on the properties of indium tin oxide powders

International Nuclear Information System (INIS)

Xie Wei

2008-01-01

This paper reports that indium tin oxide (ITO) crystalline powders are prepared by coprecipitation method. Fabrication conditions mainly as sintering temperature and Sn doping content are correlated with the phase, microstructure, infrared emissivity in and powder resistivity of indium tin oxides by means of x-ray diffraction, Fourier transform infrared, and transmission electron microscope. The optimum sintering temperature of 1350°C and Sn doping content 6∼8wt% are determined. The application of ITO in the military camouflage field is proposed. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

Experimental and numerical study of the effects of a nanocrystallisation treatment on high-temperature oxidation of a zirconium alloy

International Nuclear Information System (INIS)

Panicaud, B.; Retraint, D.; Grosseau-Poussard, J.-L.; Li, L.; Guérain, M.; Goudeau, P.; Tamura, N.; Kunz, M.

2012-01-01

Highlights: ► SMAT leads to a modification of surface properties of an M5 zirconium alloy (grain size and roughness. ► SMAT induces a change in the oxidation kinetics during high temperature oxidation. ► A diffusion model is able to reproduce kinetics and emphasise the consequences of SMAT on dissolution of oxygen in Zr. - Abstract: In the present work, the effects of a nanocrystallisation treatment on the high-temperature oxidation of a zirconium alloy are investigated. Surface Mechanical Attrition Treatment is a recent process designed to nanocrystallise the surface of materials. The particular effects of this treatment on an M5 zirconium alloy are studied using different experimental techniques at several scales. This material is of considerable interest, especially to the nuclear industry where very stringent conditions apply. High temperature oxidation was performed in order to show the benefits of this type of nanocrystallisation on the corrosion resistance of the alloy concerned. Microstructure development mechanisms, which improve the oxidation resistance of zirconium alloys have been identified during high-temperature corrosion. Those mechanisms have been discussed in further detail in relation to numerical calculations concerning the oxidation kinetics.

Sintering Characteristics of Multilayered Thermal Barrier Coatings Under Thermal Gradient and Isothermal High Temperature Annealing Conditions

Science.gov (United States)

Rai, Amarendra K.; Schmitt, Michael P.; Bhattacharya, Rabi; Zhu, Dongming; Wolfe, Douglas E.

2014-01-01

Pyrochlore oxides have most of the relevant attributes for use as next generation thermal barrier coatings such as phase stability, low sintering kinetics and low thermal conductivity. One of the issues with the pyrochlore oxides is their lower toughness and therefore higher erosion rate compared to the current state-of-the-art TBC material, yttria (6 to 8 wt%) stabilized zirconia (YSZ). In this work, sintering characteristics were investigated for novel multilayered coating consisted of alternating layers of pyrochlore oxide viz Gd2Zr2O7 and t' low k (rare earth oxide doped YSZ). Thermal gradient and isothermal high temperature (1316 C) annealing conditions were used to investigate sintering and cracking in these coatings. The results are then compared with that of relevant monolayered coatings and a baseline YSZ coating.

Trends for Methane Oxidation at Solid Oxide Fuel Cell Conditions

DEFF Research Database (Denmark)

Kleis, Jesper; Jones, Glenn; Abild-Pedersen, Frank

2009-01-01

First-principles calculations are used to predict a plausible reaction pathway for the methane oxidation reaction. In turn, this pathway is used to obtain trends in methane oxidation activity at solid oxide fuel cell (SOFC) anode materials. Reaction energetics and barriers for the elementary...... the Ni surfaces to other metals of interest. This allows the reactivity over the different metals to be understood in terms of two reactivity descriptors, namely, the carbon and oxygen adsorption energies. By combining a simple free-energy analysis with microkinetic modeling, activity landscapes of anode...

submitter Elemental composition and clustering behaviour of α-pinene oxidation products for different oxidation conditions

CERN Document Server

Praplan, A P; Bianchi, F; Rissanen, M P; Ehn, M; Jokinen, T; Junninen, H; Adamov, A; Amorim, A; Dommen, J; Duplissy, J; Hakala, J; Hansel, A; Heinritzi, M; Kangasluoma, J; Kirkby, J; Krapf, M; Kürten, A; Lehtipalo, K; Riccobono, F; Rondo, L; Sarnela, N; Simon, M; Tomé, A; Tröstl, J; Winkler, P M; Williamson, C; Ye, P; Curtius, J; Baltensperger, U; Donahue, N M; Kulmala, M; Worsnop, D R

2015-01-01

This study presents the difference between oxidised organic compounds formed by α-pinene oxidation under various conditions in the CLOUD environmental chamber: (1) pure ozonolysis (in the presence of hydrogen as hydroxyl radical (OH) scavenger) and (2) OH oxidation (initiated by nitrous acid (HONO) photolysis by ultraviolet light) in the absence of ozone. We discuss results from three Atmospheric Pressure interface Time-of-Flight (APi-TOF) mass spectrometers measuring simultaneously the composition of naturally charged as well as neutral species (via chemical ionisation with nitrate). Natural chemical ionisation takes place in the CLOUD chamber and organic oxidised compounds form clusters with nitrate, bisulfate, bisulfate/sulfuric acid clusters, ammonium, and dimethylaminium, or get protonated. The results from this study show that this process is selective for various oxidised organic compounds with low molar mass and ions, so that in order to obtain a comprehensive picture of the elemental composition o...

La-doped Al2O3 supported Au nanoparticles: highly active and selective catalysts for PROX under PEMFC operation conditions.

Science.gov (United States)

Lin, Qingquan; Qiao, Botao; Huang, Yanqiang; Li, Lin; Lin, Jian; Liu, Xiao Yan; Wang, Aiqin; Li, Wen-Cui; Zhang, Tao

2014-03-14

La-doped γ-Al2O3 supported Au catalysts show high activity and selectivity for the PROX reaction under PEMFC operation conditions. The superior performance is attributed to the formation of LaAlO3, which suppresses H2 oxidation and strengthens CO adsorption on Au sites, thereby improving competitive oxidation of CO at elevated temperature.

Indium oxide co-doped with tin and zinc: A simple route to highly conducting high density targets for TCO thin-film fabrication

Science.gov (United States)

Saadeddin, I.; Hilal, H. S.; Decourt, R.; Campet, G.; Pecquenard, B.

2012-07-01

Indium oxide co-doped with tin and zinc (ITZO) ceramics have been successfully prepared by direct sintering of the powders mixture at 1300 °C. This allowed us to easily fabricate large highly dense target suitable for sputtering transparent conducting oxide (TCO) films, without using any cold or hot pressing techniques. Hence, the optimized ITZO ceramic reaches a high relative bulk density (˜ 92% of In2O3 theoretical density) and higher than the well-known indium oxide doped with tin (ITO) prepared under similar conditions. All X-ray diagrams obtained for ITZO ceramics confirms a bixbyte structure typical for In2O3 only. This indicates a higher solubility limit of Sn and Zn when they are co-doped into In2O3 forming a solid-solution. A very low value of electrical resistivity is obtained for [In2O3:Sn0.10]:Zn0.10 (1.7 × 10-3 Ω cm, lower than ITO counterpart) which could be fabricated to high dense ceramic target suing pressure-less sintering.

Manganese oxide micro-supercapacitors with ultra-high areal capacitance

Science.gov (United States)

Wang, Xu; Myers, Benjamin D.; Yan, Jian; Shekhawat, Gajendra; Dravid, Vinayak; Lee, Pooi See

2013-05-01

A symmetric micro-supercapacitor is constructed by electrochemically depositing manganese oxide onto micro-patterned current collectors. High surface-to-volume ratio of manganese oxide and short diffusion distance between electrodes give an ultra-high areal capacitance of 56.3 mF cm-2 at a current density of 27.2 μA cm-2.A symmetric micro-supercapacitor is constructed by electrochemically depositing manganese oxide onto micro-patterned current collectors. High surface-to-volume ratio of manganese oxide and short diffusion distance between electrodes give an ultra-high areal capacitance of 56.3 mF cm-2 at a current density of 27.2 μA cm-2. Electronic supplementary information (ESI) available: Experimental procedures; optical images of micro-supercapacitors; areal capacitances of samples M-0.3C, M-0.6C and M-0.9C; illustration of interdigital finger electrodes; Nyquist plot of Co(OH)2 deposited on micro-electrodes. See DOI: 10.1039/c3nr00210a

Oxidative degradation of polybenzimidazole membranes as electrolytes for high temperature proton exchange membrane fuel cells

DEFF Research Database (Denmark)

Liao, J.H.; Li, Qingfeng; Rudbeck, H.C.

2011-01-01

the oxidative degradation of the polymer membrane was studied under the Fenton test conditions by the weight loss, intrinsic viscosity, size exclusion chromatography, scanning electron microscopy and Fourier transform infrared spectroscopy. During the Fenton test, significant weight losses depending...... on the initial molecular weight of the polymer were observed. At the same time, viscosity and SEC measurements revealed a steady decrease in molecular weight. The degradation of acid doped PBI membranes under Fenton test conditions is proposed to start by the attack of hydroxyl radicals at the carbon atom......Polybenzimidazole membranes imbibed with acid are emerging as a suitable electrolyte material for high-temperature polymer electrolyte fuel cells. The oxidative stability of polybenzimidazole has been identified as an important issue for the long-term durability of such cells. In this paper...

Transcriptional Response of Desulfovibrio vulgaris Hildenborough to Oxidative Stress Mimicking Environmental Conditions

Energy Technology Data Exchange (ETDEWEB)

Pereira, Patricia M.; He, Qiang; Xavier, Antonio V.; Zhou, Jizhong; Pereira, Ines A.C.; Louro, Ricardo O.

2008-03-12

Sulphate-reducing bacteria are anaerobes readily found in oxic-anoxic interfaces. Multiple defence pathways against oxidative conditions were identified in these organisms and proposed to be differentially expressed under different concentrations of oxygen, contributing to their ability to survive oxic conditions. In this study, Desulfovibrio vulgaris Hildenborough cells were exposed to the highest concentration of oxygen that sulphate-reducing bacteria are likely to encounter in natural habitats, and the global transcriptomic response was determined. 307 genes were responsive, with cellular roles in energy metabolism, protein fate, cell envelope and regulatory functions, including multiple genes encoding heat shock proteins, peptidases and proteins with heat shock promoters. Of the oxygen reducing mechanisms of D. vulgaris only the periplasmic hydrogen-dependent mechanism is up-regulated, involving the [NiFeSe]hydrogenase, formate dehydrogenase(s) and the Hmc membrane complex. The oxidative defence response concentrates on damage repair by metal-free enzymes. These data, together with the down regulation of the Fur operon, which restricts the availability of iron, and the lack of response of the PerR operon, suggest that a major effect of this oxygen stress is the inactivation and/or degradation of multiple metalloproteins present in D. vulgaris as a consequence of oxidative damage to their metal clusters.

Iron-Mediated Oxidation of Methoxyhydroquinone under Dark Conditions: Kinetic and Mechanistic Insights.

Science.gov (United States)

Yuan, Xiu; Davis, James A; Nico, Peter S

2016-02-16

Despite the biogeochemical significance of the interactions between natural organic matter (NOM) and iron species, considerable uncertainty still remains as to the exact processes contributing to the rates and extents of complexation and redox reactions between these important and complex environmental components. Investigations on the reactivity of low-molecular-weight quinones, which are believed to be key redox active compounds within NOM, toward iron species, could provide considerable insight into the kinetics and mechanisms of reactions involving NOM and iron. In this study, the oxidation of 2-methoxyhydroquinone (MH2Q) by ferric iron (Fe(III)) under dark conditions in the absence and presence of oxygen was investigated within a pH range of 4-6. Although Fe(III) was capable of stoichiometrically oxidizing MH2Q under anaerobic conditions, catalytic oxidation of MH2Q was observed in the presence of O2 due to further cycling between oxygen, semiquinone radicals, and iron species. A detailed kinetic model was developed to describe the predominant mechanisms, which indicated that both the undissociated and monodissociated anions of MH2Q were kinetically active species toward Fe(III) reduction, with the monodissociated anion being the key species accounting for the pH dependence of the oxidation. The generated radical intermediates, namely semiquinone and superoxide, are of great importance in reaction-chain propagation. The kinetic model may provide critical insight into the underlying mechanisms of the thermodynamic and kinetic characteristics of metal-organic interactions and assist in understanding and predicting the factors controlling iron and organic matter transformation and bioavailability in aquatic systems.

rGO-ZnO nanocomposites for high electrocatalytic effect on water oxidation obtained by microwave-hydrothermal method

Science.gov (United States)

Romeiro, Fernanda C.; Rodrigues, Mônica A.; Silva, Luiz A. J.; Catto, Ariadne C.; da Silva, Luis F.; Longo, Elson; Nossol, Edson; Lima, Renata C.

2017-11-01

Reduced graphene oxide-zinc oxide (rGO-ZnO) nanocomposites were successfully synthesized using a facile microwave-hydrothermal method under mild conditions, and their electrocatalytic properties towards O2 evolution were investigated. The microwave radiation played an important role in obtainment of well dispersed ZnO nanoparticles directly on reduced graphene oxide sheets without any additional reducing reagents or passivation agent. X-ray diffraction (XRD), Raman and infrared spectroscopies indicated the reduction of GO as well as the successful synthesis of rGO-ZnO nanocomposites. The chemical states of the samples were shown by XPS analyses. Due to the synergic effect, the resulting nanocomposites exhibited high electronic interaction between ZnO and rGO sheets, which improved the electrocatalytic oxidation of water with low onset potential of 0.48 V (vs. Ag/AgCl) in neutral pH and long-term stability, with high current density during electrolysis. The overpotential for water oxidation decreased in alkaline pH, suggesting useful insight on the catalytic mechanism for O2 evolution.

Condition of pro-oxidant and antioxidant systems in guinea pigs’ lungs under the condition of immobilization stress

Directory of Open Access Journals (Sweden)

Mykhailo Stepanovych Reheda

2017-11-01

Full Text Available We have investigated the results of alterations in indices of pro-oxidant (conjugated diene and malondialdehyde and antioxidant (superoxide dismutase, ceruloplasmin, catalase systems in guinea pigs’ lungs  under the conditions of immobilization stress. The experiment was conducted on 40 female guinea pigs weighing 0.18-0.20 kg. The animals were divided into 4 groups, each contained 10 guinea pigs: I – intact guinea pigs ( control, II–guinea pigs with model of IS on1st day of experiment;Ш–animals on 2nd  day of experiment;IV- group of animals on 34th day of experimental model of IS. The results of our experimental work showed  a significant accumulation of lipid peroxidation products in the lung`s tissure in different periods ( on 1st, 2nd and 34th days of immobilization stress. The state of antioxidant defence was characterized by moderate decrease of inzymes activity (superoxide dismutase, catalase and ceruloplasmin. disorders of balance between pro-oxidant and antioxidant systems couse oxidative stress development.

High temperature oxidation of slurry coated interconnect alloys

DEFF Research Database (Denmark)

Persson, Åsa Helen

with this interaction mechanism mainly give a geometrical protection against oxidation by blocking oxygen access at the surface of the oxide scale. The protecting effect is gradually reduced as the oxide scale grows thicker than the diameter of the coating particles. Interaction mechanism B entails a chemical reaction...... scale. The incorporated coating particles create a geometrical protection against oxidation that should not loose their effect after the oxide scale has grown thicker than the diameter of the coating particles. The two single layer coatings consisting of (La0.85Sr0.15)MnO3 + 10% excess Mn, LSM, and (La0......In this project, high temperature oxidation experiments of slurry coated ferritic alloys in atmospheres similar to the atmosphere found at the cathode in an SOFC were conducted. From the observations possible interaction mechanisms between the slurry coatings and the growing oxide scale...

Interfacial failure in dissimilar weld joint of high boron 9% chromium steel and nickel-based alloy under high-temperature creep condition

Energy Technology Data Exchange (ETDEWEB)

Matsunaga, Tetsuya, E-mail: MATSUNAGA.Tetsuya@nims.go.jp; Hongo, Hiromichi, E-mail: HONGO.Hiromichi@nims.go.jp; Tabuchi, Masaaki, E-mail: TABUCHI.Masaaki@nims.go.jp

2017-05-17

The advanced ultra-supercritical (A-USC) power generation system is expected to become the next-generation base-load power station in Japan. Dissimilar weld joints between high-Cr heat-resistant steels and nickel-based alloys with a nickel-based filler metal (Alloy 82) will need to be adopted for this purpose. However, interfacial failure between the steels and weld metal has been observed under high-temperature creep conditions. Fractography and microstructure observations showed the failure initiated in a brittle manner by an oxide notch at the bottom of the U-groove. The fracture then proceeded along the bond line in a ductile manner with shallow dimples, where micro-Vickers hardness tests showed remarkable softening in the steel next to the bond line. In addition, the steel showed a much larger total elongation and reduction of area than the weld metal at low stresses under long-term creep conditions, leading to mismatch deformation at the interface. According to the results, it can be concluded that the interfacial failure between the 9Cr steels and Alloy 82 weld metal is initiated by an oxide notch and promoted by softening and the difference in the plasticity of the steels and weld metal.

Quantities of Interest in Jet Stirred Reactor Oxidation of a High-Octane Gasoline

KAUST Repository

Chen, Bingjie

2017-03-28

This work examines the oxidation of a well-characterized, high-octane-number FACE (fuel for advanced combustion engines) F gasoline. Oxidation experiments were performed in a jet-stirred reactor (JSR) for FACE F gasoline under the following conditions: pressure, 10 bar; temperature, 530-1250 K; residence time, 0.7s; equivalence ratios, 0.5, 1.0, and 2.0. Detailed species profiles were achieved by identification and quantification from gas chromatography with mass spectrometry (GC-MS) and Fourier transform infrared spectrometry (FTIR). Four surrogates, with physical and chemical properties that mimic the real fuel properties, were used for simulations, with a detailed gasoline surrogate kinetic model. Fuel and species profiles were well-captured and-predicted by comparisons between experimental results and surrogate simulations. Further analysis was performed using a quantities of interest (QoI) approach to show the differences between experimental and simulation results and to evaluate the gasoline surrogate kinetic model. Analysis of the multicomponent surrogate kinetic model indicated that iso-octane and alkyl aromatic oxidation reactions had impact on species profiles in the high-temperature region;. however, the main production and consumption channels were related to smaller molecule reactions. The results presented here offer new insights into the oxidation chemistry of complex gasoline fuels and provide suggestions for the future development of surrogate kinetic models.

Highly selective oxidation of styrene to benzaldehyde over a tailor-made cobalt oxide encapsulated zeolite catalyst.

Science.gov (United States)

Liu, Jiangyong; Wang, Zihao; Jian, Panming; Jian, Ruiqi

2018-05-01

A tailor-made catalyst with cobalt oxide particles encapsulated into ZSM-5 zeolites (Co 3 O 4 @HZSM-5) was prepared via a hydrothermal method with the conventional impregnated Co 3 O 4 /SiO 2 catalyst as the precursor and Si source. Various characterization results show that the Co 3 O 4 @HZSM-5 catalyst has well-organized structure with Co 3 O 4 particles compatibly encapsulated in the zeolite crystals. The Co 3 O 4 @HZSM-5 catalyst was employed as an efficient catalyst for the selective oxidation of styrene to benzaldehyde with hydrogen peroxide as a green and economic oxidant. The effect of various reaction conditions including reaction time, reaction temperature, different kinds of solvents, styrene/H 2 O 2 molar ratio and catalyst dosage on the catalytic performance were systematically investigated. Under the optimized reaction condition, the yield of benzaldehyde can achieve 78.9% with 96.8% styrene conversion and 81.5% benzaldehyde selectivity. Such an excellent catalytic performance can be attributed to the synergistic effect between the confined reaction environment and the proper acidic property. In addition, the reaction mechanism with Co 3 O 4 @HZSM-5 as the catalyst for the selective oxidation of styrene to benzaldehyde was reasonably proposed. Copyright © 2018 Elsevier Inc. All rights reserved.

High permittivity materials for oxide gate stack in Ge-based metal oxide semiconductor capacitors

Energy Technology Data Exchange (ETDEWEB)

Molle, Alessandro, E-mail: alessandro.molle@mdm.infm.i [Laboratorio Nazionale MDM, CNR-INFM, via C. Olivetti 2, 20041 Agrate Brianza, Milano (Italy); Baldovino, Silvia [Laboratorio Nazionale MDM, CNR-INFM, via C. Olivetti 2, 20041 Agrate Brianza, Milano (Italy); Dipartimento di Scienza dei Materiali, Universita degli Studi di Milano Bicocca, Milano (Italy); Spiga, Sabina [Laboratorio Nazionale MDM, CNR-INFM, via C. Olivetti 2, 20041 Agrate Brianza, Milano (Italy); Fanciulli, Marco [Laboratorio Nazionale MDM, CNR-INFM, via C. Olivetti 2, 20041 Agrate Brianza, Milano (Italy); Dipartimento di Scienza dei Materiali, Universita degli Studi di Milano Bicocca, Milano (Italy)

2010-01-01

In the effort to ultimately shrink the size of logic devices towards a post-Si era, the integration of Ge as alternative channel material for high-speed p-MOSFET devices and the concomitant coupling with high permittivity dielectrics (high-k) as gate oxides is currently a key-challenge in microelectronics. However, the Ge option still suffers from a number of unresolved drawbacks and open issues mainly related to the thermodynamic and electrical compatibility of Ge substrates with high-k gate stack. Strictly speaking, two main concerns can be emphasized. On one side is the dilemma on which chemical/physical passivation is more suitable to minimize the unavoidable presence of electrically active defects at the oxide/semiconductor interface. On the other side, overcoming the SiO{sub 2} gate stack opens the route to a number of potentially outperforming high-k oxides. Two deposition approaches were here separately adopted to investigate the high-k oxide growth on Ge substrates, the molecular beam deposition (MBD) of Gd{sub 2}O{sub 3} and the atomic layer deposition (ALD) of HfO{sub 2}. In the MBD framework epitaxial and amorphous Gd{sub 2}O{sub 3} films were grown onto GeO{sub 2}-passivated Ge substrates. In this case, Ge passivation was achieved by exploiting the Ge{sup 4+} bonding state in GeO{sub 2} ultra-thin interface layers intentionally deposited in between Ge and the high-k oxide by means of atomic oxygen exposure to Ge. The composition of the interface layer has been characterized as a function of the oxidation temperature and evidence of Ge dangling bonds at the GeO{sub 2}/Ge interface has been reported. Finally, the electrical response of MOS capacitors incorporating Gd{sub 2}O{sub 3} and GeO{sub 2}-passivated Ge substrates has been checked by capacitance-voltage measurements. On the other hand, the structural and electrical properties of HfO{sub 2} films grown by ALD on Ge by using different oxygen precursors, i.e. H{sub 2}O, Hf(O{sup t}Bu){sub 2}(mmp

Lipolysis and lipid oxidation in fermented sausages depending on different processing conditions and different antioxidants.

Science.gov (United States)

Zanardi, Emanuela; Ghidini, Sergio; Battaglia, Alessandra; Chizzolini, Roberto

2004-02-01

Lipolysis and lipid oxidation in Mediterranean and North Europe type sausages were studied in relation to raw material, processing conditions and additives. In particular the effect of ascorbic acid, nitrites and spices was evaluated. Lipolysis was measured by the determination of total and free fatty acids of fresh minces and matured products and lipid oxidation was evaluated by thiobarbituric acid reactive substances and cholesterol oxidation products. The increase of free fatty acids during maturation appears to be independent from processing conditions and the differences in polyunsaturated fatty acids increment found among the formulations appear to be due to inherent variations of raw materials. The presence of ascorbic acid and/or nitrite seems important for cholesterol protection and, as a consequence, for the safety of fermented meat products while spices at doses up to 0.1% do not seem to have a remarkable effect. The effect on fatty acid oxidation of the same additives and of the different processing technologies is not significantly different and the variations linked to raw material may play the greatest role.

Detection of high levels of pyrrolizidine-N-oxides in the endangered plant Cryptantha crassipes (Terlingua Creek cat's-eye) using HPLC-ESI-MS.

Science.gov (United States)

Williams, Maria T; Warnock, Bonnie J; Betz, Joseph M; Beck, John J; Gardner, Dale R; Lee, Stephen T; Molyneux, Russell J; Colegate, Steven M

2011-01-01

A previous investigation of pyrrolizidine alkaloids produced by nine species of Cryptantha identified at least two chemotypes within the genus. Other research has postulated that pyrrolizidine-N-oxide concentrations increase as the growing conditions become harsher, particularly with respect to water availability. Cryptantha crassipes is an endangered plant with a very limited distribution range within a dry, harsh Texan ecosystem. To determine the pyrrolizidine alkaloid (and their N-oxides) profile and concentrations in Cryptantha crassipes. Methanolic extracts of Cryptantha crassipes were partitioned into dilute sulphuric acid and the alkaloids concentrated using strong cation exchange, solid-phase extraction columns. Extracts were analysed using reversed-phase high-pressure liquid chromatography coupled to electrospray ionisation ion trap mass spectrometry. The N-oxides of lycopsamine and intermedine were the major pyrrolizidine alkaloids detected in Cryptantha crassipes. Smaller to trace amounts of other pyrrolizidine alkaloids observed were: the 7- and 3'-acetylated derivatives and the 1,2-dihydro analogs of lycopsamine-N-oxide and/or intermedine-N-oxide; a pair of unidentified N-oxides, isobaric with lycopsamine-N-oxide; and the N-oxides of leptanthine, echimiplatine, amabiline, echiumine and dihydroechiumine. Only trace amounts, if any, of the parent free base pyrrolizidine alkaloids were detected. The concentration of pyrrolizidine alkaloids was estimated to be 3-5% of the dry weight of milled leaves, or 10-50 times the levels previously reported for similar chemotypes. The high levels of the N-oxides of lycopsamine and intermedine establish the genus chemotype of the endangered Cryptantha crassipes and support earlier data linking high levels of N-oxides to dry, harsh growing conditions. Copyright © 2011 John Wiley & Sons, Ltd.

Characterization of ash melting behaviour at high temperatures under conditions simulating combustible solid waste gasification.

Science.gov (United States)

Niu, Miaomiao; Dong, Qing; Huang, Yaji; Jin, Baosheng; Wang, Hongyan; Gu, Haiming

2018-05-01

To achieve high-temperature gasification-melting of combustible solid waste, ash melting behaviour under conditions simulating high-temperature gasification were studied. Raw ash (RA) and gasified ash (GA) were prepared respectively by waste ashing and fluidized bed gasification. Results of microstructure and composition of the two-ash indicated that GA showed a more porous structure and higher content of alkali and alkali earth metals among metallic elements. Higher temperature promoted GA melting and could reach a complete flowing state at about 1250°C. The order of melting rate of GA under different atmospheres was reducing condition > inert condition > oxidizing condition, which might be related to different existing forms of iron during melting and different flux content with atmosphere. Compared to RA, GA showed lower melting activity at the same condition due to the existence of an unconverted carbon and hollow structure. The melting temperature for sufficient melting and separation of GA should be at least 1250°C in this work.

Oxidation resistant high creep strength austenitic stainless steel

Science.gov (United States)

Brady, Michael P.; Pint, Bruce A.; Liu, Chain-Tsuan; Maziasz, Philip J.; Yamamoto, Yukinori; Lu, Zhao P.

2010-06-29

An austenitic stainless steel displaying high temperature oxidation and creep resistance has a composition that includes in weight percent 15 to 21 Ni, 10 to 15 Cr, 2 to 3.5 Al, 0.1 to 1 Nb, and 0.05 to 0.15 C, and that is free of or has very low levels of N, Ti and V. The alloy forms an external continuous alumina protective scale to provide a high oxidation resistance at temperatures of 700 to 800.degree. C. and forms NbC nanocarbides and a stable essentially single phase fcc austenitic matrix microstructure to give high strength and high creep resistance at these temperatures.

Efficient assessment of modified nucleoside stability under conditions of automated oligonucleotide synthesis: characterization of the oxidation and oxidative desulfurization of 2-thiouridine.

Science.gov (United States)

Sochacka, E

2001-01-01

In order to efficiently assess the chemical stability of modified nucleosides to the reagents and conditions of automated oligonucleotide synthesis, we designed, developed and tested a scheme in which the modified nucleoside, directly attached to a solid support, is exposed to the cyclic chemistry of the instrument. Stability of 2-thiouridine against different oxidizers was investigated. Tertbutyl hydroperoxide (1 M) in anhydrous acetonitrile was a more effective oxidizer for the incorporation of 2-thiouridine into oligonucleotide chains than the same oxidizer in methylene chloride. Carbon tetrachloride/water in the presence of a basic catalyst was superior in maintaining the thiocarbonyl function, but its utility for RNA synthesis has yet to be fully tested, whereas 2-phenylsulfonyloxaziridine was a very efficient reagent for oxidative desulfurization of 2-thiouridine.

9% Cr steel high temperature oxidation. Solutions investigated for improving corrosion resistance of the steel

Energy Technology Data Exchange (ETDEWEB)

Evin, Harold Nicolas; Heintz, Olivier; Chevalier, Sebastien [UMR 5209 CNRS-Bourgogne Univ. (France). Lab. Interdisciplinaire Carnot de Bourgogne; Foejer, Cecilia; Jakani, Saad; Dhont, Annick; Claessens, Serge [OCAS N.V. ArcelorMittal Global R and D, Gent (Belgium)

2010-07-01

The improvement of high temperature oxidation resistance of low chromium content steels, such as T/P91, is of great interest in regards with their application in thermal power generating plants. Indeed, they possess good creep properties, but are facing their limits of use at temperature higher than 600 C, due to accelerated corrosion phenomena. Good knowledge of the mechanisms involved during their oxidation process is needed to prevent the degradation of the materials and to extend life time of the power plants components. Oxide layers thermally grown, on 9% Cr steels (provided by OCAS N.V), during isothermal tests between 600 C and 750 C in laboratory air under atmospheric pressure were investigated, by Scanning Electron Microscopy (SEM) and X-ray diffraction (XRD). The oxidation behaviour appeared very limited at 750 C, due to the presence of a breakaway, which can be linked to iron porous oxide grown over the surface of the samples. ''In situ'' X-ray Photoelectron spectroscopy (XPS) analyses were performed in air at 600 C after short exposures (between 5 min and 25 h). A complex mixture of iron oxide, Cr{sub 2}O{sub 3} and Cr (VI) species were characterized in the scales. The in-situ analyses were compared and related to XPS analyses performed on thick oxide scales formed on samples oxidized in air at 600 C for 100h. An oxidation mechanism is then proposed to understand the oxide scale growth in the temperature range 600 - 750 C. The second step of this study consists in improving the high temperature corrosion resistance of these steels without modifying their mechanical properties. Thus several solutions were investigated such as MOCVD coatings, pack cementation coatings, and tested in cycle conditions prior. (orig.)

Propane Oxidation at High Pressure and Intermediate Temperatures

DEFF Research Database (Denmark)

Hashemi, Hamid; Christensen, Jakob Munkholt; Glarborg, Peter

Propane oxidation at intermediate temperatures (500—900 K) and high pressure (100 bar) has been characterized by conducting experiments in a laminar flow reactor over a wide range of stoichiometries. The onset of fuel oxidation was found to be 600—725 K, depending on mixture stoichiometry...

UO{sub 2} oxidation under dry storage conditions: From data gaps to research needs

Energy Technology Data Exchange (ETDEWEB)

Feria, F.; Herranz, L. E. [CIEMAT, Andalucia (Spain)

2008-10-15

Dry interim storage is becoming a major activity of today's fuel cycle. The potential contact between no grossly damaged fuel rods (i.e., rods containing tiny defects like pinhole leaks and hairline cracks) and an oxidizing atmosphere during the cask water removal might lead to unacceptable consequences. One way to prevent it is to determine the time to propagation of a defect at given conditions. This paper compiles and critically reviews the existing database concerning time at temperature profile of fuel rods containing tiny defects that are exposed to oxidizing atmospheres. This review has pointed out significant drawbacks and limitations that would hinder its reliable application to assess the potential for defect propagation of current LWR fuels to be loaded in dry storage casks. Those weaknesses come essentially from data scarcity and lack of tests representativity. Based on this study, three main areas of work are recommended to fill the existing knowledge gaps: sound characterization of fuel rod responses in the low burnup range (<30 GWd/tU), extension of the database to high burnups characteristic of current discharged LWR fuels (<60GWd/tU), assessment of availability (i.e., amount and nature) of oxidizing agents. The result of the work suggested would result in a more complete and extensive database that would strongly support the potential use of 'time at temperature' curves.

Stability of Ruddlesden–Popper-structured oxides in humid conditions

Energy Technology Data Exchange (ETDEWEB)

Lehtimäki, M.; Yamauchi, H.; Karppinen, M., E-mail: maarit.karppinen@aalto.fi

2013-08-15

Some of layered transition-metal oxides are known to react with atmospheric humidity to form through topotactic intercalation reactions new water-containing layered structures. Here we investigate the influence of oxygen content (7−δ) of the Ruddlesden–Popper-structured Sr{sub 3}FeMO{sub 7−δ} (M=Ni, Mn, Ti) oxides on the water-intercalation reaction. It is found that their oxygen contents influence greatly the reactivity of the phases with water. Other factors possibly affecting the reactivity are discussed on the basis of the present data in combination with a comprehensive review of previous works on Ruddlesden–Popper and related layered oxide phases. - Graphical abstract: Many of the Ruddlesden–Popper-structured A{sub 3}B{sub 2}O{sub 7−δ} oxides readily react with water via intercalation reactions. Three possible factors affecting the water intercalation are identified: oxygen content of the phase, ionic radius of cation A and valence state of cation B. The resultant layered water-derivative phases can be categorised into two groups, depending on the crystal symmetry of the phase. Highlights: • Ruddlesden–Popper oxides A{sub 3}B{sub 2}O{sub 7−δ} often accommodate water via intercalation reaction. • The lower the oxygen content 7−δ is the more readily the intercalation reaction occurs. • The second factor promoting the reaction is the large size of cation A. • The third possible factor is the high valence state of cation B. • Resultant water-derivatives can be categorised into two groups depending on symmetry.

Stability of Ruddlesden–Popper-structured oxides in humid conditions

International Nuclear Information System (INIS)

Lehtimäki, M.; Yamauchi, H.; Karppinen, M.

2013-01-01

Some of layered transition-metal oxides are known to react with atmospheric humidity to form through topotactic intercalation reactions new water-containing layered structures. Here we investigate the influence of oxygen content (7−δ) of the Ruddlesden–Popper-structured Sr 3 FeMO 7−δ (M=Ni, Mn, Ti) oxides on the water-intercalation reaction. It is found that their oxygen contents influence greatly the reactivity of the phases with water. Other factors possibly affecting the reactivity are discussed on the basis of the present data in combination with a comprehensive review of previous works on Ruddlesden–Popper and related layered oxide phases. - Graphical abstract: Many of the Ruddlesden–Popper-structured A 3 B 2 O 7−δ oxides readily react with water via intercalation reactions. Three possible factors affecting the water intercalation are identified: oxygen content of the phase, ionic radius of cation A and valence state of cation B. The resultant layered water-derivative phases can be categorised into two groups, depending on the crystal symmetry of the phase. Highlights: • Ruddlesden–Popper oxides A 3 B 2 O 7−δ often accommodate water via intercalation reaction. • The lower the oxygen content 7−δ is the more readily the intercalation reaction occurs. • The second factor promoting the reaction is the large size of cation A. • The third possible factor is the high valence state of cation B. • Resultant water-derivatives can be categorised into two groups depending on symmetry

Contribution to the study of iron-manganese alloy oxidation in oxygen at high temperatures

International Nuclear Information System (INIS)

Olivier, Francoise

1972-01-01

This research thesis reports a systematic investigation of the oxidation of three relatively pure iron-manganese alloys in oxygen, under atmospheric pressure, and between 400 and 1000 C, these alloys being annealed as well as work-hardened. It also compares their behaviour with that of non-alloyed iron oxidized under the same conditions. The author describes the experimental techniques and installations, discusses the morphology of oxide films formed under the experimental conditions, discusses the film growth kinetics which is studied by thermogravimetry, proposes interpretations of results, and outlines the influence of manganese addition to iron on iron oxidation

ALTERATION OF U(VI)-PHASES UNDER OXIDIZING CONDITIONS

Energy Technology Data Exchange (ETDEWEB)

A.P. Deditius; S. Utsunomiya; R.C. Ewing

2006-02-21

Uranium-(VI) phases are the primary alteration products of the UO{sub 2} in spent nuclear fuel and the UO{sub 2+x}, in natural uranium deposits. The U(VI)-phases generally form sheet structures of edge-sharing UO{sub 2}{sup 2+} polyhedra. The complexity of these structures offers numerous possibilities for coupled-substitutions of trace metals and radionuclides. The incorporation of radionuclides into U(VI)-structures provides a potential barrier to their release and transport in a geologic repository that experiences oxidizing conditions. In this study, we have used natural samples of UO{sub 2+x}, to study the U(VI)-phases that form during alteration and to determine the fate of the associated trace elements.

ALTERATION OF U(VI)-PHASES UNDER OXIDIZING CONDITIONS

International Nuclear Information System (INIS)

A.P. Deditius; S. Utsunomiya; R.C. Ewing

2006-01-01

Uranium-(VI) phases are the primary alteration products of the UO 2 in spent nuclear fuel and the UO 2+x , in natural uranium deposits. The U(VI)-phases generally form sheet structures of edge-sharing UO 2 2+ polyhedra. The complexity of these structures offers numerous possibilities for coupled-substitutions of trace metals and radionuclides. The incorporation of radionuclides into U(VI)-structures provides a potential barrier to their release and transport in a geologic repository that experiences oxidizing conditions. In this study, we have used natural samples of UO 2+x , to study the U(VI)-phases that form during alteration and to determine the fate of the associated trace elements

Ultra‐high performance supercritical fluid chromatography of lignin‐derived phenols from alkaline cupric oxide oxidation

Science.gov (United States)

Sun, Mingzhe; Lidén, Gunnar; Sandahl, Margareta

2016-01-01

Traditional chromatographic methods for the analysis of lignin‐derived phenolic compounds in environmental samples are generally time consuming. In this work, an ultra‐high performance supercritical fluid chromatography method with a diode array detector for the analysis of major lignin‐derived phenolic compounds produced by alkaline cupric oxide oxidation was developed. In an analysis of a collection of 11 representative monomeric lignin phenolic compounds, all compounds were clearly separated within 6 min with excellent peak shapes, with a limit of detection of 0.5–2.5 μM, a limit of quantification of 2.5–5.0 μM, and a dynamic range of 5.0–2.0 mM (R 2 > 0.997). The new ultra‐high performance supercritical fluid chromatography method was also applied for the qualitative and quantitative analysis of lignin‐derived phenolic compounds obtained upon alkaline cupric oxide oxidation of a commercial humic acid. Ten out of the previous eleven model compounds could be quantified in the oxidized humic acid sample. The high separation power and short analysis time obtained demonstrate for the first time that supercritical fluid chromatography is a fast and reliable technique for the analysis of lignin‐derived phenols in complex environmental samples. PMID:27452148

Assessing the High Temperature, High Pressure Subsurface for Anaerobic Methane Oxidation

Science.gov (United States)

Harris, R. L.; Bartlett, D.; Byrnes, A. W.; Walsh, K. M.; Lau, C. Y. M.; Onstott, T. C.

2017-12-01

The anaerobic oxidation of methane (AOM) is an important sink in the global methane (CH4) budget. ANMEs are known to oxidize CH4 either independently or in consortia with bacteria, coupling the reduction of electron acceptors such as, SO42-, NO2-, NO3-, Mn4+, or Fe3+. To further constrain the contribution of AOM to the global CH4 budget, it is important to assess unexplored environments where AOM is thermodynamically possible such as the high pressure, high temperature deep biosphere. Provided plausible electron acceptor availability, increased temperature and pCH4 yield favorable Gibbs free energies for AOM reactions and the production of ATP (Fig. 1). To date, only sulfate-dependent AOM metabolism has been documented under high temperature conditions (50-72˚C), and AOM has not been assessed above 10.1 MPa. Given that ANMEs share close phylogenetic and metabolic heritage with methanogens and that the most heat-tolerant microorganism known is a barophilic methanogen, there possibly exist thermophilic ANMEs. Here we describe preliminary results from high pressure, high temperature stable isotope tracer incubation experiments on deep biosphere samples. Deep sub-seafloor sediments collected by IODP 370 from the Nankai Trough (257 - 865 m below seafloor) and deep fracture fluid from South Africa (1339 m below land surface) were incubated anaerobically in hydrostatic pressure vessels at 40 MPa in simulated in situ temperatures (40˚ - 80˚C). Sediments and fracture fluid were incubated in sulfate-free artificial seawater, a 2:98 13CH4:N2 headspace, and treated with one of the potential electron acceptors listed above in addition to kill and endogenous activity (i.e. no added electron acceptor) controls. Stable isotope analysis of dissolved inorganic carbon (DIC) suggests that AOM occurred within 60 days of incubation for all investigated electron acceptors and temperatures except 50˚C. Sulfate-dependent AOM rates are consistent with those previously reported in the

Astaxanthin degradation and lipid oxidation of Pacific white shrimp oil: kinetics study and stability as affected by storage conditions

Directory of Open Access Journals (Sweden)

Sirima Takeungwongtrakul

2016-02-01

Full Text Available Abstract The kinetics of astaxanthin degradation and lipid oxidation in shrimp oil from hepatopancreas of Pacific white shrimp (Litopenaeus vannamei as affected by storage temperature were studied. When shrimp oil was incubated at different temperatures (4, 30, 45 and 60 °C for 16 h, the rate constants (k of astaxanthin degradation and lipid oxidation in shrimp oil increased with increasing temperatures (p < 0.05. Thus, astaxanthin degradation and lipid oxidation in shrimp oil were augmented at high temperature. When shrimp oils with different storage conditions (illumination, oxygen availability and temperature were stored for up to 40 days, astaxanthin contents in all samples decreased throughout storage (p < 0.05. All factors were able to enhance astaxanthin degradation during 40 days of storage. With increasing storage time, the progressive formation of primary and secondary oxidation products were found in all samples as evidenced by the increases in both peroxide values (PV and thiobarbituric acid reactive substances (TBARS (p < 0.05. Light, air and temperatures therefore had the marked effect on astaxanthin degradation and lipid oxidation in shrimp oils during the extended storage.

Facile synthesis of iron oxides/reduced graphene oxide composites: application for electromagnetic wave absorption at high temperature.

Science.gov (United States)

Zhang, Lili; Yu, Xinxin; Hu, Hongrui; Li, Yang; Wu, Mingzai; Wang, Zhongzhu; Li, Guang; Sun, Zhaoqi; Chen, Changle

2015-03-19

Iron oxides/reduced graphene oxide composites were synthesized by facile thermochemical reactions of graphite oxide and FeSO4 · 7H2O. By adjusting reaction temperature, α-Fe2O3/reduced graphene oxide and Fe3O4/reduced graphene oxide composites can be obtained conveniently. Graphene oxide and reduced graphene oxide sheets were demonstrated to regulate the phase transition from α-Fe2O3 to Fe3O4 via γ-Fe2O3, which was reported for the first time. The hydroxyl groups attached on the graphene oxide sheets and H2 gas generated during the annealing of graphene oxide are believed to play an important role during these phase transformations. These samples showed good electromagnetic wave absorption performance due to their electromagnetic complementary effect. These samples possess much better electromagnetic wave absorption properties than the mixture of separately prepared Fe3O4 with rGO, suggesting the crucial role of synthetic method in determining the product properties. Also, these samples perform much better than commercial absorbers. Most importantly, the great stability of these composites is highly advantageous for applications as electromagnetic wave absorption materials at high temperatures.

A novel advanced oxidation process——wet electrocatalytic oxidation for high concentrated organic wastewater treatment

Institute of Scientific and Technical Information of China (English)

DAI QiZhou; ZHOU MingHua; LEI LeCheng; ZHANG Xing Wang

2007-01-01

A novel advanced oxidation process-wet electrocatalytic oxidation(WEO)was studied with p-nitrophenol as model pollutant and β-PbO2 electrode as the anode.Compared with the effect of the individual wet air oxidation(WAO)and electrochemical oxidation(EO),the effect of WEO showed synergistic effect on COD removal under the conditions of temperature 160℃,C=1000mg·L-1,PN2=0.50MPa,Po2=0.9 MPa,current density=3 mA·cm-2,Na2SO4 3 g·L-1.And the synergistic factor got the best value of 0.98 within 120 min after 180 min treatment.The synergistic factor was studied after 120 min treatment at 100℃,120℃,140℃and 160℃,and the effect of 120℃was the best with the value of 1.26.Possible mechanism for the synergistic effect was discussed based on the analysis of free-radical generation and intermediates detected by HPLC and GC/MS.

Stability of solid oxide fuel cell materials

Energy Technology Data Exchange (ETDEWEB)

Armstrong, T.R.; Bates, J.L.; Chick, L.A. [Pacific Northwest Lab., Richland, WA (United States)

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.

Low temperature high density plasma nitriding of stainless steel molds for stamping of oxide glasses

Directory of Open Access Journals (Sweden)

Aizawa Tatsuhiko

2016-01-01

Full Text Available Various kinds of stainless steels have been widely utilized as a die for mold- and direct-stamping processes of optical oxide glasses. Since they suffered from high temperature transients and thermal cycles in practice, they must be surface-treated by dry and wet coatings, or, by plasma nitriding. Martensitic stainless steel mold was first wet plated by the nickel phosphate (NiP, which was unstable at the high temperature stamping condition; and, was easy to crystalize or to fracture by itself. This issue of nuisance significantly lowered the productivity in fabrication of optical oxide-glass elements. In the present paper, the stainless steel mold was surface-treated by the low-temperature plasma nitriding. The nitrided layer by this surface modification had higher nitrogen solute content than 4 mass%; the maximum solid-solubility of nitrogen is usually 0.1 mass% in the equilibrium phase diagram. Owing to this solid-solution with high nitrogen concentration, the nitrided layer had high hardness over 1400 HV within its thickness of 50 μm without any formation of nitrides after plasma nitriding at 693 K for 14.4 ks. This plasma-nitrided mold was utilized for mold-stamping of two colored oxide glass plates at 833 K; these plates were successfully deformed and joined into a single glass plate by this stamping without adhesion or galling of oxide glasses onto the nitrided mold surface.

ZIF-67-derived hollow nanocages with layered double oxides shell as high-Efficiency catalysts for CO oxidation

Science.gov (United States)

Kong, Wenpeng; Li, Jing; Chen, Yao; Ren, Yuqing; Guo, Yonghua; Niu, Shengli; Yang, Yanzhao

2018-04-01

Constructing non-precious hybrid metal oxides with specific morphology as cost-effective and highly efficient catalysts is a promising way for the automotive exhaust purification. In this work, we report a facile strategy for the fabrication of a unique hollow Co-Ni layered double oxides (HLDO) nanocages by using zeolitic imidazole frameworks (ZIFs) as template. The synthesis of intermediate core-shell and hollow Co-Ni layered double hydroxides (HLDH) nanoflakes as well as the corresponding Co-Ni oxides products were successfully controlled, and the formation process was also explained. Among ZIF-67-derived oxides, HLDO exhibits excellent catalytic activities (complete conversion of CO into CO2 at 118 °C) and long-term stability for CO oxidation. The remarkable catalytic activities of HLDO can be attributed to high surface area (258 m2 g-1) inherited from the HLDH, which could provide more active sites for CO oxidation. In addition, active oxygen species indicated by the O 1 s XPS spectrum and improved synergistic effect between NiO and Co3O4 reflected by H2-TPR, further explain the enhanced performance of the HLDO catalysts. The presented strategy for controlled design and synthesis of hollow multicomponent metal oxides will provide prospects in developing highly effective catalysts.

Manganese oxide/graphene oxide composites for high-energyaqueous asymmetric electrochemical capacitors

CSIR Research Space (South Africa)

Jafta, CJ

2013-11-01

Full Text Available A high-energy aqueous asymmetric electrochemical capacitor was developed using manganese diox-ide ( -MnO2)/graphene oxide (GO) nanocomposites. The nanostructured -MnO2was prepared frommicron-sized commercial electrolytic manganese dioxide (EMD) via...

Stability of sputter deposited cuprous oxide (Cu2O) subjected to ageing conditions for photovoltaic applications

Science.gov (United States)

Camacho-Espinosa, E.; Rimmaudo, I.; Riech, I.; Mis-Fernández, R.; Peña, J. L.

2018-02-01

Among various metal oxide p-type semiconductors, cuprous oxide (Cu2O) stands out as a nontoxic and abundant material, which also makes it a suitable candidate as a low-cost absorber for photovoltaic applications. However, the chemical stability of the absorber layer is critical for the solar cell lifetime, in particular, for Cu-based materials, concerning to its oxidation state changes. In this paper, we addressed the Cu2O stability depositing films of 170 nm by reactive radio frequency magnetron sputtering and subsequently ageing them in conditions similar to the typical accelerated life test for the solar module, in a period of time from one to five weeks. The stability of the optical, electrical, and structural properties of the Cu2O thin films was investigated using UV-VIS-near infrared transmittance, 4-probes electrical resistance characterization, high precision profilometry, X-ray photoelectron spectroscopy, and grazing incidence X-ray diffraction. Finally, we demonstrated that the aging tests affected only the surface of the films, while the bulk remained unaltered, making Cu2O a promising candidate for production of stable devices, including solar cells.

High temperature oxidation of thin FeCrAl strips

International Nuclear Information System (INIS)

Andrieu, E.; Germidis, A.; Molins, R.

1997-01-01

This study concerns the oxidation behaviour between 850 and 1100 C of FeCrAl thin strips. Oxidation kinetics have been continuously recorded on a thermobalance as well as discontinuously in an ''industrial'' furnace. Detailed observations of oxide layers have been performed in transmission electron microscopy on oxidized thin foil cross-sections. Oxide morphologies are correlated with kinetics: Slow kinetics and columnar α alumina grains above 950 C, fast kinetics and transition alumina platelets (γ-alumina) at 850 C and 900 C, followed by small α-alumina grains formation underneath. The weight gains in the industrial furnace displayed significant scatter and were generally greater than those measured in the thermobalance. The effect of extrinsic factors such as specimen size and shape, atmosphere, air flow conditions on the early formation of transition aluminas explains the observed differences. It appears then that in given cases parabolic constant identification from TGA recordings is difficult, or even impossible. This might contribute to explain the differences in the results presented in the literature. (orig.)

Isothermal oxidation behavior of ternary Zr-Nb-Y alloys at high temperature

Energy Technology Data Exchange (ETDEWEB)

Prajitno, Djoko Hadi, E-mail: djokohp@batan.go.id [Research Center for Nuclear Materials and Radiometry, Jl. Tamansari 71, Bandung 40132 (Indonesia); Soepriyanto, Syoni; Basuki, Eddy Agus [Metallurgy Engineering, Institute Technology Bandung, Jl. Ganesha 10, Bandung 40132 (Indonesia); Wiryolukito, Slameto [Materials Engineering, Institute Technology Bandung, Jl. Ganesha 10, Bandung 40132 (Indonesia)

2014-03-24

The effect of yttrium content on isothermal oxidation behavior of Zr-2,5%Nb-0,5%Y, Zr-2,5%Nb-1%Y Zr-2,5%Nb-1,5%Y alloy at high temperature has been studied. High temperature oxidation carried out at tube furnace in air at 600,700 and 800°C for 1 hour. Optical microscope is used for microstructure characterization of the alloy. Oxidized and un oxidized specimen was characterized by x-ray diffraction. In this study, kinetic oxidation of Zr-2,5%Nb with different Y content at high temperature has also been studied. Characterization by optical microscope showed that microstructure of Zr-Nb-Y alloys relatively unchanged and showed equiaxed microstructure. X-ray diffraction of the alloys depicted that the oxide scale formed during oxidation of zirconium alloys is monoclinic ZrO2 while unoxidised alloy showed two phase α and β phase. SEM-EDS examination shows that depletion of Zr composition took place under the oxide layer. Kinetic rate of oxidation of zirconium alloy showed that increasing oxidation temperature will increase oxidation rate but increasing yttrium content in the alloys will decrease oxidation rate.

Mn-Catalyzed Highly Efficient Aerobic Oxidative Hydroxyazidation of Olefins: A Direct Approach to β-Azido Alcohols.

Science.gov (United States)

Sun, Xiang; Li, Xinyao; Song, Song; Zhu, Yuchao; Liang, Yu-Feng; Jiao, Ning

2015-05-13

An efficient Mn-catalyzed aerobic oxidative hydroxyazidation of olefins for synthesis of β-azido alcohols has been developed. The aerobic oxidative generation of azido radical employing air as the terminal oxidant is disclosed as the key process for this transformation. The reaction is appreciated by its broad substrate scope, inexpensive Mn-catalyst, high efficiency, easy operation under air, and mild conditions at room temperature. This chemistry provides a novel approach to high value-added β-azido alcohols, which are useful precursors of aziridines, β-amino alcohols, and other important N- and O-containing heterocyclic compounds. This chemistry also provides an unexpected approach to azido substituted cyclic peroxy alcohol esters. A DFT calculation indicates that Mn catalyst plays key dual roles as an efficient catalyst for the generation of azido radical and a stabilizer for peroxyl radical intermediate. Further calculation reasonably explains the proposed mechanism for the control of C-C bond cleavage or for the formation of β-azido alcohols.

Synthesis of iron oxides nanoparticles with very high saturation magnetization form TEA-Fe(III) complex via electrochemical deposition for supercapacitor applications

Science.gov (United States)

Elrouby, Mahmoud; Abdel-Mawgoud, A. M.; El-Rahman, Rehab Abd

2017-11-01

This work is devoted to the synthesis of magnetic iron oxides nanoparticles with very high saturation magnetization to be qualified for supercapacitor applications using, a simple electrodeposition technique. It is found that the electrochemical reduction process depends on concentration, temperature, deposition potential and the scan rate of potential. The nature of electrodeposition process has been characterized via voltammetric and chronoamperometric techniques. The morphology of the electrodeposits has been investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The structure and phase content of these investigated electrodeposits have been examined and calculated. The obtained iron oxides show a high saturation magnetization (Ms) of about 229 emu g-1. The data exhibited a relation between Ms of electrodeposited iron oxide and specific capacitance. This relation exhibits that the highest Ms value of electrodeposited iron oxides gives also highest specific capacitance of about 725 Fg-1. Moreover, the electrodeposited iron oxides exhibit a very good stability. The new characteristics of the electro synthesized iron oxides at our optimized conditions, strongly qualify them as a valuable material for high-performance supercapacitor applications.

In situ one-pot preparation of reduced graphene oxide/polyaniline composite for high-performance electrochemical capacitors

International Nuclear Information System (INIS)

Chen, Nali; Ren, Yapeng; Kong, Peipei; Tan, Lin; Feng, Huixia; Luo, Yongchun

2017-01-01

Highlights: • A new method to prepare reduced graphene oxide/polyaniline composite is developed. • Aniline serves as a reduction for graphene oxide under weak alkali condition. • Different characterizations confirm that GO can be effectively reduced by aniline. • A high specific capacitance of 524.4 F·g"−"1 is obtained at 0.5 A·g"−"1. - Abstract: Reduced graphene oxide/polyaniline (rGO/PANI) composites are prepared through an effective in situ one-pot synthesis route that includes the reduction of graphene oxide (GO) by aniline under weak alkali condition via hydrothermal method and then followed by in situ polymerization of aniline. X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, ultraviolet-visible spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscope and transmission electron microscope are employed to reveal that GO is successfully reduced by aniline under weak alkali condition and PANI can be deposited on the surfaces of reduced graphene oxide (rGO) sheets. The effect of rGO is optimized by tuning the mass ratios of aniline to GO to improve the electrochemical performance of rGO/PANI composites. The maximum specific capacitance of rGO/PANI composites achieves 524.4 F/g with a mass ratio of aniline to GO 10:1 at a current density of 0.5 A/g, in comparison to the specific capacitance of 397 F/g at the same current density of pure PANI. Particularly, the specific capacity retention rate is 81.1% after 2000 cycles at 100 mv/s scan rate, which is an improvement over that of pure PANI (55.5%).

In situ one-pot preparation of reduced graphene oxide/polyaniline composite for high-performance electrochemical capacitors

Energy Technology Data Exchange (ETDEWEB)

Chen, Nali [College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou 730050, Gansu (China); State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals, Lanzhou University of Technology, Lanzhou 730050, Gansu (China); Ren, Yapeng; Kong, Peipei; Tan, Lin [College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou 730050, Gansu (China); Feng, Huixia, E-mail: fenghx@lut.cn [College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou 730050, Gansu (China); Luo, Yongchun, E-mail: luoyc@lut.cn [State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals, Lanzhou University of Technology, Lanzhou 730050, Gansu (China)

2017-01-15

Highlights: • A new method to prepare reduced graphene oxide/polyaniline composite is developed. • Aniline serves as a reduction for graphene oxide under weak alkali condition. • Different characterizations confirm that GO can be effectively reduced by aniline. • A high specific capacitance of 524.4 F·g{sup −1} is obtained at 0.5 A·g{sup −1}. - Abstract: Reduced graphene oxide/polyaniline (rGO/PANI) composites are prepared through an effective in situ one-pot synthesis route that includes the reduction of graphene oxide (GO) by aniline under weak alkali condition via hydrothermal method and then followed by in situ polymerization of aniline. X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, ultraviolet-visible spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscope and transmission electron microscope are employed to reveal that GO is successfully reduced by aniline under weak alkali condition and PANI can be deposited on the surfaces of reduced graphene oxide (rGO) sheets. The effect of rGO is optimized by tuning the mass ratios of aniline to GO to improve the electrochemical performance of rGO/PANI composites. The maximum specific capacitance of rGO/PANI composites achieves 524.4 F/g with a mass ratio of aniline to GO 10:1 at a current density of 0.5 A/g, in comparison to the specific capacitance of 397 F/g at the same current density of pure PANI. Particularly, the specific capacity retention rate is 81.1% after 2000 cycles at 100 mv/s scan rate, which is an improvement over that of pure PANI (55.5%).

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

International Nuclear Information System (INIS)

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

2010-01-01

A chemical synthesis method is presented for the fabrication of high-definition segmented metal-oxide-metal (MOM) nanowires in two different ferroelectric oxide systems: Au-BaTiO 3 -Au and Au-PbTiO 3 -Au. This method entails electrodeposition of segmented nanowires of Au-TiO 2 -Au inside anodic aluminum oxide (AAO) templates, followed by topotactic hydrothermal conversion of the TiO 2 segments into BaTiO 3 or PbTiO 3 segments. Two-terminal devices from individual MOM nanowires are fabricated, and their ferroelectric properties are measured directly, without the aid of scanning probe microscopy (SPM) methods. The MOM nanowire architecture provides high-quality end-on electrical contacts to the oxide segments, and allows direct measurement of properties of nanoscale volume, strain-free oxide segments. Unusually high ferroelectric responses, for chemically synthesized oxides, in these MOM nanowires are reported, and are attributed to the lack of residual strain in the oxides. The ability to measure directly the active properties of nanoscale volume, strain-free oxides afforded by the MOM nanowire architecture has important implications for fundamental studies of not only ferroelectric nanostructures but also nanostructures in the emerging field of multiferroics.

Evaluation of advanced hot conditioning process for PHWRS

International Nuclear Information System (INIS)

Chandramohan, P.; Srinivasan, M.P.; Velmurugan, S.

2015-01-01

Hot-conditioning/hot functional test process is carried out to the PHT system of reactor before reactor going to critical/operational. The process is aimed in checking the component functionalities at high temperature and high pressure conditions, the process also checks/removes the suspended corrosion products in heat transport circuit. This process leads to formation of a passive or corrosion oxide film on the heat transport circuit surfaces which protects/mitigates the corrosion of the system circuits during the operation of plant. Major concerned alloy in the Primary Heat Transport (PHT) system of Indian PHWRs during the hot conditioning process and also during operation is the carbon steel due to its high corrosion. Hot-conditioning process mitigates the corrosion of carbon steel by the formation of iron oxide (Fe 3 O 4 ) as major oxide phase layer on the carbon steel surface with a typical thickness of 1.0 μm with particle size of 1μm after 336 h of process at 250 °C. But this passive oxide film thickness increase with time of operation of system with c.a. 10μm for 2.2 EFYP. The protectiveness of passive layer can be further enhanced by reducing the particle sizes in the passive film to nano meter range. The process can impact on the compactness of passive oxide layer with reduced pores in the oxide layer and properties of the nano nature oxide (transport properties) impacting the corrosion mitigation. The corrosion mitigation reduce the source term in the activated corrosion product generation. To achieve this a new process 'Advanced hot conditioning' was developed in water steam chemistry division, BARC for getting a passive oxide film with a lowered particle size in the passive film. The AHC process with 1g/L of PEG-8000 at 250 °C for 336 h showed a particle size <100 nm. The process was tested under the normal operating conditions as function of the time, the corrosion parameter like oxide film thickness, corrosion rate and metal ion

Unchanged cerebral blood flow and oxidative metabolism after acclimatization to high altitude

DEFF Research Database (Denmark)

Møller, Kirsten; Paulson, Olaf B; Hornbein, Thomas F.

2002-01-01

The authors investigated the effect of acclimatization to high altitude on cerebral blood flow and oxidative metabolism at rest and during exercise. Nine healthy, native sea-level residents were studied 3 weeks after arrival at Chacaltaya, Bolivia (5,260 m) and after reacclimatization to sea level....... At high altitude at rest, arterial carbon dioxide tension, oxygen saturation, and oxygen tension were significantly reduced, and arterial oxygen content was increased because of an increase in hemoglobin concentration. Global cerebral blood flow was similar in the four conditions. Cerebral oxygen delivery...... and cerebral metabolic rates of oxygen and glucose also remained unchanged, whereas cerebral metabolic rates of lactate increased slightly but nonsignificantly at high altitude during exercise compared with high altitude at rest. Reaction time was unchanged. The data indicate that cerebral blood flow...

Ultra-high performance supercritical fluid chromatography of lignin-derived phenols from alkaline cupric oxide oxidation.

Science.gov (United States)

Sun, Mingzhe; Lidén, Gunnar; Sandahl, Margareta; Turner, Charlotta

2016-08-01

Traditional chromatographic methods for the analysis of lignin-derived phenolic compounds in environmental samples are generally time consuming. In this work, an ultra-high performance supercritical fluid chromatography method with a diode array detector for the analysis of major lignin-derived phenolic compounds produced by alkaline cupric oxide oxidation was developed. In an analysis of a collection of 11 representative monomeric lignin phenolic compounds, all compounds were clearly separated within 6 min with excellent peak shapes, with a limit of detection of 0.5-2.5 μM, a limit of quantification of 2.5-5.0 μM, and a dynamic range of 5.0-2.0 mM (R(2) > 0.997). The new ultra-high performance supercritical fluid chromatography method was also applied for the qualitative and quantitative analysis of lignin-derived phenolic compounds obtained upon alkaline cupric oxide oxidation of a commercial humic acid. Ten out of the previous eleven model compounds could be quantified in the oxidized humic acid sample. The high separation power and short analysis time obtained demonstrate for the first time that supercritical fluid chromatography is a fast and reliable technique for the analysis of lignin-derived phenols in complex environmental samples. © 2016 The Authors, Journal of Separation Science Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-temperature oxidation of advanced FeCrNi alloy in steam environments

Science.gov (United States)

Elbakhshwan, Mohamed S.; Gill, Simerjeet K.; Rumaiz, Abdul K.; Bai, Jianming; Ghose, Sanjit; Rebak, Raul B.; Ecker, Lynne E.

2017-12-01

Alloys of iron-chromium-nickel are being explored as alternative cladding materials to improve safety margins under severe accident conditions. Our research focuses on non-destructively investigating the oxidation behavior of the FeCrNi alloy "Alloy 33" using synchrotron-based methods. The evolution and structure of oxide layer formed in steam environments were characterized using X-ray diffraction, hard X-ray photoelectron spectroscopy, X-ray fluorescence methods and scanning electron microscopy. Our results demonstrate that a compact and continuous oxide scale was formed consisting of two layers, chromium oxide and spinel phase (FeCr2O4) oxides, wherein the concentration of the FeCr2O4 phase decreased from the surface to the bulk-oxide interface.

WATER-GAS SHIFT KINETICS OVER IRON OXIDE CATALYSTS AT MEMBRANE REACTOR CONDITIONS; A

International Nuclear Information System (INIS)

Carl R.F. Lund

2001-01-01

This report covers the second year of a project investigating water-gas shift catalysts for use in membrane reactors. It has been established that a simple iron high temperature shift catalyst becomes ineffective in a membrane reactor because the reaction rate is severely inhibited by the build-up of the product CO(sub 2). During the past year, an improved microkinetic model for water-gas shift over iron oxide was developed. Its principal advantage over prior models is that it displays the correct asymptotic behavior at all temperatures and pressures as the composition approaches equilibrium. This model has been used to explore whether it might be possible to improve the performance of iron high temperature shift catalysts under conditions of high CO(sub 2) partial pressure. The model predicts that weakening the surface oxygen bond strength by less than 5% should lead to higher catalytic activity as well as resistance to rate inhibition at higher CO(sub 2) partial pressures. Two promoted iron high temperature shift catalysts were studied. Ceria and copper were each studied as promoters since there were indications in the literature that they might weaken the surface oxygen bond strength. Ceria was found to be ineffective as a promoter, but preliminary results with copper promoted FeCr high temperature shift catalyst show it to be much more resistant to rate inhibition by high levels of CO(sub 2). Finally, the performance of sulfided CoMo/Al(sub 2)O(sub 3) catalysts under conditions of high CO(sub 2) partial pressure was simulated using an available microkinetic model for water-gas shift over this catalyst. The model suggests that this catalyst might be quite effective in a medium temperature water-gas shift membrane reactor, provided that the membrane was resistant to the H(sub 2)S that is required in the feed

Molybdenum Disilicide Oxidation Kinetics in High Temperature Steam

Energy Technology Data Exchange (ETDEWEB)

Wood, Elizabeth Sooby [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Parker, Stephen Scott [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Nelson, Andrew Thomas [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2016-09-07

The Fuel Cycle Research and Development program’s Advanced Fuels Campaign is currently supporting a range of experimental efforts aimed at the development and qualification of ‘accident tolerant’ nuclear fuel forms. One route to enhance the accident tolerance of nuclear fuel is to replace the zirconium alloy cladding, which is prone to rapid oxidation in steam at elevated temperatures, with a more oxidation-resistant cladding. Several cladding replacement solutions have been envisaged. The cladding can be completely replaced with a more oxidation resistant alloy, a layered approach can be used to optimize the strength, creep resistance, and oxidation tolerance of various materials, or the existing zirconium alloy cladding can be coated with a more oxidation-resistant material. Molybdenum is one candidate cladding material favored due to its high temperature creep resistance. However, it performs poorly under autoclave testing and suffers degradation under high temperature steam oxidation exposure. Development of composite cladding architectures consisting of a molybdenum core shielded by a molybdenum disilicide (MoSi₂) coating is hypothesized to improve the performance of a Mo-based cladding system. MoSi₂ was identified based on its high temperature oxidation resistance in O₂ atmospheres (e.g. air and “wet air”). However, its behavior in H₂O is less known. This report presents thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and x-ray diffraction (XRD) results for MoSi₂ exposed to 670-1498 K water vapor. Synthetic air (80-20%, Ar-O₂) exposures were also performed, and those results are presented here for a comparative analysis. It was determined that MoSi₂ displays drastically different oxidation behavior in water vapor than in dry air. In the 670-1498 K temperature range, four distinct behaviors are observed. Parabolic oxidation is exhibited in only 670

Evaluation of Capacity on a High Throughput Vol-oxidizer for Operability

International Nuclear Information System (INIS)

Kim, Young Hwan; Park, Geun Il; Lee, Jung Won; Jung, Jae Hoo; Kim, Ki Ho; Lee, Yong Soon; Lee, Do Youn; Kim, Su Sung

2010-01-01

KAERI is developing a pyro-process. As a piece of process equipment, a high throughput vol-oxidizer which can handle a several tens kg HM/batch was developed to supply U 3 O 8 powders to an electrolytic reduction(ER) reactor. To increase the reduction yield, UO 2 pellets should be converted into uniform powders. In this paper, we aim at the evaluation of a high throughput vol-oxidizer for operability. The evaluation consisted of 3 targets, a mechanical motion test, a heating test and hull separation test. In order to test a high throughput vol-oxidizer, By using a control system, mechanical motion tests of the vol-oxidizer were conducted, and heating rates were analyzed. Also the separation tests of hulls for recovery rate were conducted. The test results of the vol-oxidizer are going to be applied for operability. A study on the characteristics of the volatile gas produced during a vol-oxidation process is not included in this study

Influence of the heat treatment condition of alloy AlCu4Mg1 on the microstructure and properties of anodic oxide layers

Science.gov (United States)

Morgenstern, R.; Dietrich, D.; Sieber, M.; Lampke, T.

2017-03-01

Due to their outstanding specific mechanical properties, high-strength, age-hardenable aluminum alloys offer a high potential for lightweight security-related applications. However, the use of copper-alloyed aluminum is limited because of their susceptibility to selective corrosion and their low wear resistance. These restrictions can be overcome and new applications can be opened up by the generation of protective anodic aluminum oxide layers. In contrast to the anodic oxidation of unalloyed aluminum, oxide layers produced on copper-rich alloys exhibit a significantly more complex pore structure. It is the aim of the investigation to identify the influence of microstructural parameters such as size and distribution of the strengthening precipitations on the coating microstructure. The aluminum alloy EN AW-2024 (AlCu4Mg1) in different heat treatment conditions serves as substrate material. The influence of the strengthening precipitations’ size and distribution on the development of the pore structure is investigated by the use of high-resolution scanning electron microscopy. Integral coating properties are characterized by non-destructive and light-microscopic thickness measurements and instrumented indentation tests.

An Overview of High-k Oxides on Hydrogenated-Diamond for Metal-Oxide-Semiconductor Capacitors and Field-Effect Transistors

Directory of Open Access Journals (Sweden)

Jiangwei Liu

2018-06-01

Full Text Available Thanks to its excellent intrinsic properties, diamond is promising for applications of high-power electronic devices, ultraviolet detectors, biosensors, high-temperature tolerant gas sensors, etc. Here, an overview of high-k oxides on hydrogenated-diamond (H-diamond for metal-oxide-semiconductor (MOS capacitors and MOS field-effect transistors (MOSFETs is demonstrated. Fabrication routines for the H-diamond MOS capacitors and MOSFETs, band configurations of oxide/H-diamond heterointerfaces, and electrical properties of the MOS and MOSFETs are summarized and discussed. High-k oxide insulators are deposited using atomic layer deposition (ALD and sputtering deposition (SD techniques. Electrical properties of the H-diamond MOS capacitors with high-k oxides of ALD-Al2O3, ALD-HfO2, ALD-HfO2/ALD-Al2O3 multilayer, SD-HfO2/ALD-HfO2 bilayer, SD-TiO2/ALD-Al2O3 bilayer, and ALD-TiO2/ALD-Al2O3 bilayer are discussed. Analyses for capacitance-voltage characteristics of them show that there are low fixed and trapped charge densities for the ALD-Al2O3/H-diamond and SD-HfO2/ALD-HfO2/H-diamond MOS capacitors. The k value of 27.2 for the ALD-TiO2/ALD-Al2O3 bilayer is larger than those of the other oxide insulators. Drain-source current versus voltage curves show distinct pitch-off and p-type channel characteristics for the ALD-Al2O3/H-diamond, SD-HfO2/ALD-HfO2/H-diamond, and ALD-TiO2/ALD-Al2O3/H-diamond MOSFETs. Understanding of fabrication routines and electrical properties for the high-k oxide/H-diamond MOS electronic devices is meaningful for the fabrication of high-performance H-diamond MOS capacitor and MOSFET gas sensors.

Powder processing of high Tc oxide superconductors and their properties

International Nuclear Information System (INIS)

Vajpei, A.C.; Upadhyaya, G.S.

1992-01-01

Powder processing of ceramics is an established technology and in the area of high T c superconductors, its importance is felt even more significantly. The present monograph is an attempt in this direction to explore the perspectives and practice of powder processing routes towards control and optimization of the microstructure and pertinent properties of high T c oxide superconductors. The monograph consists of 6 chapters. After a very brief introduction (Chapter 1), Chapter 2 describes various classes of high T c oxide superconductors and their phase equilibria. Chapter 3 highlights the preparation of oxide superconductor powders through various routes and details their subtle distinctions. Chapter 4 briefly covers characterisation of the oxide superconductors, laying emphasis on the process-analysis and microstructure. Chapter 5 describes in detail various fabrication techniques for bulk superconductors through the powder routes. The last Chapter (Chapter 6) describing properties of bulk oxide superconductors, discusses the role of subtituents, compositional variations and processing methods on such properties. References are given at the end of each chapter. (orig.)

Microbial Anaerobic Ammonium Oxidation Under Iron Reducing Conditions, Alternative Electron Acceptors

Science.gov (United States)

Ruiz-Urigüen, M.; Jaffe, P. R.

2015-12-01

Autotrophic Acidimicrobiaceae-bacterium named A6 (A6), part of the Actinobacteria phylum have been linked to anaerobic ammonium (NH4+) oxidation under iron reducing conditions. These organisms obtain their energy by oxidizing NH4+ and transferring the electrons to a terminal electron acceptor (TEA). Under environmental conditions, the TEAs are iron oxides [Fe(III)], which are reduced to Fe(II), this process is known as Feammox. Our studies indicate that alternative forms of TEAs can be used by A6, e.g. iron rich clays (i.e. nontronite) and electrodes in bioelectrochemical systems such as Microbial Electrolysis Cells (MECs), which can sustain NH4+removal and A6 biomass production. Our results show that nontronite can support Feammox and promote bacterial cell production. A6 biomass increased from 4.7 x 104 to 3.9 x 105 cells/ml in 10 days. Incubations of A6 in nontronite resulted in up to 10 times more NH4+ removal and 3 times more biomass production than when ferrihydrite is used as the Fe(III) source. Additionally, Fe in nontronite can be reoxidized by aeration and A6 can reutilize it; however, Fe is still finite in the clay. In contrast, in MECs, A6 harvest electrons from NH4+ and use an anode as an unlimited TEA, as a result current is produced. We operated multiple MECs in parallel using a single external power source, as described by Call & Logan (2011). MECs were run with an applied voltage of 0.7V and different growing mediums always containing initial 5mM NH4+. Results show that current production is favored when anthraquinone-2,6-disulfonate (AQDS), an electron shuttled, is present in the medium as it facilitates the transfer of electrons from the bacterial cell to the anode. Additionally, A6 biomass increased from 1 x 104 to 9.77 x 105cells/ml in 14 days of operation. Due to Acidimicrobiaceae-bacterium A6's ability to use various TEAs, MECs represent an alternative, iron-free form, for optimized biomass production of A6 and its application in NH4

Role of Oxides and Porosity on High-Temperature Oxidation of Liquid-Fueled HVOF Thermal-Sprayed Ni50Cr Coatings

Science.gov (United States)

Song, B.; Bai, M.; Voisey, K. T.; Hussain, T.

2017-02-01

High chromium content in Ni50Cr thermally sprayed coatings can generate a dense and protective scale at the surface of coating. Thus, the Ni50Cr coating is widely used in high-temperature oxidation and corrosion applications. A commercially available gas atomized Ni50Cr powder was sprayed onto a power plant steel (ASME P92) using a liquid-fueled high velocity oxy-fuel thermal spray with three processing parameters in this study. Microstructure of as-sprayed coatings was examined using oxygen content analysis, mercury intrusion porosimetry, scanning electron microscope (SEM), energy-dispersive x-ray spectroscopy (EDX) and x-ray diffraction (XRD). Short-term air oxidation tests (4 h) of freestanding coatings (without boiler steel substrate) in a thermogravimetric analyzer at 700 °C were performed to obtain the kinetics of oxidation of the as-sprayed coating. Long-term air oxidation tests (100 h) of the coated substrates were performed at same temperature to obtain the oxidation products for further characterization in detail using SEM/EDX and XRD. In all samples, oxides of various morphologies developed on top of the Ni50Cr coatings. Cr2O3 was the main oxidation product on the surface of all three coatings. The coating with medium porosity and medium oxygen content has the best high-temperature oxidation performance in this study.

Metallic oxide nano-clusters synthesis by ion implantation in high purity Fe10Cr alloy

International Nuclear Information System (INIS)

Zheng, Ce

2015-01-01

ODS (Oxide Dispersed Strengthened) steels, which are reinforced with metal dispersions of nano-oxides (based on Y, Ti and O elements), are promising materials for future nuclear reactors. The detailed understanding of the mechanisms involved in the precipitation of these nano-oxides would improve manufacturing and mechanical properties of these ODS steels, with a strong economic impact for their industrialization. To experimentally study these mechanisms, an analytical approach by ion implantation is used, to control various parameters of synthesis of these precipitates as the temperature and concentration. This study demonstrated the feasibility of this method and concerned the behaviour of alloys models (based on aluminium oxide) under thermal annealing. High purity Fe-10Cr alloys were implanted with Al and O ions at room temperature. Transmission electron microscopy observations showed that the nano-oxides appear in the Fe-10Cr matrix upon ion implantation at room temperature without subsequent annealing. The mobility of implanted elements is caused by the defects created during ion implantation, allowing the nucleation of these nanoparticles, of a few nm in diameter. These nanoparticles are composed of aluminium and oxygen, and also chromium. The high-resolution experiments show that their crystallographic structure is that of a non-equilibrium compound of aluminium oxide (cubic γ-Al 2 O 3 type). The heat treatment performed after implantation induces the growth of the nano-sized oxides, and a phase change that tends to balance to the equilibrium structure (hexagonal α-Al 2 O 3 type). These results on model alloys are fully applicable to industrial materials: indeed ion implantation reproduces the conditions of milling and heat treatments are at equivalent temperatures to those of thermo-mechanical treatments. A mechanism involving the precipitation of nano-oxide dispersed in ODS alloys is proposed in this manuscript based on the obtained experimental results

Influence of the conditions for the preparation and thermal destruction of ammonium tetravanadate on the composition of oxide-vanadic electro-functional materials

Directory of Open Access Journals (Sweden)

Luskan К. V.

2017-09-01

Full Text Available The work represents the investigation of the influence of technological stages of ammonium tetravanadate preparation on the final composition of vanadium oxide products. The purpose of experimental studies is to determine the technological parameters for the production of highly dispersed vanadium oxides with different degrees of oxidation (V2O3, VO2, V2O5. The synthesis of ammonium tetravanadate comprises three main steps: the reaction of 3 g of V2O5 and 8.32 g of H2C2O4 ∙ 2H2O dissolving in 100 ml of water, followed by product precipitation with 30 % ammonium hydroxide, separation of the precipitate by centrifugation or sublimation. Vanadium oxides are formed in the fourth stage of thermal decomposition of ammonium tetravanadate. X-ray diffraction analysis samples was performed on “DRON-3”. Differential thermal analysis (DTA samples was carried out on a derivatograph “Q-150”. The influence of separation conditions and thermal decomposition of the sediment on the composition of the final products (V2O3, VO2, V2O5 was studied. With the X-ray analysis it was determined that when using the centrifugation the final product of thermodestruction in an inert atmosphere is VO2, while sublimation drying leads to V2O3, and highly dispersed V2O5 is formed in an oxygen atmosphere. Highly dispersed vanadium oxides with different degrees of oxidation can be synthesized according to the introduced manufacturing scheme.

A metalloenzyme-like catalytic system for the chemoselective oxidative cross-coupling of primary amines to imines under ambient conditions.

Science.gov (United States)

Largeron, Martine; Fleury, Maurice-Bernard

2015-02-23

The direct oxidative cross-coupling of primary amines is a challenging transformation as homocoupling is usually preferred. We report herein the chemoselective preparation of cross-coupled imines through the synergistic combination of low loadings of Cu(II) metal-catalyst and o-iminoquinone organocatalyst under ambient conditions. This homogeneous cooperative catalytic system has been inspired by the reaction of copper amine oxidases, a family of metalloenzymes with quinone organic cofactors that mediate the selective oxidation of primary amines to aldehydes. After optimization, the desired cross-coupled imines are obtained in high yields with broad substrate scope through a transamination process that leads to the homocoupled imine intermediate, followed by dynamic transimination. The ability to carry out the reactions at room temperature and with ambient air, rather than molecular oxygen as the oxidant, and equimolar amounts of each coupling partner is particularly attractive from an environmentally viewpoint. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The high temperature oxidation behaviour of austenitic stainless steels

International Nuclear Information System (INIS)

Hales, R.

1977-04-01

High temperature annealing in a dynamic vacuum has been utilised to induce the growth of duplex oxide over the whole surface of stainless steel specimens. It is found that duplex oxide grows at a rate which does not obey a simple power law. The oxidation kinetics and oxide morphology have also been studied for a series of ternary austenitic alloys which cover a range of composition between 5 and 20% chromium. A model has been developed to describe the formation of duplex oxide and the subsequent formation of a 'healing layer' which virtually causes the oxidation process to stop. This phase tends to form at grain boundaries and a relationship has been derived for the reaction kinetics which relates the reaction rate with grain size of the substrate. (author)

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

Energy Technology Data Exchange (ETDEWEB)

Herderick, Edward D; Padture, Nitin P [Department of Materials Science and Engineering, Center for Emergent Materials, Ohio State University, Columbus, OH 43210 (United States); Polomoff, Nicholas A; Huey, Bryan D, E-mail: padture.1@osu.edu [Department of Chemical, Materials, and Biomolecular Engineering, Institute of Materials Science, University of Connecticut, Storrs, CT 06269 (United States)

2010-08-20

A chemical synthesis method is presented for the fabrication of high-definition segmented metal-oxide-metal (MOM) nanowires in two different ferroelectric oxide systems: Au-BaTiO{sub 3}-Au and Au-PbTiO{sub 3}-Au. This method entails electrodeposition of segmented nanowires of Au-TiO{sub 2}-Au inside anodic aluminum oxide (AAO) templates, followed by topotactic hydrothermal conversion of the TiO{sub 2} segments into BaTiO{sub 3} or PbTiO{sub 3} segments. Two-terminal devices from individual MOM nanowires are fabricated, and their ferroelectric properties are measured directly, without the aid of scanning probe microscopy (SPM) methods. The MOM nanowire architecture provides high-quality end-on electrical contacts to the oxide segments, and allows direct measurement of properties of nanoscale volume, strain-free oxide segments. Unusually high ferroelectric responses, for chemically synthesized oxides, in these MOM nanowires are reported, and are attributed to the lack of residual strain in the oxides. The ability to measure directly the active properties of nanoscale volume, strain-free oxides afforded by the MOM nanowire architecture has important implications for fundamental studies of not only ferroelectric nanostructures but also nanostructures in the emerging field of multiferroics.

A Status of Art-Report on the Fission Products Behavior Released from Spent Fuel at High Temperature Conditions

International Nuclear Information System (INIS)

Park, Geun Il; Kim, J. H.; Lee, J. W.

2003-04-01

The experiments on the fission products release behavior from spent fuel at high temperature assuming reactor accident conditions have been carried out at Oak Ridge Nation Laboratory of USA in HI/VI tests, CEA of France in HEVA/VERCOS tests, AEA of England and CRNL of Canada in HOX test. The VEGA program to study the fission product release behavior from LWR irradiated fuel was recently initiated at JAERI. The key parameter affecting the fission product(FP) release behavior is temperature. In addition, other parameters such as fuel oxidation, burnup, pre-transient conditions are found to affect the FP releases considerably in the earlier tests. The atmosphere conditions such as oxidizing atmosphere (steam or air) or reducing atmosphere (hydrogen) can cause significant change of FPs release and transport behavior due to chemical forms of the reactive FPs which is dependent on the oxidation potential. The effect of fuel burnup on the Kr-85 or Cs-137 release showed that the release rates of these radionuclides increased with the increase of burnup, meaning that release rates are dominated by the atomic diffusions in the grains and they are primarily a function of temperature. However, the data on FPs release behavior using higher burnups above 50,000 MWD/MTU are not so many reported up to now. This report summarizes the test results of FPs release behavior in reactor accident conditions produced from other countries mentioned above. This review and analysis on earlier studies would be useful for predicting the release characteristics of FPs from domestic spent fuel. The release rates of fission gas or FPs from spent fuel at high temperature conditions during fabrication process of dry recycling fuel were also analyzed using many data obtained from earlier tests

Reduced graphene oxide synthesis by high energy ball milling

Energy Technology Data Exchange (ETDEWEB)

Mondal, O. [Department of Physics, M.U.C Women' s College, Burdwan 713104 (India); Mitra, S. [MLS Prof' s Unit, Indian Association for the Cultivation of Science, Kolkata 700032 (India); Pal, M. [CSIR-Central Glass and Ceramic Research Institute, Kolkata 700032 (India); Datta, A. [University School of Basic and Applied Science (USBAS), Guru Gobind Singh Indraprastha University, New Delhi 110075 (India); Dhara, S. [Surface and Nanoscience Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Chakravorty, D., E-mail: mlsdc@iacs.res.in [MLS Prof' s Unit, Indian Association for the Cultivation of Science, Kolkata 700032 (India)

2015-07-01

Graphene oxide is transformed to reduced graphene oxide by high energy ball milling in inert atmosphere. The process of ball milling introduces defects and removes oxygen functional groups, thereby creating the possibility of fine tuning the band gap of all intermediate stages of the structural evolution. A limit of the backbone sp{sup 2} network structure has been found which should be able to accommodate defects, before amorphization sets in. The amorphization of graphene oxide is achieved rather quickly in comparison to that of graphite. From thermogravimetric and differential scanning calorimetric analysis along with Fourier transform infrared (FTIR) and Raman spectroscopic studies, it is found that the number of oxygen-containing groups decreases at a faster rate than that of aromatic double bonds with increasing ball milling time with a maximum limit of 3 h. Several characterization techniques (FTIR, Raman, UV–Visible and X-ray photoelectron spectroscopy) have confirmed that the material synthesized is, indeed, reduced graphene oxide. - Highlights: • Graphene oxide is transformed to reduced graphene oxide by high energy ball milling in inert atmosphere. • Fine tuning the band gap by introducing defects and removing oxygen functional groups. • Introduction of excess defects leads to amorphization. • Photoluminescence has been observed in the UV-blue region.

Electronic States of High-k Oxides in Gate Stack Structures

Science.gov (United States)

Zhu, Chiyu

In this dissertation, in-situ X-ray and ultraviolet photoemission spectroscopy have been employed to study the interface chemistry and electronic structure of potential high-k gate stack materials. In these gate stack materials, HfO2 and La2O3 are selected as high-k dielectrics, VO2 and ZnO serve as potential channel layer materials. The gate stack structures have been prepared using a reactive electron beam system and a plasma enhanced atomic layer deposition system. Three interrelated issues represent the central themes of the research: 1) the interface band alignment, 2) candidate high-k materials, and 3) band bending, internal electric fields, and charge transfer. 1) The most highlighted issue is the band alignment of specific high-k structures. Band alignment relationships were deduced by analysis of XPS and UPS spectra for three different structures: a) HfO2/VO2/SiO2/Si, b) HfO 2-La2O3/ZnO/SiO2/Si, and c) HfO 2/VO2/ HfO2/SiO2/Si. The valence band offset of HfO2/VO2, ZnO/SiO2 and HfO 2/SiO2 are determined to be 3.4 +/- 0.1, 1.5 +/- 0.1, and 0.7 +/- 0.1 eV. The valence band offset between HfO2-La2O3 and ZnO was almost negligible. Two band alignment models, the electron affinity model and the charge neutrality level model, are discussed. The results show the charge neutrality model is preferred to describe these structures. 2) High-k candidate materials were studied through comparison of pure Hf oxide, pure La oxide, and alloyed Hf-La oxide films. An issue with the application of pure HfO2 is crystallization which may increase the leakage current in gate stack structures. An issue with the application of pure La2O3 is the presence of carbon contamination in the film. Our study shows that the alloyed Hf-La oxide films exhibit an amorphous structure along with reduced carbon contamination. 3) Band bending and internal electric fields in the gate stack structure were observed by XPS and UPS and indicate the charge transfer during the growth and process. The oxygen

High glucose-mediated oxidative stress impairs cell migration.

Directory of Open Access Journals (Sweden)

Marcelo L Lamers

Full Text Available Deficient wound healing in diabetic patients is very frequent, but the cellular and molecular causes are poorly defined. In this study, we evaluate the hypothesis that high glucose concentrations inhibit cell migration. Using CHO.K1 cells, NIH-3T3 fibroblasts, mouse embryonic fibroblasts and primary skin fibroblasts from control and diabetic rats cultured in 5 mM D-glucose (low glucose, LG, 25 mM D-glucose (high glucose, HG or 25 mM L-glucose medium (osmotic control--OC, we analyzed the migration speed, protrusion stability, cell polarity, adhesion maturation and the activity of the small Rho GTPase Rac1. We also analyzed the effects of reactive oxygen species by incubating cells with the antioxidant N-Acetyl-Cysteine (NAC. We observed that HG conditions inhibited cell migration when compared to LG or OC. This inhibition resulted from impaired cell polarity, protrusion destabilization and inhibition of adhesion maturation. Conversely, Rac1 activity, which promotes protrusion and blocks adhesion maturation, was increased in HG conditions, thus providing a mechanistic basis for the HG phenotype. Most of the HG effects were partially or completely rescued by treatment with NAC. These findings demonstrate that HG impairs cell migration due to an increase in oxidative stress that causes polarity loss, deficient adhesion and protrusion. These alterations arise, in large part, from increased Rac1 activity and may contribute to the poor wound healing observed in diabetic patients.

Uranium Metal to Oxide Conversion by Air Oxidation –Process Development

Energy Technology Data Exchange (ETDEWEB)

Duncan, A

2001-12-31

Published technical information for the process of metal-to-oxide conversion of uranium components has been reviewed and summarized for the purpose of supporting critical decisions for new processes and facilities for the Y-12 National Security Complex. The science of uranium oxidation under low, intermediate, and high temperature conditions is reviewed. A process and system concept is outlined and process parameters identified for uranium oxide production rates. Recommendations for additional investigations to support a conceptual design of a new facility are outlined.

High temperature oxidation and electrochemical investigations on nickel-base alloys

International Nuclear Information System (INIS)

Obigodi-Ndjeng, Georgia

2011-01-01

This study examined high-temperature oxidation behavior of different Ni-base alloys. In addition, electrochemical characterization of the alloy's corrosion behavior was carried out, including comparison of the properties of native passive films grown at room temperature and high temperature oxide scales. PWA 1483 (single-crystalline Ni-base superalloy) and model alloys Ni-Cr-X (where X is either Co or Al) were oxidized at 800 and 900 C in air for different time periods. The superalloy showed the best oxidation behavior at both temperatures, which might be due to the fact that the oxidation growth function is subparabolic for the model alloys and parabolic for the superalloy at 800 C. At higher temperatures, changes in the kinetics are induced, as the oxides grow faster, thus only PWA 1483 growth follows the parabolic law. Different scales in a typical sandwich form were detected, with the inner layer comprised of mostly Cr 2 O 3 , the middle layer was mixture of different oxides and spinels, depending on the alloying elements, and the oxide at the interface oxygen/oxide was found to be NiO. The influence of sample preparation could also be shown, as rougher surfaces change the oxidation kinetics from parabolic and subparabolic for polished samples to linear. The influence of moisture on the oxidation behavior of the 2 nd generation single crystal Ni-base superalloys (PWA 1484, PWA 1487, CMSX 4, Rene N5 and Rene N5+) was studied at 1000 C after 100 h oxidation period. It was found that the moisture increased the oxidation rate and mostly the transient oxides growth rate. The water vapor content in air also influenced the behavior of these alloys, as they showed a higher mass gain in air + 30% water vapor than in air + 10% water vapor. The alloys PWA 1484 and CMSX 4 showed respectively the worst and best behavior in all the studied atmospheres. The addition of reactive elements, such as Yttrium, Hafnium and Lanthanum is likely to enhance the oxidation behavior of PWA

Solubility of Tc(IV) oxides

International Nuclear Information System (INIS)

Liu, D.J.; Fan, X.H.

2005-01-01

Full text of publication follows: The deep geological disposal of the high level radioactive wastes is expected to be a safer disposal method in most countries. The long-lived fission product 99 Tc is present in large quantities in nuclear wastes and its chemical behavior in aqueous solution is of considerable interest. Under the reducing conditions, expected to exist in a deep geological repository, it is generally predicted that technetium will be present as TcO 2 .nH 2 O. The solubility of Tc(IV) is used as a source term in performance assessment of radioactive waste repository. Technetium oxide was prepared by reduction of a technetate solution with Sn 2+ . The solubility of Tc(IV) oxide has been determined in simulated groundwater and re-distilled water under aerobic and anaerobic conditions. The effects of pH and CO 3 2- concentration of solution on solubility of Tc(IV) oxide were studied. The concentration of total technetium and Tc(IV) species in the solutions were periodically determined by separating the oxidized and reduced technetium species using a solvent extraction procedure and counting the beta activity of the 99 Tc with a liquid scintillation counter. The experimental results show that the rate of oxidation of Tc(IV) in simulated groundwater and re-distilled water is about (1.49∼1.86) x 10 -9 mol/(L.d) under aerobic conditions, but Tc(IV) in simulated groundwater and re-distilled water is not oxidized under anaerobic conditions. Under aerobic or anaerobic conditions the solubility of Tc(IV) oxide in simulated groundwater and re-distilled water is equal on the whole after centrifugation or ultrafiltration. The solubility of Tc(IV) oxide decreases with the increase of pH at pH 10 and is pH independent in the range 2 -8 to 10 -9 mol/L at 2 3 2- concentration. These data could be used to estimate the Tc(IV) solubility for cases where solubility limits transport of technetium in reducing environments of high-level waste repositories. (authors)

Synthesis and characterization of nanoporous anodic oxide film on aluminum in H3PO4 + KMnO4 electrolyte mixture at different anodization conditions

Science.gov (United States)

Verma, Naveen; Jindal, Jitender; Singh, Krishan Chander; Mari, Bernabe

2016-04-01

The micro structural properties of nanoporous anodic oxide film formed in H3PO4 were highly influenced by addition of a low concentration of KMnO4 (0.0005 M) in 1 M H3PO4 solution. The KMnO4 as additive enhanced the growth rate of oxide film formation as well as thickness of pore walls. Furthermore the growth rate was found increased with increase in applied current density. The increase in temperature and lack of stirring during anodization causes the thinness of pore wall which leads to increase in pore volume. With the decrease in concentration of H3PO4 in anodizing electrolyte from 1M to 0.3 M, keeping all other conditions constant, the decrease in porosity was observed. This might be due to the dissolution of aluminium oxide film in highly concentrated acidic solution.

Functionalization of 2D macroporous silicon under the high-pressure oxidation

Science.gov (United States)

Karachevtseva, L.; Kartel, M.; Kladko, V.; Gudymenko, O.; Bo, Wang; Bratus, V.; Lytvynenko, O.; Onyshchenko, V.; Stronska, O.

2018-03-01

Addition functionalization after high-pressure oxidation of 2D macroporous silicon structures is evaluated. X-ray diffractometry indicates formation of orthorhombic SiO2 phase on macroporous silicon at oxide thickness of 800-1200 nm due to cylindrical symmetry of macropores and high thermal expansion coefficient of SiO2. Pb center concentration grows with the splitting energy of LO- and TO-phonons and SiO2 thickness in oxidized macroporous silicon structures. This increase EPR signal amplitude and GHz radiation absorption and is promising for development of high-frequency devices and electronically controlled elements.

High Performance Nitrous Oxide Analyzer for Atmospheric Research, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — This project targets the development of a highly sensitive gas sensor to monitor atmospheric nitrous oxide. Nitrous oxide is an important species in Earth science...

Experimental and Modeling Investigation of the Effectof H2S Addition to Methane on the Ignition and Oxidation at High Pressures

DEFF Research Database (Denmark)

Gersen, Sander; van Essen, Martijn; Darmeveil, Harry

2017-01-01

The autoignition and oxidation behavior of CH4/H2S mixtures has been studied experimentally in a rapid compression machine (RCM) and a high-pressure flow reactor. The RCM measurements show that the addition of 1% H2S to methane reduces the autoignition delay time by a factor of 2 at pressures....... A comparison of the flow reactordata to modeling predictions shows satisfactory agreement under stoichiometric conditions, while at very reducing conditions, the model underestimates the consumption of both H2S and CH4. Similar to the RCM experiments, the presence of H2S is predicted to promote oxidation...

Combination of nitric oxide therapy, anti-oxidative therapy, low level laser therapy, plasma rich platelet therapy and stem cell therapy as a novel therapeutic application to manage the pain and treat many clinical conditions

Science.gov (United States)

Halasa, Salaheldin; Dickinson, Eva

2014-02-01

From hypertension to diabetes, cancer to HIV, stroke to memory loss and learning disorders to septic shock, male impotence to tuberculosis, there is probably no pathological condition where nitric oxide does not play an important role. Nitric oxide is an analgesic, immune-modulator, vasodilator, anti-apoptotic, growth modulator, angiogenetic, anti-thrombotic, anti-inflammatory and neuro-modulator. Because of the above actions of nitric oxide, many clinical conditions associated with abnormal Nitric oxide (NO) production and bioavailability. Our novel therapeutic approach is to restore the homeostasis of nitric oxide and replace the lost cells by combining nitric oxide therapy, anti-oxidative therapy, low level laser therapy, plasma rich platelet therapy and stem cell therapy.

Highly conducting and transparent sprayed indium tin oxide

Energy Technology Data Exchange (ETDEWEB)

Rami, M.; Benamar, E.; Messaoudi, C.; Sayah, D.; Ennaoui, A. (Faculte des Sciences, Rabat (Morocco). Lab. de Physique des Materiaux)

1998-03-01

Indium tin oxide (ITO) has a wide range of applications in solar cells (e.g. by controlling the resistivity, we can use low conductivity ITO as buffer layer and highly conducting ITO as front contact in thin films CuInS[sub 2] and CuInSe[sub 2] based solar cells) due to its wide band gap (sufficient to be transparent) in both visible and near infrared range, and high carrier concentrations with metallic conduction. A variety of deposition techniques such as reactive electron beam evaporation, DC magnetron sputtering, evaporation, reactive thermal deposition, and spray pyrolysis have been used for the preparation of undoped and tin doped indium oxide. This latter process which makes possible the preparation of large area coatings has attracted considerable attention due to its simplicity and large scale with low cost fabrication. It has been used here to deposit highly transparent and conducting films of tin doped indium oxide onto glass substrates. The electrical, optical and structural properties have been investigated as a function of various deposition parameters namely dopant concentrations, temperature and nature of substrates. X-ray diffraction patterns have shown that deposited films are polycrystalline without second phases and have preferred orientation [400]. INdium tin oxide layers with small resistivity value around 7.10[sup -5] [omega].cm and transmission coefficient in the visible and near IR range of about 85-90% have been easily obtained. (authors) 13 refs.

Catalytic aerobic oxidation of bio-renewable chemicals

DEFF Research Database (Denmark)

Gorbanev, Yury

, EDS, XRF and other methods. Supported gold and ruthenium hydroxide catalyst systems were explored for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDA), a potential polymer building block for the plastic industry, or its dimethyl ester (FDMC). High product......-free conditions. Moreover, a detailed study on the performance and stability of the ruthenium hydroxide catalysts on magnesium-containing supports under reaction conditions was conducted. The aerobic oxidation of HMF to form another value-added chemical, 2,5-diformylfuran (DFF), was also investigated......Ox deposited on various metal oxides. Furthermore, this thesis presents the results of the catalytic aerobic oxidative degradation of higher alcohols over supported ruthenium hydroxide catalysts. A very efficient oxidative cleavage of vic-diols to form respective acids was also shown under examined conditions...

Long Term Stability Investigation of Solid Oxide Electrolysis Cell with Infiltrated Porous YSZ Air Electrode Under High Current

DEFF Research Database (Denmark)

Veltzé, Sune; Ovtar, Simona; Simonsen, Søren Bredmose

2015-01-01

stabilised zirconia (YSZ) backbone air electrode and Ni/YSZ cermet fuel electrode. The SOC was tested at electrolysis conditions under high current (up to -1 A/cm2). The porous YSZ electrodes was infiltrated with gadolinium-doped ceria oxide (CGO), to act as a barrier layer between the catalyst...

Clay mineral formation under oxidized conditions and implications for paleoenvironments and organic preservation on Mars.

Science.gov (United States)

Gainey, Seth R; Hausrath, Elisabeth M; Adcock, Christopher T; Tschauner, Oliver; Hurowitz, Joel A; Ehlmann, Bethany L; Xiao, Yuming; Bartlett, Courtney L

2017-11-01

Clay mineral-bearing locations have been targeted for martian exploration as potentially habitable environments and as possible repositories for the preservation of organic matter. Although organic matter has been detected at Gale Crater, Mars, its concentrations are lower than expected from meteoritic and indigenous igneous and hydrothermal reduced carbon. We conducted synthesis experiments motivated by the hypothesis that some clay mineral formation may have occurred under oxidized conditions conducive to the destruction of organics. Previous work has suggested that anoxic and/or reducing conditions are needed to synthesize the Fe-rich clay mineral nontronite at low temperatures. In contrast, our experiments demonstrated the rapid formation of Fe-rich clay minerals of variable crystallinity from aqueous Fe 3+ with small amounts of aqueous Mg 2+ . Our results suggest that Fe-rich clay minerals such as nontronite can form rapidly under oxidized conditions, which could help explain low concentrations of organics within some smectite-containing rocks or sediments on Mars.

Clay mineral formation under oxidized conditions and implications for paleoenvironments and organic preservation on Mars

Energy Technology Data Exchange (ETDEWEB)

Gainey, Seth R.; Hausrath, Elisabeth M.; Adcock, Christopher T.; Tschauner, Oliver; Hurowitz, Joel A.; Ehlmann, Bethany L.; Xiao, Yuming; Bartlett, Courtney L. (CIW); (UNLV); (CIT); (SBU)

2017-11-01

Clay mineral-bearing locations have been targeted for martian exploration as potentially habitable environments and as possible repositories for the preservation of organic matter. Although organic matter has been detected at Gale Crater, Mars, its concentrations are lower than expected from meteoritic and indigenous igneous and hydrothermal reduced carbon. We conducted synthesis experiments motivated by the hypothesis that some clay mineral formation may have occurred under oxidized conditions conducive to the destruction of organics. Previous work has suggested that anoxic and/or reducing conditions are needed to synthesize the Fe-rich clay mineral nontronite at low temperatures. In contrast, our experiments demonstrated the rapid formation of Fe-rich clay minerals of variable crystallinity from aqueous Fe3+ with small amounts of aqueous Mg2+. Our results suggest that Fe-rich clay minerals such as nontronite can form rapidly under oxidized conditions, which could help explain low concentrations of organics within some smectite-containing rocks or sediments on Mars.

Segregation across the metal/oxide interface occurring during oxidation at high temperatures of diluted iron based alloys

International Nuclear Information System (INIS)

Geneve, D.; Rouxel, D.; Weber, B.; Confente, M.

2006-01-01

Industrial steels being elaborated in air at high temperature oxidize and cover with a complex oxide layer. The oxidation reaction drastically alters the surface composition. Such modifications have been investigated, in this work, by Auger Electron Spectroscopy (AES) using an original method to characterize the composition of the metal/oxide interfaces. Analysis of the concentration gradients across the interfaces allows to better understand how the alloy elements contribute to the oxidation process. The development of new alloy phases, the interdependencies between elements and the diffusion of different species are discussed considering thermodynamic properties of each element

Cellular membrane accommodation of copper-induced oxidative conditions in the coral Seriatopora caliendrum

Energy Technology Data Exchange (ETDEWEB)

Tang, Chuan-Ho, E-mail: chtang@nmmba.gov.tw [Institute of Marine Biodiversity and Evolutionary Biology, National Dong Hwa University, Pingtung, Taiwan, ROC (China); National Museum of Marine Biology and Aquarium, Pingtung, Taiwan, ROC (China); Lin, Ching-Yu [Institute of Environmental Health, National Taiwan University, Taipei City, Taiwan, ROC (China); Lee, Shu-Hui [Center of General Education, National Kaohsiung Marine University, Kaohsiung, Taiwan, ROC (China); Wang, Wei-Hsien [National Museum of Marine Biology and Aquarium, Pingtung, Taiwan, ROC (China); Department of Marine Biotechnology and Resources and Asia-Pacific Ocean Research Center, National Sun Yat-sen University, Kaohsiung, Taiwan, ROC (China)

2014-03-01

Highlights: • Coral cells alter membrane lipid to accommodate copper-induce oxidative conditions • Coral membrane repair occur due to lipid alterations • Zooxanthellae release results from membrane repair by symbiosome fusion • Copper-induced lipid alterations perturb membrane-related functions in coral cells • Copper chronic effect on coral fitness are related to long-term membrane perturbation - Abstract: Oxidative stress has been associated with copper-induced toxicity in scleractinian corals. To gain insight into the accommodation of the cellular membrane to oxidative conditions, a pocilloporid coral, Seriatopora caliendrum, was exposed to copper at distinct, environmentally relevant dose for various lengths of time. Glycerophosphocholine profiling of the response of the coral to copper exposure was characterized using a validated method. The results indicate that coral lipid metabolism is programmed to induce membrane alterations in response to the cellular deterioration that occurs during the copper exposure period. Decreasing lyso-phosphatidylcholines and exchanging polyunsaturated phosphatidylcholines for polyunsaturated plasmanylcholines were the initial actions taken to prevent membrane permeabilization. To relax/resist the resulting membrane strain caused by cell/organelle swelling, the coral cells inversely exchanged polyunsaturated plasmanylcholines for polyunsaturated phosphatidylcholines and further increased the levels of monounsaturated glycerophosphocholines. At the same time, the levels of saturated phosphatidylcholines were also increased to increase membrane rigidity and protect against oxidative attack. Interestingly, such alterations in lipid metabolism were also required for membrane fusion to repair the deteriorated membranes by repopulating them with proximal lipid reservoirs, similar to symbiosome membranes. Additionally, increasing saturated and monounsaturated plasmanylcholines and inhibiting the suppression of saturated lyso

Cellular membrane accommodation of copper-induced oxidative conditions in the coral Seriatopora caliendrum

International Nuclear Information System (INIS)

Tang, Chuan-Ho; Lin, Ching-Yu; Lee, Shu-Hui; Wang, Wei-Hsien

2014-01-01

Highlights: • Coral cells alter membrane lipid to accommodate copper-induce oxidative conditions • Coral membrane repair occur due to lipid alterations • Zooxanthellae release results from membrane repair by symbiosome fusion • Copper-induced lipid alterations perturb membrane-related functions in coral cells • Copper chronic effect on coral fitness are related to long-term membrane perturbation - Abstract: Oxidative stress has been associated with copper-induced toxicity in scleractinian corals. To gain insight into the accommodation of the cellular membrane to oxidative conditions, a pocilloporid coral, Seriatopora caliendrum, was exposed to copper at distinct, environmentally relevant dose for various lengths of time. Glycerophosphocholine profiling of the response of the coral to copper exposure was characterized using a validated method. The results indicate that coral lipid metabolism is programmed to induce membrane alterations in response to the cellular deterioration that occurs during the copper exposure period. Decreasing lyso-phosphatidylcholines and exchanging polyunsaturated phosphatidylcholines for polyunsaturated plasmanylcholines were the initial actions taken to prevent membrane permeabilization. To relax/resist the resulting membrane strain caused by cell/organelle swelling, the coral cells inversely exchanged polyunsaturated plasmanylcholines for polyunsaturated phosphatidylcholines and further increased the levels of monounsaturated glycerophosphocholines. At the same time, the levels of saturated phosphatidylcholines were also increased to increase membrane rigidity and protect against oxidative attack. Interestingly, such alterations in lipid metabolism were also required for membrane fusion to repair the deteriorated membranes by repopulating them with proximal lipid reservoirs, similar to symbiosome membranes. Additionally, increasing saturated and monounsaturated plasmanylcholines and inhibiting the suppression of saturated lyso

Solid oxide fuel cell performance under severe operating conditions

DEFF Research Database (Denmark)

Koch, Søren; Hendriksen, P.V.; Mogensen, Mogens Bjerg

2006-01-01

The performance and degradation of Solid Oxide Fuel Cells (SOFC) were studied under severe operating conditions. The cells studied were manufactured in a small series by ECN, in the framework of the EU funded CORE-SOFC project. The cells were of the anode-supported type with a double layer LSM...... cathode. They were operated at 750 °C or 850 °C in hydrogen with 5% or 50% water at current densities ranging from 0.25 A cm–2 to 1 A cm–2 for periods of 300 hours or more. The area specific cell resistance, corrected for fuel utilisation, ranged between 0.20 Ω cm2 and 0.34 Ω cm2 at 850 °C and 520 m......V, and between 0.51 Ω cm2 and 0.92 Ω cm2 at 750 °C and 520 mV. The degradation of cell performance was found to be low (ranging from 0 to 8%/1,000 hours) at regular operating conditions. Voltage degradation rates of 20 to 40%/1,000 hours were observed under severe operating conditions, depending on the test...

Subsurface Conditions Controlling Uranium Incorporation in Iron Oxides: A Redox Stable Sink

International Nuclear Information System (INIS)

Fendorf, Scott

2016-01-01

Toxic metals and radionuclides throughout the U.S. Department of Energy Complex pose a serious threat to ecosystems and to human health. Of particular concern is the redox-sensitive radionuclide uranium, which is classified as a priority pollutant in soils and groundwaters at most DOE sites owing to its large inventory, its health risks, and its mobility with respect to primary waste sources. The goal of this research was to contribute to the long-term mission of the Subsurface Biogeochemistry Program by determining reactions of uranium with iron (hydr)oxides that lead to long-term stabilization of this pervasive contaminant. The research objectives of this project were thus to (1) identify the (bio)geochemical conditions, including those of the solid-phase, promoting uranium incorporation in Fe (hydr)oxides, (2) determine the magnitude of uranium incorporation under a variety of relevant subsurface conditions in order to quantify the importance of this pathway when in competition with reduction or adsorption; (3) identify the mechanism(s) of U(VI/V) incorporation in Fe (hydr)oxides; and (4) determine the stability of these phases under different biogeochemical (inclusive of redox) conditions. Our research demonstrates that redox transformations are capable of achieving U incorporation into goethite at ambient temperatures, and that this transformation occurs within days at U and Fe(II) concentrations that are common in subsurface geochemical environments with natural ferrihydrites - inclusive of those with natural impurities. Increasing Fe(II) or U concentration, or initial pH, made U(VI) reduction to U(IV) a more competitive sequestration pathway in this system, presumably by increasing the relative rate of U reduction. Uranium concentrations commonly found in contaminated subsurface environments are often on the order of 1-10 μM, and groundwater Fe(II) concentrations can reach exceed 1 mM in reduced zones of the subsurface. The redox-driven U(V) incorporation

Subsurface Conditions Controlling Uranium Incorporation in Iron Oxides: A Redox Stable Sink

Energy Technology Data Exchange (ETDEWEB)

Fendorf, Scott [Stanford Univ., CA (United States)

2016-04-05

Toxic metals and radionuclides throughout the U.S. Department of Energy Complex pose a serious threat to ecosystems and to human health. Of particular concern is the redox-sensitive radionuclide uranium, which is classified as a priority pollutant in soils and groundwaters at most DOE sites owing to its large inventory, its health risks, and its mobility with respect to primary waste sources. The goal of this research was to contribute to the long-term mission of the Subsurface Biogeochemistry Program by determining reactions of uranium with iron (hydr)oxides that lead to long-term stabilization of this pervasive contaminant. The research objectives of this project were thus to (1) identify the (bio)geochemical conditions, including those of the solid-phase, promoting uranium incorporation in Fe (hydr)oxides, (2) determine the magnitude of uranium incorporation under a variety of relevant subsurface conditions in order to quantify the importance of this pathway when in competition with reduction or adsorption; (3) identify the mechanism(s) of U(VI/V) incorporation in Fe (hydr)oxides; and (4) determine the stability of these phases under different biogeochemical (inclusive of redox) conditions. Our research demonstrates that redox transformations are capable of achieving U incorporation into goethite at ambient temperatures, and that this transformation occurs within days at U and Fe(II) concentrations that are common in subsurface geochemical environments with natural ferrihydrites—inclusive of those with natural impurities. Increasing Fe(II) or U concentration, or initial pH, made U(VI) reduction to U(IV) a more competitive sequestration pathway in this system, presumably by increasing the relative rate of U reduction. Uranium concentrations commonly found in contaminated subsurface environments are often on the order of 1-10 μM, and groundwater Fe(II) concentrations can reach exceed 1 mM in reduced zones of the subsurface. The redox-driven U(V) incorporation

Photo-oxidation of histidine peptides yields high concentrations of unstable peroxides

International Nuclear Information System (INIS)

Policarpio, V.V.; Hawkins, C.L.; Davies, M.J.

2003-01-01

Oxidation of proteins by UV, and visible light in the presence of sensitizers, results in side chain modification as well as aggregation and fragmentation. In particular, singlet oxygen has been reported to oxidize Met, Trp, Tyr, Cys and His side chains in a selective manner. In this study the oxidation of histidine and its derivatives, and His-containing peptides is examined using a range of sensitizers, to determine whether peroxides are major intermediates, and the mechanism of formation of these species. Visible light-sensitised oxidation of Gly-His-Gly in the presence of oxygen and rose bengal gives unstable substrate-derived peroxides with the peroxide yield increasing with increasing photolysis time. Similar behaviour was detected with other photosensitizers, though the peroxide yields varied with the sensitizer at identical concentrations with rose bengal > aluminium phthalocyanine > hematoporphyrin IX > zinc phthalocyanine > tetrakisporphine. The peroxide yield was decreased in the presence of azide and enhanced when deuterium oxide was employed as the solvent, consistent with peroxide formation being singlet oxygen mediated. Experiments using anoxic conditions gave low yields of peroxides confirming the oxygen-dependence of these reactions. HPLC analysis showed rapid loss of the parent peptide, with subsequent formation of both stable and unstable products; these are currently being characterized by MS and NMR. Similar behavior has been observed with other His derivatives. The yield of singlet oxygen formed in these reactions has been estimated using a bleaching assay (N, N-dimethyl-4-nitrosoaniline). Quantification of singlet oxygen formation and Gly-His-Gly derived peroxide during rose bengal-mediated photooxidation indicated a conversion efficiency of the initial singlet oxygen into substrate-derived peroxides of ca. 75% indicating that peroxide formation is a highly efficient and major reaction pathway

High temperature mechanisms and kinetics of SiC oxidation under low partial pressures of oxygen: application to the fuel cladding of gas fast reactors

International Nuclear Information System (INIS)

Hun, N.

2011-01-01

Gas Fast Reactor (GFR) is one of the different Generation IV concepts under investigation for energy production. SiC/SiC composites are candidates of primary interest for a GFR fuel cladding use, thanks to good corrosion resistance among other properties. The mechanisms and kinetics of SiC oxidation under operating conditions have to be identified and quantified as the corrosion can decrease the mechanical properties of the composite. An experimental device has been developed to study the oxidation of silicon carbide under high temperature and low oxygen partial pressure. The results pointed out that not only parabolic oxidation, but also interfacial reactions and volatilization occur under such conditions. After determining the kinetics of each mechanism, as functions of oxygen partial pressure and temperature, the data are used for the modeling of the composites oxidation. The model will be used to predict the lifetime of the composite in operating conditions. (author) [fr

Molecular-beam-deposited yttrium-oxide dielectrics in aluminum-gated metal - oxide - semiconductor field-effect transistors: Effective electron mobility

International Nuclear Information System (INIS)

Ragnarsson, L.-A degree.; Guha, S.; Copel, M.; Cartier, E.; Bojarczuk, N. A.; Karasinski, J.

2001-01-01

We report on high effective mobilities in yttrium-oxide-based n-channel metal - oxide - semiconductor field-effect transistors (MOSFETs) with aluminum gates. The yttrium oxide was grown in ultrahigh vacuum using a reactive atomic-beam-deposition system. Medium-energy ion-scattering studies indicate an oxide with an approximate composition of Y 2 O 3 on top of a thin layer of interfacial SiO 2 . The thickness of this interfacial oxide as well as the effective mobility are found to be dependent on the postgrowth anneal conditions. Optimum conditions result in mobilities approaching that of SiO 2 -based MOSFETs at higher fields with peak mobilities at approximately 210 cm 2 /Vs. [copyright] 2001 American Institute of Physics

Effect of total pressure on graphite oxidation

International Nuclear Information System (INIS)

Burnette, R.D.; Hoot, C.G.

1983-04-01

Graphite corrosion in the high-temperature gas-cooled reactor (HTGR) is calculated using two key assumptions: (1) the kinetic, catalysis, and transport characteristics of graphite determined by bench-scale tests apply to large components at reactor conditions and (2) the effects of high pressure and turbulent flow are predictable. To better understand the differences between laboratory tests and reactor conditions, a high-pressure test loop (HPTL) has been constructed and used to perform tests at reactor temperature, pressure, and flow conditions. The HPTL is intended to determine the functional dependence of oxidation rate and characteristics on total pressure and gas velocity and to compare the oxidation results with calculations using models and codes developed for the reactor

Anaerobic oxidation of 2-chloroethanol under denitrifying conditions by Pseudomonas stutzeri strain JJ.

Science.gov (United States)

Dijk, J A; Stams, A J M; Schraa, G; Ballerstedt, H; de Bont, J A M; Gerritse, J

2003-11-01

A bacterium that uses 2-chloroethanol as sole energy and carbon source coupled to denitrification was isolated from 1,2-dichloroethane-contaminated soil. Its 16 S rDNA sequence showed 98% similarity with the type strain of Pseudomonas stutzeri (DSM 5190) and the isolate was tentatively identified as Pseudomonas stutzeri strain JJ. Strain JJ oxidized 2-chloroethanol completely to CO(2) with NO(3)(- )or O(2) as electron acceptor, with a preference for O(2) if supplied in combination. Optimum growth on 2-chloroethanol with nitrate occurred at 30 degrees C with a mu(max) of 0.14 h(-1) and a yield of 4.4 g protein per mol 2-chloroethanol metabolized. Under aerobic conditions, the mu(max) was 0.31 h(-1). NO(2)(-) also served as electron acceptor, but reduction of Fe(OH)(3), MnO(2), SO(4)(2-), fumarate or ClO(3)(-) was not observed. Another chlorinated compound used as sole energy and carbon source under aerobic and denitrifying conditions was chloroacetate. Various different bacterial strains, including some closely related Pseudomonas stutzeri strains, were tested for their ability to grow on 2-chloroethanol as sole energy and carbon source under aerobic and denitrifying conditions, respectively. Only three strains, Pseudomonas stutzeri strain LMD 76.42, Pseudomonas putida US2 and Xanthobacter autotrophicus GJ10, grew aerobically on 2-chloroethanol. This is the first report of oxidation of 2-chloroethanol under denitrifying conditions by a pure bacterial culture.

Cyclopentadienyl molybdenum(II/VI) N-heterocyclic carbene complexes: Synthesis, structure, and reactivity under oxidative conditions

KAUST Repository

Li, Shenyu

2010-04-26

A series of N-heterocyclic carbene (NHC) complexes CpMo(CO) 2(NHC)X (NHC = IMe = 1,3-dimethylimidazol-2-ylidene, X = Br, 1; NHC = 1,3-dipropylimidazol-2-ylidene, X = Br, 2; NHC = IMes = 1,3-bis(2,4,6- trimethylphenyl)imidazol-2-ylidene, X = Br, 3; NHC = IBz = 1,3-dibenzylimidazol- 2-ylidene, X = Br, 4a, and X = Cl, 4b; NHC = 1-methyl-3-propylimidazol-2- ylidene, X = Br, 5) and [CpMo(CO)2(IMes)(CH3CN)][BF 4] (6) have been synthesized and fully characterized. The stability of metal-NHC ligand bonds in these compounds under oxidative conditions has been investigated. The thermally stable Mo(VI) dioxo NHC complex [CpMoO 2(IMes)][BF4] (9) has been isolated by the oxidation of the ionic complex 6 by TBHP (tert-butyl hydrogen peroxide). Complex 6 can be applied as a very active (TOFs up to 3400 h-1) and selective olefin epoxidation catalyst. While under oxidative conditions (in the presence of TBHP), compounds 1-5 decompose into imidazolium bromide and imidazolium polyoxomolybdate. The formation of polyoxomolybdate as oxidation products had not been observed in a similar epoxidation catalyzed by Mo(II) and Mo(VI) complexes. DFT studies suggest that the presence of Br- destabilizes the CpMo(VI) oxo NHC carbene species, consistent with the experimental observations. © 2010 American Chemical Society.

Elaboration and characterisation of yttrium oxide and hafnium oxide powders by the sol-gel process

International Nuclear Information System (INIS)

Hours, T.

1988-01-01

The two classical sol-gel processes, colloidal and polymeric are studied for the preparation of yttrium oxide and hafnium oxide high performance powders. In the colloidal process, controlled and reproducible conditions for the preparation of yttrium oxide and hafnium oxide sols from salts or alkoxides are developed and the hydrothermal synthesis monodisperse hafnium oxide colloids is studied. The polymeric process is studied with hafnium ethyl-hexylate, hydrolysis kinetics for controlled preparation of sols and gels is investigated. Each step of preparation is detailed and powders obtained are characterized [fr

High temperature oxidation characteristics of developed Ni-Cr-W superalloys in air

International Nuclear Information System (INIS)

Suzuki, Tomio; Shindo, Masami

1996-11-01

For expanding utilization of the Ni-Cr-W superalloy, which has been developed as one of new high temperature structural materials used in the advanced High Temperature Gas-cooled Reactors (HTGRs), in various engineering fields including the structural material for heat utilization system, the oxidation behavior of this alloy in air as one of high oxidizing environments becomes one of key factors. The oxidation tests for the industrial scale heat of Ni-Cr-W superalloy with the optimized chemical composition and five kinds of experimental Ni-Cr-W alloys with different Cr/W ratio were carried out at high temperatures in the air compared with Hastelloy XR. The conclusions were obtained as follows. (1) The oxidation resistance of the industrial scale heat of Ni-Cr-W superalloy with the optimized chemical composition was superior to that of Hastelloy XR. (2) The most excellent oxidation resistance was obtained in an alloy with 19% Cr of the industrial scale heat of Ni-Cr-W superalloy. (author)

Experimental simulations of oxidizing conditions and organic decomposition on the surface of Mars

International Nuclear Information System (INIS)

Stoker, C.R.; Mancinelli, R.L.; Mckay, C.P.

1988-01-01

One important scientific objective of a Mars Rover Sample Return mission would be to look for traces of living and extinct life on Mars. An instrument to search for organic carbon may be the simplest instrument that could screen samples which are interesting from a biological point of view. An experimental program is described which would help to understand the nature of the oxidizing soil on Mars and the mechanism responsible for organic degradation on the Martian surface. This is approached by lab simulations of the actual conditions that occur on Mars, particularly the oxidant production by atmospheric photochemistry, and the combined effects of UV light and oxidants in decomposing organic compounds. The results will be used to formulate models of the photochemistry of the atmospheric, the atmosphere-soil interaction, and the diffusion of reactive compounds into the soils. This information will provide insights and constraints on the design of a sampling strategy to search for organic compounds on Mars

Analysis of metallogenic conditions of sandstone type uranium deposits in interlayer oxidation zone in the northwest of Junggar basin, Xinjiang

International Nuclear Information System (INIS)

Lin Shuangxing

1997-01-01

From various aspects such as the basin structures, structure features of the sedimentary cover, lithofacies features of basin sediments, geochemical characteristics of sedimentary rocks, regional hydrogeologic conditions and epigenetic reworking of the sedimentary cover and so on, the author analyzes the metallogenic conditions of sandstone type uranium deposits in interlayer oxidation zone in the northwest of Junggar basin. The author proposes that the area has abundant uranium sources, and possesses favourable stratigraphic combinations for the development of interlayer oxidation zone. Secondarily oxidized sandstone bodies present universally at places from the source area to stream channel facies. Reducing beds and secondarily reducing barrier are developed at the front of the secondarily oxidized sandstone body. The tectonic features of the sedimentary cover indicate that the area belongs to a relatively-stable suborogenic region and possesses secondary mobilization and reworking conditions during the uplifting and contraction stage of the basin. Epigenetic metallization is evident in the sedimentary cover of the basin

Oxidation and nitrosation of meat proteins under gastro-intestinal conditions: Consequences in terms of nutritional and health values of meat.

Science.gov (United States)

de La Pomélie, Diane; Santé-Lhoutellier, Véronique; Sayd, Thierry; Gatellier, Philippe

2018-03-15

The chemical changes (oxidation/nitrosation) of meat proteins during digestion lead to a decrease in their nutritional value. Moreover, oxidized and nitrosated amino acids are suspected to promote various human pathologies. To investigate the mechanisms and the kinetics of these endogenous protein modifications, we used a dynamic artificial digestive system (DIDGI®) that mimics the physicochemical conditions of digestion. The combined effect of meat cooking and endogenous addition of ascorbate and nitrite was evaluated on protein oxidation (by measuring carbonyl groups), protein nitrosation (by measuring nitrosamines), and proteolysis. Considerable carbonylation was observed in the digestive tract, especially under the acidic conditions of the stomach. Nitrosamines, caused by ammonia oxidation, were formed in conditions in which no nitrite was added, although the addition of nitrite in the model significantly increased their levels. Meat cooking and nitrite addition significantly decreased protein digestion. The interactions between all the changes affecting the proteins are discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Pivotal role of oxidative stress in tumor metastasis under diabetic conditions in mice.

Science.gov (United States)

Ikemura, Mai; Nishikawa, Makiya; Kusamori, Kosuke; Fukuoka, Miho; Yamashita, Fumiyoshi; Hashida, Mitsuru

2013-09-10

Diabetic patients are reported to have a high incidence and mortality of cancer, but little is known about the linkage. In this study, we investigated whether high oxidative stress is involved in the acceleration of tumor metastasis in diabetic mice. Murine melanoma B16-BL6 cells stably labeled with firefly luciferase (B16-BL6/Luc) were inoculated into the tail vein of streptozotocin (STZ)-treated or untreated mice. A luciferase assay demonstrated that tumor cells were present largely in the lung of untreated mice, whereas large numbers of tumor cells were detected in both the lung and liver of STZ-treated mice. Repeated injections of polyethylene glycol-conjugated catalase (PEG-catalase), a long-circulating derivative, reduced the elevated fasting blood glucose levels and plasma lipoperoxide levels of STZ-treated mice, but had no significant effects on these parameters in untreated mice. In addition, the injections significantly reduced the number of tumor cells in the lung and liver in both untreated and STZ-treated mice. Culture of B16-BL6/Luc cells in medium containing over 45 mg/dl glucose hardly affected the proliferation of the cells, whereas the addition of plasma of STZ-treated mice to the medium significantly increased the number of cells. Plasma samples of STZ-treated mice receiving PEG-catalase exhibited no such effect on proliferation. These findings indicate that a hyperglycemia-induced increase in oxidative stress is involved in the acceleration of tumor metastasis, and the removal of systemic hydrogen peroxide by PEG-catalase can inhibit the progression of diabetic conditions and tumor metastasis in diabetes. Copyright © 2013 Elsevier B.V. All rights reserved.

Oxidation Kinetics of Ferritic Alloys in High-Temperature Steam Environments

Science.gov (United States)

Parker, Stephen S.; White, Josh; Hosemann, Peter; Nelson, Andrew

2018-02-01

High-temperature isothermal steam oxidation kinetic parameters of several ferritic alloys were determined by thermogravimetric analysis. The oxidation kinetic constant ( k) was measured as a function of temperature from 900°C to 1200°C. The results show a marked increase in oxidation resistance compared to reference Zircaloy-2, with kinetic constants 3-5 orders of magnitude lower across the experimental temperature range. The results of this investigation supplement previous findings on the properties of ferritic alloys for use as candidate cladding materials and extend kinetic parameter measurements to high-temperature steam environments suitable for assessing accident tolerance for light water reactor applications.

The influence of nitric oxide and mercury chloride on leaf mesophyll structure under natural drought conditions

Directory of Open Access Journals (Sweden)

Mykola M. Musiyenko

2012-03-01

Full Text Available It is established that under natural drought conditions starch was accumulated in the central part of chloroplasts of mesophyll cells and chloroplasts were localized on the periphery of cells at plasmalemma. After treatment wheat plants by nitric oxide donor the decreasing of starch deposits number and close contacts between chloroplasts were indicated, elongated nucleus was localized in the centre of cells. After treatment wheat plant by mercury chloride chloroplasts in the cells lost their oval shape and contacts, increased eventually deposition of starch, indicating the acceleration of aging tissues. Thus, nitric oxide in drought conditions reduced the destructive effect of drought on mesophyll cells, and mercury chloride caused deformation of the membrane cell.

Functions of Nitric Oxide (NO in Roots during Development and under Adverse Stress Conditions

Directory of Open Access Journals (Sweden)

Francisco J. Corpas

2015-05-01

Full Text Available The free radical molecule, nitric oxide (NO, is present in the principal organs of plants, where it plays an important role in a wide range of physiological functions. Root growth and development are highly regulated by both internal and external factors such as nutrient availability, hormones, pattern formation, cell polarity and cell cycle control. The presence of NO in roots has opened up new areas of research on the role of NO, including root architecture, nutrient acquisition, microorganism interactions and the response mechanisms to adverse environmental conditions, among others. Additionally, the exogenous application of NO throughout the roots has the potential to counteract specific damages caused by certain stresses. This review aims to provide an up-to-date perspective on NO functions in the roots of higher plants.

Nonreactive spreading at high temperature: molten metals and oxides on molybdenum.

Science.gov (United States)

Saiz, E; Tomsia, A P; Rauch, N; Scheu, C; Ruehle, M; Benhassine, M; Seveno, D; de Coninck, J; Lopez-Esteban, S

2007-10-01

The spontaneous spreading of small liquid metal (Cu, Ag, Au) and oxide drops on Mo substrates has been studied using a drop transfer setup combined with high-speed video. Under the experimental conditions used in this work, spreading occurs in the absence of interfacial reactions or ridging. The analysis of the spreading data indicates that dissipation at the triple junction (that can be described in terms of a triple-line friction) is playing a dominant role in the movement of the liquid front. This is due, in part, to the much stronger atomic interactions in high-temperature systems when compared to organic liquids. As a result of this analysis, a comprehensive view of spreading emerges in which the strength of the atomic interactions (solid-liquid, liquid-liquid) determines the relative roles of viscous impedance and dissipation at the triple junction in spreading kinetics.

Halogen effect for improving high temperature oxidation resistance of Ti-50Al by anodization

Science.gov (United States)

Mo, Min-Hua; Wu, Lian-Kui; Cao, Hua-Zhen; Lin, Jun-Pin; Zheng, Guo-Qu

2017-06-01

The high temperature oxidation resistance of Ti-50Al was significantly improved via halogen effect which was achieved by anodizing in an ethylene glycol solution containing with fluorine ion. The anodized Ti-50Al with holes and micro-cracks could be self-repaired during oxidation at 1000 °C. The thickness of the oxide scale increases with the prolonging of oxidation time. On the basis of halogen effect for improving the high temperature oxidation resistance of Ti-50Al by anodization, only fluorine addition into the electrolyte can effectively improve the high temperature oxidation resistance of Ti-50Al.

Flow-Tube Reactor Experiments on the High Temperature Oxidation of Carbon Weaves

Science.gov (United States)

Panerai, Francesco; White, Jason D.; Robertson, Robert; Borner, Arnaud; Ferguson, Joseph C.; Mansour, Nagi N.

2017-01-01

Under entry conditions carbon weaves used in thermal protection systems (TPS) decompose via oxidation. Modeling this phenomenon is challenging due to the different regimes encountered along a flight trajectory. Approaches using equilibrium chemistry may lead to over-estimated mass loss and recession at certain conditions. Concurrently, there is a shortcoming of experimental data on carbon weaves to enable development of improved models. In this work, a flow-tube test facility was used to measure the oxidation of carbon weaves at temperatures up to 1500 K. The material tested was the 3D carbon weave used for the heat shield of the NASA Adaptive Deployable Entry and Placement Technology, ADEPT. Oxidation was characterized by quantifying decomposition gases (CO and CO2), by mass measurements, and by microscale surface analysis. The current set of measurements contributes to the development of finite rate chemistry models for carbon fabrics used in woven TPS materials.

Conditioning of Si-interfaces by wet-chemical oxidation: Electronic interface properties study by surface photovoltage measurements

Energy Technology Data Exchange (ETDEWEB)

Angermann, Heike, E-mail: angermann@helmholtz-berlin.de

2014-09-01

Highlights: • Determination of electronic interface properties by contact-less surface photovoltage (SPV) technique. • Systematic correlations of substrate morphology and surface electronic properties. • Optimization of surface pre-treatment for flat, saw damage etched, and textured Si solar cell substrates. • Ultra-thin passivating Si oxide layers with low densities of rechargeable states by wet-chemical oxidation and subsequent annealing. • Environmentally acceptable processes, utilizing hot water, diluted HCl, or ozone low cost alternative to current approaches with concentrated chemicals. • The effect of optimized wet-chemical pre-treatments can be preserved during subsequent layer deposition. - Abstract: The field-modulated surface photovoltage (SPV) method, a very surface sensitive technique, was utilized to determine electronic interface properties on wet-chemically oxidized and etched silicon (Si) interfaces. The influence of preparation-induced surface micro-roughness and un-stoichiometric oxides on the resulting the surface charge, energetic distribution D{sub it}(E), and density D{sub it,min} of rechargeable states was studied by simultaneous, spectroscopic ellipsometry (SE) measurements on polished Si(111) and Si(100) substrates. Based on previous findings and new research, a study of conventional and newly developed wet-chemical oxidation methods was established, correlating the interactions between involved oxidizing and etching solutions and the initial substrate morphology to the final surface conditioning. It is shown, which sequences of wet-chemical oxidation and oxide removal, have to be combined in order to achieve atomically smooth, hydrogen terminated surfaces, as well as ultra-thin oxide layers with low densities of rechargeable states on flat, saw damage etched, and textured Si substrates, as commonly applied in silicon device and solar cell manufacturing. These conventional strategies for wet-chemical pre-treatment are mainly

Conditioning of Si-interfaces by wet-chemical oxidation: Electronic interface properties study by surface photovoltage measurements

International Nuclear Information System (INIS)

Angermann, Heike

2014-01-01

Highlights: • Determination of electronic interface properties by contact-less surface photovoltage (SPV) technique. • Systematic correlations of substrate morphology and surface electronic properties. • Optimization of surface pre-treatment for flat, saw damage etched, and textured Si solar cell substrates. • Ultra-thin passivating Si oxide layers with low densities of rechargeable states by wet-chemical oxidation and subsequent annealing. • Environmentally acceptable processes, utilizing hot water, diluted HCl, or ozone low cost alternative to current approaches with concentrated chemicals. • The effect of optimized wet-chemical pre-treatments can be preserved during subsequent layer deposition. - Abstract: The field-modulated surface photovoltage (SPV) method, a very surface sensitive technique, was utilized to determine electronic interface properties on wet-chemically oxidized and etched silicon (Si) interfaces. The influence of preparation-induced surface micro-roughness and un-stoichiometric oxides on the resulting the surface charge, energetic distribution D it (E), and density D it,min of rechargeable states was studied by simultaneous, spectroscopic ellipsometry (SE) measurements on polished Si(111) and Si(100) substrates. Based on previous findings and new research, a study of conventional and newly developed wet-chemical oxidation methods was established, correlating the interactions between involved oxidizing and etching solutions and the initial substrate morphology to the final surface conditioning. It is shown, which sequences of wet-chemical oxidation and oxide removal, have to be combined in order to achieve atomically smooth, hydrogen terminated surfaces, as well as ultra-thin oxide layers with low densities of rechargeable states on flat, saw damage etched, and textured Si substrates, as commonly applied in silicon device and solar cell manufacturing. These conventional strategies for wet-chemical pre-treatment are mainly based on

Highly efficient Cu-decorated iron oxide nanocatalyst for low pressure CO 2 conversion

Energy Technology Data Exchange (ETDEWEB)

Halder, Avik; Kilianová, Martina; Yang, Bing; Tyo, Eric C.; Seifert, Soenke; Prucek, Robert; Panáček, Aleš; Suchomel, Petr; Tomanec, Ondřej; Gosztola, David J.; Milde, David; Wang, Hsien-Hau; Kvítek, Libor; Zbořil, Radek; Vajda, Stefan

2018-06-01

We report a nanoparticulate iron oxide based catalyst for CO2 conversion with high efficiency at low pressures and on the effect of the presence of copper on the catalyst's restructuring and its catalytic performance. In situ X-ray scattering reveals the restructuring of the catalyst at the nanometer scale. In situ X-ray absorption near edge structure (XANES) shows the evolution of the composition and oxidation state of the iron and copper components under reaction conditions along with the promotional effect of copper on the chemical transformation of the iron component. X-ray diffraction (XRD), XANES and Raman spectroscopy proved that the starting nano catalyst is composed of iron oxides differing in chemical nature (alpha-Fe2O3, Fe3O4, FeO(OH)) and dimensionality, while the catalyst after CO2 conversion was identified as a mixture of alpha-Fe, Fe3C, and traces of Fe5C2. The significant increase of the rate CO2 is turned over in the presence of copper nanoparticles indicates that Cu nanoparticles activate hydrogen, which after spilling over to the neighbouring iron sites, facilitate a more efficient conversion of carbon dioxide.

Regulation of taurine transport at the blood-placental barrier by calcium ion, PKC activator and oxidative stress conditions

Directory of Open Access Journals (Sweden)

Lee Na-Young

2010-08-01

Full Text Available Abstract Background In the present study, we investigated the changes of uptake and efflux transport of taurine under various stress conditions using rat conditionally immortalized syncytiotrophoblast cell line (TR-TBT cells, as in vitro blood-placental barrier (BPB model. Methods The transport of taurine in TR-TBT cells were characterized by cellular uptake study using radiolabeled taurine. The efflux of taurine was measured from the amount of radiolabeled taurine remaining in the cells after the uptake of radiolabeled taurine for 60 min. Results Taurine uptake was significantly decreased by phosphorylation of protein kinase C (PKC activator in TR-TBT cells. Also, calcium ion (Ca2+ was involved in taurine transport in TR-TBT cells. Taurine uptake was inhibited and efflux was enhanced under calcium free conditions in the cells. In addition, oxidative stress induced the change of taurine transport in TR-TBT cells, but the changes were different depending on the types of oxidative stress inducing agents. Tumor necrosis factor-α (TNF-α, lipopolysaccharide (LPS and diethyl maleate (DEM significantly increased taurine uptake, but H2O2 and nitric oxide (NO donor decreased taurine uptake in the cells. Taurine efflux was down-regulated by TNF-α in TR-TBT cells. Conclusion Taurine transport in TR-TBT cells were regulated diversely at extracellular Ca2+ level, PKC activator and oxidative stress conditions. It suggested that variable stresses affected the taurine supplies from maternal blood to fetus and taurine level of fetus.

Optimized high temperature oxidation and cleaning at Bugey 3

International Nuclear Information System (INIS)

Ranchoux, Gilles; Wintergerst, Matthieu; Bachet, Martin; Leclercq, Stephanie; Duron, Jean-Daniel; Meunier, Jean-Pierre; Blond, Serge; Dacquait Frederic

2012-09-01

As a part of the EDF Source Term Reduction project, an experimental procedure was carried out at Bugey 3 further to the steam generator replacement. This innovative procedure consists in theory in two complementary phases /1/: - Phase 1: a SG tubes optimized oxidation performed during pre-critical hot functional tests (basic and reducing chemistry) aims to generate an as protective as possible inner oxide layer allowing to reduce the later nickel release, - Phase 2: a cleaning procedure of the primary circuit performed under acid and reducing chemical conditioning at 170 deg. C intends to dissolve and eliminate the outer oxide layer by a simultaneous purification. The objective of such a procedure is to reduce corrosion products inventory (mainly nickel) generated by the first SG tube oxidation during hot functional tests and first operation months by carrying out an appropriate cleaning procedure. Gains were expected not only on RCS and auxiliary systems contamination, dose rates and thus collective dose but also on next outages duration. The objective of this paper is to describe the process implementation at Bugey 3: effective procedure put in place, monitoring program (chemistry and dose rate measurements, EMECC campaign) and firsts results. (authors)

Monomeric adiponectin increases cell viability in porcine aortic endothelial cells cultured in normal and high glucose conditions: Data on kinases activation

Directory of Open Access Journals (Sweden)

Elena Grossini

2016-09-01

Full Text Available We found that monomeric adiponectin was able to increase cell viability in porcine aortic endothelial cells (PAE cultured both in normal and high glucose condition. Moreover, in normal glucose condition monomeric adiponectin increased p38MAPK, Akt, ERK1/2 and eNOS phosphorylation in a dose- and time-dependent way. Also in high glucose condition monomeric adiponectin increased eNOS and above kinases phosphorylation with similar patterns but at lower extent. For interpretation of the data presented in this article, please see the research article “Monomeric adiponectin modulates nitric oxide release and calcium movements in porcine aortic endothelial cells in normal/high glucose conditions” (Grossini et al., in press [1].

Gold nanoclusters confined in a supercage of Y zeolite for aerobic oxidation of HMF under mild conditions.

Science.gov (United States)

Cai, Jiaying; Ma, Hong; Zhang, Junjie; Song, Qi; Du, Zhongtian; Huang, Yizheng; Xu, Jie

2013-10-11

Au nanoclusters with an average size of approximately 1 nm size supported on HY zeolite exhibit a superior catalytic performance for the selective oxidation of 5-hydroxymethyl-2-furfural (HMF) into 2,5-furandicarboxylic acid (FDCA). It achieved >99 % yield of 2,5-furandicarboxylic acid in water under mild conditions (60 °C, 0.3 MPa oxygen), which is much higher than that of Au supported on metal oxides/hydroxide (TiO2 , CeO2 , and Mg(OH)2 ) and channel-type zeolites (ZSM-5 and H-MOR). Detailed characterizations, such as X-ray diffraction, transmission electron microscopy, N2 -physisorption, and H2 -temperature-programmed reduction (TPR), revealed that the Au nanoclusters are well encapsulated in the HY zeolite supercage, which is considered to restrict and avoid further growing of the Au nanoclusters into large particles. The acidic hydroxyl groups of the supercage were proven to be responsible for the formation and stabilization of the gold nanoclusters. Moreover, the interaction between the hydroxyl groups in the supercage and the Au nanoclusters leads to electronic modification of the Au nanoparticles, which is supposed to contribute to the high efficiency in the catalytic oxidation of HMF to FDCA. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solubility study of Tc(IV) oxides

International Nuclear Information System (INIS)

Liu, D.J.; Fan, X.H.

2005-01-01

The deep geological disposal of the high level radioactive wastes is expected to be a safer disposal method in most countries. The long-lived fission product 99 Tc is present in large quantities in nuclear wastes and its chemical behavior in aqueous solution is of considerable interest. Under oxidizing conditions technetium exists as the anionic species TcO 4 - whereas under the reducing conditions, expected to exist in a deep geological repository, it is generally predicted that technetium will be present as TcO 2 ·nH 2 O. Hence, the mobility of Tc(IV) in reducing groundwater may be limited by the solubility of TcO 2 ·nH 2 O under these conditions. Due to this fact it is important to investigate the solubility of TcO 2 ·nH 2 O. The solubility determines the release of radionuclides from waste form and is used as a source term in radionuclide migration analysis in performance assessment of radioactive waste repository. Technetium oxide was prepared by reduction of a technetate solution with Sn 2 + . The solubility of Tc(IV) oxide has been determined in simulated groundwater and redistilled water under aerobic and anaerobic conditions. The effects of pH and CO 3 2- concentration of solution on solubility of Tc(IV) oxide were studied. The concentration of total technetium and Tc(IV) species in the solutions were periodically determined by separating the oxidized and reduced technetium species using a solvent extraction procedure and counting the beta activity of the 99 Tc with a liquid scintillation counter. The experimental results show that the rate of oxidation of Tc(IV) in simulated groundwater and redistilled water is about (1.49-1.86) x 10 -9 mol/(L·d) under aerobic conditions, but Tc(IV) in simulated groundwater and redistilled water is not oxidized under anaerobic conditions. Under aerobic or anaerobic conditions the solubility of Tc(IV) oxide in simulated groundwater and redistilled water is equal on the whole after centrifugation or ultrafiltration. The

Photocatalytic organic transformation by layered double hydroxides: highly efficient and selective oxidation of primary aromatic amines to their imines under ambient aerobic conditions.

Science.gov (United States)

Yang, Xiu-Jie; Chen, Bin; Li, Xu-Bing; Zheng, Li-Qiang; Wu, Li-Zhu; Tung, Chen-Ho

2014-06-25

We report the first application of layered double hydroxide as a photocatalyst in the transformation of primary aromatic amines to their corresponding imines with high efficiency and selectivity by using oxygen in an air atmosphere as a terminal oxidant under light irradiation.

Terbium oxide at high pressures

International Nuclear Information System (INIS)

Dogra, Sugandha; Sharma, Nita Dilawar; Singh, Jasveer; Bandhyopadhyay, A.K.

2011-01-01

In this work we report the behaviour of terbium oxide at high pressures. The as received sample was characterized at ambient by X-ray diffraction and Raman spectroscopy. The X-ray diffraction showed the sample to be predominantly cubic Tb 4 O 7 , although a few peaks also match closely with Tb 2 O 3 . In fact in a recent study done on the same sample, the sample has been shown to be a mixture of Tb 4 O 7 and Tb 2 O 3 . The sample was subjected to high pressures using a Mao-Bell type diamond anvil cell upto a pressure of about 42 GPa with ruby as pressure monitor

High-temperature oxidation behavior of dense SiBCN monoliths: Carbon-content dependent oxidation structure, kinetics and mechanisms

International Nuclear Information System (INIS)

Li, Daxin; Yang, Zhihua; Jia, Dechang; Wang, Shengjin; Duan, Xiaoming; Zhu, Qishuai; Miao, Yang; Rao, Jiancun; Zhou, Yu

2017-01-01

Highlights: •The scale growth for all investigated monoliths at 1500 °C cannot be depicted by a linear or parabolic rate law. •The carbon-rich monoliths oxidize at 1500 °C according to a approximately linear weight loss equation. •The excessive carbon in SiBCN monoliths deteriorates the oxidation resistance. •The oxidation resistance stems from the characteristic oxide structures and increased oxidation resistance of BN(C). -- Abstract: The high temperature oxidation behavior of three SiBCN monoliths: carbon-lean SiBCN with substantial Si metal, carbon-moderate SiBCN and carbon-rich SiBCN with excessive carbon, was investigated at 1500 °C for times up to15 h. Scale growth for carbon-lean and −moderate monoliths at 1500 °C cannot be described by a linear or parabolic rate law, while the carbon-rich monoliths oxidize according to a approximately linear weight loss equation. The microstructures of the oxide scale compose of three distinct layers. The passivating layer of carbon and boron containing amorphous SiO 2 and increased oxidation resistance of BN(C) both benefit the oxidation resistance.

Asymmetric oxidation of 1,3-dithianes to 1,3-dithiane 1-oxides

OpenAIRE

Yoshihiko, Watanabe; Yojiro, Ono; Yoshio, Ueno; Takeshi, Toru

1998-01-01

Oxidation of 2-(1-hydroxy-1-methylethyl)-1,3-dithiane with the Sharpless reagent has been examined under various reaction conditions. Oxidation of 2-(1-hydroxy-1-methylethyl)-1,3-dithiane with Ti(OPri)4-diethyl L-(+)-tartrate-tert-butyl hydroperoxide (1:2:1.5) in CH2Cl2 in the presence of 4 A molecular sieves gives (1S,2S)-2-(1-hydroxy-1-methylethyl)-1,3-dithiane 1-oxide with high trans selectivity and with moderate enantioselectivity. The enantioselectivity depends upon the substituent at t...

Asymptotic Slavery in the Copper Oxide High Temperature Superconductors

Science.gov (United States)

Phillips, Philip

2004-05-01

Vast progress in theoretical solid state physics has been made by constructing models which mimic the low-energy properties of solids. Essential to the success of this program is the separability of the high and low energy degrees of freedom. While it is hoped that a high energy reduction can be made to solve the problem of high temperature superconductivity in the copper oxide materials, I will show that no consistent theory is possible if the high energy scale is removed. At the heart of the problem is the mixing of all energy scales (that is, UV-IR mixing) in the copper-oxide materials. Optical experiments demonstrate that the number of low-energy degrees of freedom is derived from a high energy scale. The implications of the inseparability of the high and low energy degrees of freedom on the phase diagram of the cuprates is discussed.

Oxidation of laser-induced plasma species in different background conditions

Science.gov (United States)

Bator, Matthias; Schneider, Christof W.; Lippert, Thomas; Wokaun, Alexander

2013-08-01

The evolution of Lu and LuO species in a laser ablation plasma from different targets has been investigated by simultaneously performing mass spectrometry and plasma imaging. Ablation was achieved with a 248 nm KrF laser from a Lu, a Lu2O5 and a LuMnO3 target under different background gas conditions. Mass spectrometry measurements show very similar intensities and ratios for the respective species for all three targets under the same ablation conditions. This indicates only a small influence of the target on the final Lu and LuO contents in the plasma, with the major influence coming from collisions with the background gas. Furthermore, spatially, timely and spectrally resolved plasma imaging was utilized to clearly identify the shockwave at the plasma front as the main region for Lu oxidation. A strong decrease of Lu intensities together with a directly correlated increase of LuO was observed toward the outer regions of the plasma.

Stability of silver nanoparticles: agglomeration and oxidation in biological relevant conditions

Science.gov (United States)

Valenti, Laura E.; Giacomelli, Carla E.

2017-05-01

Silver nanoparticles (Ag-NP) are the most used nanomaterial in consumer products due to the intrinsic antimicrobial capacity of silver. However, Ag-NP may be also harmful to algae, aquatic species, mammalian cells, and higher plants because both Ag+ and nanoparticles are responsible of cell damages. The oxidative dissolution of Ag-NP would proceed to completion under oxic conditions, but the rate and extent of the dissolution depend on several factors. This work correlates the effect of the capping agent (albumin and citrate) with the stability of Ag-NP towards agglomeration in simulated body fluid (SBF) and oxidation in the presence of ROS species (H2O2). Capping provides colloidal stability only through electrostatic means, whereas albumin acts as bulky ligands giving steric and electrostatic repulsion, inhibiting the agglomeration in SBF. However, citrate capping protects Ag-NP from dissolution to a major extent than albumin does because of its reducing power. Moreover, citrate in solution minimizes the oxidation of albumin-coated Ag-NP even after long incubation times. H2O2-induced dissolution proceeds to completion with Ag-NP incubated in SBF, while incubation in citrate leads to an incomplete oxidation. In short, albumin is an excellent capping agent to minimize Ag-NP agglomeration whereas citrate provides a mild-reductive medium that prevents dissolution in biological relevant media as well as in the presence of ROS species. These results provide insight into how the surface properties and media composition affect the release of Ag+ from Ag-NP, related to the cell toxicity and relevant to the storage and lifetime of silver-containing nanomaterials.

Stability of silver nanoparticles: agglomeration and oxidation in biological relevant conditions

Energy Technology Data Exchange (ETDEWEB)

Valenti, Laura E.; Giacomelli, Carla E., E-mail: giacomel@fcq.unc.edu.ar [Universidad Nacional de Córdoba, Ciudad Universitaria, Instituto de Investigaciones en Físico Química de Córdoba (INFIQC) CONICET-UNC, Departamento de Fisicoquímica, Facultad de Ciencias Químicas (Argentina)

2017-05-15

Silver nanoparticles (Ag-NP) are the most used nanomaterial in consumer products due to the intrinsic antimicrobial capacity of silver. However, Ag-NP may be also harmful to algae, aquatic species, mammalian cells, and higher plants because both Ag{sup +} and nanoparticles are responsible of cell damages. The oxidative dissolution of Ag-NP would proceed to completion under oxic conditions, but the rate and extent of the dissolution depend on several factors. This work correlates the effect of the capping agent (albumin and citrate) with the stability of Ag-NP towards agglomeration in simulated body fluid (SBF) and oxidation in the presence of ROS species (H{sub 2}O{sub 2}). Capping provides colloidal stability only through electrostatic means, whereas albumin acts as bulky ligands giving steric and electrostatic repulsion, inhibiting the agglomeration in SBF. However, citrate capping protects Ag-NP from dissolution to a major extent than albumin does because of its reducing power. Moreover, citrate in solution minimizes the oxidation of albumin-coated Ag-NP even after long incubation times. H{sub 2}O{sub 2}-induced dissolution proceeds to completion with Ag-NP incubated in SBF, while incubation in citrate leads to an incomplete oxidation. In short, albumin is an excellent capping agent to minimize Ag-NP agglomeration whereas citrate provides a mild-reductive medium that prevents dissolution in biological relevant media as well as in the presence of ROS species. These results provide insight into how the surface properties and media composition affect the release of Ag{sup +} from Ag-NP, related to the cell toxicity and relevant to the storage and lifetime of silver-containing nanomaterials.

Oxidation characteristics of MgF2 in air at high temperature

Science.gov (United States)

Chen, H. K.; Jie, Y. Y.; Chang, L.

2017-02-01

High temperature oxidation properties of MgF2 in air were studied. The changes of phase composition, macro surface morphology, weight and elemental composition of MgF2 samples with temperature were investigated by using XRD, EDS and gravimetric analyses. The results show that the oxidation reaction of MgF2 converted to MgO occurred at high temperature, and the reaction was accelerated by the increase of temperature and the presence of impurities. This result clarifies the understanding of the high temperature oxidation behavior of MgF2 in air, and provides a theoretical basis for the reasonable application of MgF2 in optical coating materials, electronic ceramic materials and magnesium melt protection.

Global Transcriptional Responses to Osmotic, Oxidative, and Imipenem Stress Conditions in Pseudomonas putida.

Science.gov (United States)

Bojanovič, Klara; D'Arrigo, Isotta; Long, Katherine S

2017-04-01

Bacteria cope with and adapt to stress by modulating gene expression in response to specific environmental cues. In this study, the transcriptional response of Pseudomonas putida KT2440 to osmotic, oxidative, and imipenem stress conditions at two time points was investigated via identification of differentially expressed mRNAs and small RNAs (sRNAs). A total of 440 sRNA transcripts were detected, of which 10% correspond to previously annotated sRNAs, 40% to novel intergenic transcripts, and 50% to novel transcripts antisense to annotated genes. Each stress elicits a unique response as far as the extent and dynamics of the transcriptional changes. Nearly 200 protein-encoding genes exhibited significant changes in all stress types, implicating their participation in a general stress response. Almost half of the sRNA transcripts were differentially expressed under at least one condition, suggesting possible functional roles in the cellular response to stress conditions. The data show a larger fraction of differentially expressed sRNAs than of mRNAs with >5-fold expression changes. The work provides detailed insights into the mechanisms through which P. putida responds to different stress conditions and increases understanding of bacterial adaptation in natural and industrial settings. IMPORTANCE This study maps the complete transcriptional response of P. putida KT2440 to osmotic, oxidative, and imipenem stress conditions at short and long exposure times. Over 400 sRNA transcripts, consisting of both intergenic and antisense transcripts, were detected, increasing the number of identified sRNA transcripts in the strain by a factor of 10. Unique responses to each type of stress are documented, including both the extent and dynamics of the gene expression changes. The work adds rich detail to previous knowledge of stress response mechanisms due to the depth of the RNA sequencing data. Almost half of the sRNAs exhibit significant expression changes under at least one

Nitrous Oxide Production and Fluxes from Coastal Sediments under Varying Environmental Conditions

Science.gov (United States)

Ziebis, W.; Wankel, S. D.; de Beer, D.; Dentinger, J.; Buchwald, C.; Charoenpong, C.

2014-12-01

Although coastal zones represent important contributors to the increasing levels of atmospheric nitrous oxide (N2O), it is still unclear which role benthic processes play and whether marine sediments represent sinks or sources for N2O, since interactions among closely associated microbial groups lead to a high degree of variability. In addition, coastal areas are extremely dynamic regions, often exposed to increased nutrient loading and conditions of depleted oxygen. We investigated benthic N2O fluxes and how environmental conditions affect N2O production in different sediments at 2 different geographical locations (German Wadden Sea, a California coastal lagoon). At each location, a total of 32 sediment cores were taken in areas that differed in sediment type, organic content and pore-water nutrient concentrations, as well as in bioturbation activity. Parallel cores were incubated under in-situ conditions, low oxygen and increased nitrate levels for 10 days. Zones of N2O production and consumption were identified in intact cores by N2O microprofiles at the beginning and end of the experiments. In a collaborative effort to determine the dominant sources of N2O, samples were taken throughout the course of the experiments for the determination of the isotopic composition of N2O (as well as nitrate, nitrite and ammonium). Our results indicate that both, nitrate addition and low oxygen conditions in the overlying water, caused an increase of subsurface N2O production in most sediments, with a high variability between different sediment types. N2O production in the sediments was accompanied by N2O consumption, reducing the fluxes to the water column. In general, organic rich sediments showed the strongest response to environmental changes with increased production and efflux of N2O into the overlying water. Bioturbation activity added to the complexity of N2O dynamics by an increase in nitrification-denitrification processes, as well as enhanced pore-water transport

Preparation of highly oxidized RBa.sub.2 Cu.sub.4 O.sub.8 superconductors

Science.gov (United States)

Morris, Donald E.

1991-01-01

Novel superconducting materials in the form of compounds, structures or phases are formed by performing otherwise known syntheses in a highly oxidizing atmosphere rather than that created by molecular oxygen at atmospheric pressure or below. This leads to the successful synthesis of novel superconducting compounds which are thermodynamically stable at the conditions under which they are formed. The compounds and structures thus formed are substantially nonsusceptible to variations in their oxygen content when subjected to changing temperatures, thereby forming a temperature-stable substantially single phase crystal.

Non-activated high surface area expanded graphite oxide for supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Vermisoglou, E.C.; Giannakopoulou, T.; Romanos, G.E.; Boukos, N.; Giannouri, M. [Institute of Nanoscience and Nanotechnology “Demokritos”, 153 43 Ag. Paraskevi, Attikis (Greece); Lei, C.; Lekakou, C. [Division of Mechanical, Medical, and Aerospace Engineering, Faculty of Engineering and Physical Sciences, University of Surrey, Guildford GU2 7XH (United Kingdom); Trapalis, C., E-mail: c.trapalis@inn.demokritos.gr [Institute of Nanoscience and Nanotechnology “Demokritos”, 153 43 Ag. Paraskevi, Attikis (Greece)

2015-12-15

Graphical abstract: - Highlights: • One-step exfoliation and reduction of graphite oxide via microwave irradiation. • Effect of pristine graphite (type, flake size) on the microwave expanded material. • Effect of pretreatment and oxidation cycles on the produced expanded material. • Expanded graphene materials with high BET surface areas (940 m{sup 2}/g–2490 m{sup 2}/g). • Non-activated graphene based materials suitable for supercapacitors. - Abstract: Microwave irradiation of graphite oxide constitutes a facile route toward production of reduced graphene oxide, since during this treatment both exfoliation and reduction of graphite oxide occurs. In this work, the effect of pristine graphite (type, size of flakes), pretreatment and oxidation cycles on the finally produced expanded material was examined. All the types of graphite that were tested afforded materials with high BET surface areas ranging from 940 m{sup 2}/g to 2490 m{sup 2}/g, without intervening an activation stage at elevated temperature. SEM and TEM images displayed exfoliated structures, where the flakes were significantly detached and curved. The quality of the reduced graphene oxide sheets was evidenced both by X-ray photoelectron spectroscopy and Raman spectroscopy. The electrode material capacitance was determined via electrochemical impedance spectroscopy and cyclic voltammetry. The materials with PEDOT binder had better performance (∼97 F/g) at low operation rates while those with PVDF binder performed better (∼20 F/g) at higher rates, opening up perspectives for their application in supercapacitors.

Template synthesis of highly crystalline and monodisperse iron oxide pigments of nanosize

International Nuclear Information System (INIS)

Sreeram, Kalarical Janardhanan; Indumathy, Ramasamy; Rajaram, Ananthanarayanan; Nair, Balachandran Unni; Ramasami, Thirumalachari

2006-01-01

Synthesis of highly crystalline and monodisperse iron oxide nanoparticles is reported. The separation of Fe centers through site-specific binding to a polysaccharide-alginate matrix enables the generation of particles with a monodisperse or narrow size distribution character, resulting in transparent pigments. Site-specific interactions coupled with gel like character of alginate is proposed as the mechanism behind generation of lower particle sizes. Alginate-Fe complexes developed were subjected to heat treatment to provide for crystalline character and development of hematite (α-Fe 2 O 3 ). Conditions most ideal for achieving monodispersity and lower sizes have been optimized and confirmed through microscopic and photon correlation spectroscopic measurements

High Velocity Oxidation and Hot Corrosion Resistance of Some ODS Alloys

Science.gov (United States)

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

1977-01-01

Several oxide dispersion strengthened (ODS) alloys were tested for cyclic, high velocity, oxidation, and hot corrosion resistance. These results were compared to the resistance of an advanced, NiCrAl coated superalloy. An ODS FeCrAl were identified as having sufficient oxidation and hot corrosion resistance to allow potential use in an aircraft gas turbine without coating.

Application of Moessbauer spectroscopy in the study of high temperature oxidation of steel

International Nuclear Information System (INIS)

Seberini, M.; Volenik, K.

1975-01-01

The applicability was tested of etching by solutions of bromine or iodine in methyl alcohol in separating oxide films from substrates to make possible the measurement of absorption spectra. Prior to etching, scattering spectra of oxidized samples had been measured and the results were compared. Oxide films grown under various conditions on low carbon steel CSN 41 1373 were used in the experiment. The Moessbauer absorption spectrum measurement was found to be useful in the quantitative determination of phase composition. (L.O.)

Atomistic study of ternary oxides as high-temperature solid lubricants

Science.gov (United States)

Gao, Hongyu

Friction and wear are important tribological phenomena tightly associated with the performance of tribological components/systems such as bearings and cutting machines. In the process of contact and sliding, friction and wear lead to energy loss, and high friction and wear typically result in shortened service lifetime. To reduce friction and wear, solid lubricants are generally used under conditions where traditional liquid lubricants cannot be applied. However, it is challenging to maintain the functionality of those materials when the working environment becomes severe. For instance, at elevated temperatures (i.e., above 400 °C), most traditional solid lubricants, such as MoS2 and graphite, will easily oxidize or lose lubricity due to irreversible chemical changes. For such conditions, it is necessary to identify materials that can remain thermally stable as well as lubricious over a wide range of temperatures. Among the currently available high-temperature solid lubricants, Ag-based ternary metal oxides have recently drawn attention due to their low friction and ability to resist oxidation. A recent experimental study showed that the Ag-Ta-O ternary exhibited an extremely low coefficient of friction (0.06) at 750 °C. To fully uncover the lubricious nature of this material as a high-temperature solid lubricant, a series of tribological investigations were carried out based on one promising candidate - silver tantalate (AgTaO3). The study was then extended to alternative materials, Cu-Ta-O ternaries, to accommodate a variety of application requirements. We aimed to understand, at an atomic level, the effects of physical and chemical properties on the thermal, mechanical and tribological behavior of these materials at high temperatures. Furthermore, we investigated potassium chloride films on a clean iron surface as a representative boundary lubricating system in a nonextreme environment. This investigation complemented the study of Ag/Cu-Ta-O and enhanced the

Nanostructured oxide materials and modules for high temperature power generation from waste heat

DEFF Research Database (Denmark)

Van Nong, Ngo; Pryds, Nini

2013-01-01

are not easily satisfied by conventional thermoelectric materials. Not only they must possess a sufficient thermoelectric performance, they should also be stable at high temperatures, nontoxic and low-cost comprising elements, and must be also able to be processed and shaped cheaply. Oxides are among...... the strongest candidate materials for this purpose. In this review, the progress in the development of two representative p- and n-type novel oxide materials based on Ca3Co4O9 and doped-ZnO is presented. Thermoelectric modules built up from these oxides were fabricated, tested at high temperatures, and compared...... with other similar oxide modules reported in the literature. A maximum power density of 4.5 kW/m2 was obtained for an oxide module comprising of 8 p-n couples at a temperature difference of 496 K, an encouraging result in the context of the present high temperature oxide modules....

Removal of organic substances and oxidation of ammonium nitrogen by a down-flow hanging sponge (DHS) reactor under high salinity conditions.

Science.gov (United States)

Uemura, Shigeki; Suzuki, Saori; Abe, Kenichi; Kubota, Keiichi; Yamaguchi, Takashi; Ohashi, Akiyoshi; Takemura, Yasuyuki; Harada, Hideki

2010-07-01

A down-flow hanging sponge (DHS) reactor, constructed by connecting three identical treatment units in series, was fed with highly saline artificial coke-plant wastewater containing 1400 mg L(-1) of phenol in terms of chemical oxygen demand (COD) and 500 mg-NL(-1) of ammonium nitrogen. The COD was removed by the 1st unit, achieving 92% removal at an average COD loading rate of 3.0 kg-COD m(-3)d(-1) for all units, with oxidation of ammonium nitrogen occurring primarily in the two downstream units. Microbial assays of the different units of the reactor revealed greater numbers of nitrifying bacteria in the 2nd and 3rd units than in the 1st unit, corresponding with the observed ammonium oxidation pattern of the reactor. These findings suggest that a succession of microflora was successfully established along the DHS. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Study of nitric oxide catalytic oxidation on manganese oxides-loaded activated carbon at low temperature

Energy Technology Data Exchange (ETDEWEB)

You, Fu-Tian [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China); Yu, Guang-Wei, E-mail: gwyu@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Wang, Yin, E-mail: yinwang@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Xing, Zhen-Jiao [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Liu, Xue-Jiao; Li, Jie [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China)

2017-08-15

Highlights: • Loading manganese oxides on activated carbon effectively promotes NO oxidation. • NO adsorption-desorption on activated carbon is fundamental to NO oxidation. • A high Mn{sup 4+}/Mn{sup 3+} ratio contributes to NO oxidation by promoting lattice O transfer. - Abstract: Nitric oxide (NO) is an air pollutant that is difficult to remove at low concentration and low temperature. Manganese oxides (MnO{sub x})-loaded activated carbon (MLAC) was prepared by a co-precipitation method and studied as a new catalyst for NO oxidation at low temperature. Characterization of MLAC included X-ray diffraction (XRD), scanning electron microscopy (SEM), N{sub 2} adsorption/desorption and X-ray photoelectron spectroscopy (XPS). Activity tests demonstrated the influence of the amount of MnO{sub x} and the test conditions on the reaction. MLAC with 7.5 wt.% MnO{sub x} (MLAC003) exhibits the highest NO conversion (38.7%) at 1000 ppm NO, 20 vol.% O{sub 2}, room temperature and GHSV ca. 16000 h{sup −1}. The NO conversion of MLAC003 was elevated by 26% compared with that of activated carbon. The results of the MLAC003 activity test under different test conditions demonstrated that NO conversion is also influenced by inlet NO concentration, inlet O{sub 2} concentration, reaction temperature and GHSV. The NO adsorption-desorption process in micropores of activated carbon is fundamental to NO oxidation, which can be controlled by pore structure and reaction temperature. The activity elevation caused by MnO{sub x} loading is assumed to be related to Mn{sup 4+}/Mn{sup 3+} ratio. Finally, a mechanism of NO catalytic oxidation on MLAC based on NO adsorption-desorption and MnO{sub x} lattice O transfer is proposed.

Efficient One-Pot Synthesis of Colloidal Zirconium Oxide Nanoparticles for High-Refractive-Index Nanocomposites.

Science.gov (United States)

Liu, Chao; Hajagos, Tibor Jacob; Chen, Dustin; Chen, Yi; Kishpaugh, David; Pei, Qibing

2016-02-01

Zirconium oxide nanoparticles are promising candidates for optical engineering, photocatalysis, and high-κ dielectrics. However, reported synthetic methods for the colloidal zirconium oxide nanoparticles use unstable alkoxide precursors and have various other drawbacks, limiting their wide application. Here, we report a facile one-pot method for the synthesis of colloidally stable zirconium oxide nanoparticles. Using a simple solution of zirconium trifluoroacetate in oleylamine, highly stable zirconium oxide nanoparticles have been synthesized with high yield, following a proposed amidization-assisted sol-gel mechanism. The nanoparticles can be readily dispersed in nonpolar solvents, forming a long-term stable transparent solution, which can be further used to fabricate high-refractive-index nanocomposites in both monolith and thin-film forms. In addition, the same method has also been extended to the synthesis of titanium oxide nanoparticles, demonstrating its general applicability to all group IVB metal oxide nanoparticles.

Influence of chemical composition of zirconium alloy E110 on embrittlement under LOCA conditions - Part 1: Oxidation kinetics and macrocharacteristics of structure and fracture

Science.gov (United States)

Nikulin, S. A.; Rozhnov, A. B.; Belov, V. A.; Li, E. V.; Glazkina, V. S.

2011-11-01

Exploratory investigations of the influence of alloying and impurity content in the E110 alloy cladding tubes on the behavior under conditions of Loss of Coolant Accidents (LOCA) has been performed. Three alloys of E110 type have been tested: E110 alloy of nominal composition Zr-1%Nb (E110), E110 alloy of modified composition Zr-1%Nb-0.12%Fe-0.13%O (E110M), E110 alloy of nominal composition Zr-1%Nb with reduced impurity content (E110G). Alloys E110 and E110M were manufactured on the electrolytic basis and alloy E110G was manufactured on the basis of zirconium sponge. The high temperature oxidation tests in steam ( T = 1100 °C, 18% of equivalent cladding reacted (ECR)) have been conducted, kinetics of oxidation was investigated. Quantitative research of structure and fracture macrocharacteristics was performed by means of optical and electron microscopy. The results received were compared with the residual ductility of specimens. The results of the investigation showed the existence of "breakaway oxidation" kinetics and white spalling oxide in E110 and E110M alloys while the specimen oxidation kinetics in E110G alloy was characterized by a parabolic law and specimens had a dense black oxide. Oxygen and iron alloying in the E110 alloy positively changed the macrocharacteristics of structure and fracture. However, in general, it did not improve the resistance to embrittlement in LOCA conditions apparently because of a strong impurity influence caused by electrolytic process of zirconium production.

Weekend ethanol consumption and high-sucrose diet: resveratrol effects on energy expenditure, substrate oxidation, lipid profile, oxidative stress and hepatic energy metabolism.

Science.gov (United States)

Rocha, Katiucha Karolina Honório Ribeiro; Souza, Gisele Aparecida; Seiva, Fábio Rodrigues Ferreira; Ebaid, Geovana Xavier; Novelli, Ethel Lourenzi Barbosa

2011-01-01

The present study analyzed the association between weekend ethanol and high-sucrose diet on oxygen consumption, lipid profile, oxidative stress and hepatic energy metabolism. Because resveratrol (RS, 3,5,4'-trans-trihydroxystilbene) has been implicated as a modulator of alcohol-independent cardiovascular protection attributed to red wine, we also determined whether RS could change the damage done by this lifestyle. Male Wistar 24 rats receiving standard chow were divided into four groups (n = 6/group): (C) water throughout the experimental period; (E) 30% ethanol 3 days/week, water 4 days/week; (ES) a mixture of 30% ethanol and 30% sucrose 3 days/week, drinking 30% sucrose 4 days/week; (ESR) 30% ethanol and 30% sucrose containing 6 mg/l RS 3 days/week, drinking 30% sucrose 4 days/week. After 70 days the body weight was highest in ESR rats. E rats had higher energy expenditure (resting metabolic rate), oxygen consumption (VO(2)), fat oxidation, serum triacylglycerol (TG) and very low-density lipoprotein (VLDL) than C. ES rats normalized calorimetric parameters and enhanced carbohydrate oxidation. ESR ameliorated calorimetric parameters, reduced TG, VLDL and lipid hydroperoxide/total antioxidant substances, as well enhanced high-density lipoprotein (HDL) and HDL/TG ratio. Hepatic hydroxyacyl coenzyme-A dehydrogenase (OHADH)/citrate synthase ratio was lower in E and ES rats than in C. OHADH was highest in ESR rats. The present study brought new insights on weekend alcohol consumption, demonstrating for the first time, that this pattern of ethanol exposure induced dyslipidemic profile, calorimetric and hepatic metabolic changes which resemble that of the alcoholism. No synergistic effects were found with weekend ethanol and high-sucrose intake. RS was advantageous in weekend drinking and high-sucrose intake condition ameliorating hepatic metabolism and improving risk factors for cardiovascular damage.

Highly n-Type Titanium Oxide as an Electronically Active Support for Platinum in the Catalytic Oxidation of Carbon Monoxide

KAUST Repository

Baker, L. Robert

2011-08-18

The role of the oxide-metal interface in determining the activity and selectivity of chemical reactions catalyzed by metal particles on an oxide support is an important topic in science and industry. A proposed mechanism for this strong metal-support interaction is electronic activation of surface adsorbates by charge carriers. Motivated by the goal of using electronic activation to drive nonthermal chemistry, we investigated the ability of the oxide support to mediate charge transfer. We report an approximately 2-fold increase in the turnover rate of catalytic carbon monoxide oxidation on platinum nanoparticles supported on stoichiometric titanium dioxide (TiO2) when the TiO2 is made highly n-type by fluorine (F) doping. However, for nonstoichiometric titanium oxide (TiOX<2) the effect of F on the turnover rate is negligible. Studies of the titanium oxide electronic structure show that the energy of free electrons in the oxide determines the rate of reaction. These results suggest that highly n-type TiO2 electronically activates adsorbed oxygen (O) by electron spillover to form an active O- intermediate. © 2011 American Chemical Society.

Mechanism of the rapid dissolution of Pu02 under oxidizing conditions and applications

International Nuclear Information System (INIS)

Madic, C.; Lecomte, M.; Bourges, J.; Koehly, G.

1991-01-01

Until the recent years, plutonium dioxide was known to be among the metallic oxides the most difficult to dissolve. From thermodynamic calculations it can be predicted that PuO 2 will dissolve under oxidizing conditions. This can be achieved using Ag(II) species possibly regenerated by electrochemical means. The mechanism of such a process has been elucidated using carbon paste electrochemistry and 18 O labelling. These studies demonstrate that the chemical reaction limiting the overall proces is located on the surface of the solid PuO 2 , and that the first step consists in the oxidation of the plutonium into Pu(V) species. Applications of the dissolution process of PuO 2 by electrogenerated Ag(II) were growing in the recent years in FRANCE. These applications developed often in collaboration with SGN and COGEMA, concern the treatment of: out of specifications PuO 2 , incineration ashes, wastes produced during MOX fuel fabrication, and during the dismantling of old nuclear facilities. A general overview of these different applications is given

Heterogeneous oxidation of mercury in simulated post combustion conditions

Energy Technology Data Exchange (ETDEWEB)

Glenn A. Norton; Hongqun Yang; Robert C. Brown; Dennis L. Laudal; Grant E. Dunham; John Erjavec [Iowa State University, Ames, IA (United States). Center for Sustainable Environmental Technologies

2003-01-01

Heterogeneous mercury oxidation was studied by exposing whole fly ash samples and magnetic, nonmagnetic, and size-classified fly ash fractions to elemental mercury vapor in simulated flue gas streams. Fly ash from sub-bituminous Wyodak-Anderson PRB coal and bituminous Blacksville coal were used. Scanning electron microscopy, X-ray diffraction, thermogravimetric analyses, and BET N{sub 2} isothermal sorption analyses were performed to characterize the fly ash samples. Mercury speciation downstream from the ash was determined using the Ontario Hydro method. Results showed that the presence of fly ash was critical for mercury oxidation, and the surface area of the ash appears to be an important parameter. However, for a given fly ash, there were generally no major differences in catalytic oxidation potential between different fly ash fractions. This includes fractions enriched in unburned carbon and iron oxides. The presence of NO{sub 2}, HCl, and SO{sub 2} resulted in greater levels of mercury oxidation, while NO inhibited mercury oxidation. The gas matrix affected mercury oxidation more than the fly ash composition. 21 refs., 10 figs., 2 tabs.

Tantalum high-temperature oxidation kinetics

International Nuclear Information System (INIS)

Grigor'ev, Yu.M.; Sarkisyan, A.A.; Merzhanov, A.G.

1981-01-01

Kinetics of heat release and scale growth during tantalum oxidation within 650-1300 deg C temperature range in oxygen-containing media is investigated. Kinetic equations and temperature and pressure dependences of constants are ound Applicability of the kinetic Lorie mechanism for the description of the tantalum oxidation kinetics applicably to rapid-passing processes is shown. It is stated that the process rate (reaction ability) is determined by adsorption desorption factors on the external surface of the ''protective'' oxide for the ''linear'' oxidation stage [ru

Evaluation of a Ductility after High Temperature Oxidation with the Three-Point Bend Test in Zirconium Alloys

International Nuclear Information System (INIS)

Jung, Yang Il; Park, Sang Yoon; Park, Jeong Yong; Jeong, Yong Hwan

2010-01-01

In a light water reactor, the fuel cladding play an important role of preventing leakage of radioactive materials into the coolant, and thus the mechanical integrity of the cladding should be guaranteed under the conditions of normal and transient operation. In the case of a loss of coolant accident (LOCA), the cladding is subjected to a high temperature oxidation which is finally quenched because of an emergency coolant reflooding into the core. In this situation, the current LOCA criteria consist of five separate requirements: i) peak cladding temperature, ii) maximum cladding oxidation, iii) maximum hydrogen generation, iv) coolable geometry, and v) long-term cooling. The claddings lose their ductility due to the microstructural phase transformation from beta to martensite alpha-prime. and hydrogen up-take after LOCA. Since the reduction in ductility can induce embrittlement of claddings, post-quench ductility is one of the major concerns in transient operation circumstances. For the analysis, usually ring compression test are performed on ring samples cut from the tube to examine the oxidized cladding ductility. However, the test would not be applicable to the platelet samples which are general form of a specimen for developing alloys. As a high burn-up fuel cladding materials, Zircaloys are being replaced by modern zirconium alloys such as ZIRLO, and M5. Korea has also developed a new fuel cladding material HANA (high performance alloy for nuclear application) by the Korea Atomic Energy Research Institute. Because of the different composition of the newer claddings in comparison with the conventional Zircaloy-4, the high temperature oxidation behavior and the ductility after the oxidation would be different, and the properties should be evaluated how much the newer claddings were improved

High temperature oxidation and electrochemical studies on novel co-base superalloys

Energy Technology Data Exchange (ETDEWEB)

Klein, Leonhard

2013-02-27

Isothermal oxidation in air was carried out on novel γ'-strengthened Cobalt-base superalloys of the system Co-Al-W-B. After fast initial oxide formation, a multi-layered structure establishes, consisting of an outer cobalt oxide layer, a middle spinel-containing layer, and an inner Al{sub 2}O{sub 3}-rich region. Ion diffusion in outward direction is hindered by the development of Al{sub 2}O{sub 3}, that can be either present as a continuous and protective layer or as a discontinuous Al{sub 2}O{sub 3}-rich area without comparable protective effect. Furthermore, high temperature oxidation leads to phase transformation (from γ/γ' into γ/Co{sub 3}W) at the alloy/oxide layer interface due to aluminium depletion. Pure cobalt and ternary Co-Al-W alloys exhibit parabolic oxide growth due to the lack or insufficient amounts of protective oxides, whereas quaternary Co-Al-W-B alloys possess sub-parabolic oxidation behaviour (at 900 C). At lower temperatures (800 C), even a blockage of further oxidation can be observed. High amounts of B (0.12 at%) significantly improve oxidation resistance mainly due to its beneficial effect on inner Al{sub 2}O{sub 3}-formation at the alloy/oxide interface. Furthermore, B prevents decohesion of high temperature scales due to the formation of B-rich phases (presumably tungsten borides) in the middle oxide layer. Appropriate amounts of chromium (8 at%) as additional alloying element to Co-Al-W-B alloys lead to the formation of an inner duplex layer composed of protective Cr{sub 2}O{sub 3} and Al{sub 2}O{sub 3} phases. In this respect, chromium also benefits selective oxidation of aluminium, which results in higher Al{sub 2}O{sub 3}-contents compared to chromium-free alloys. Major drawbacks of chromium additions are, on the one hand, the formation of volatile chromium-containing species at temperatures exceeding 1000 C and on the other hand, the instability of the γ/γ'-microstructure. Titanium and silicon additions lead to

Nitrosative/oxidative stress conditions regulate thioredoxin-interacting protein (TXNIP) expression and thioredoxin-1 (TRX-1) nuclear localization.

Science.gov (United States)

Ogata, Fernando Toshio; Batista, Wagner Luiz; Sartori, Adriano; Gesteira, Tarsis Ferreira; Masutani, Hiroshi; Arai, Roberto Jun; Yodoi, Junji; Stern, Arnold; Monteiro, Hugo Pequeno

2013-01-01

Thioredoxin (TRX-1) is a multifunctional protein that controls the redox status of other proteins. TRX-1 can be found in the extracellular milieu, cytoplasm and nucleus, and it has distinct functions in each environment. Previously, we studied the intracellular localization of TRX-1 and its relationship with the activation of the p21Ras-ERK1/2 MAP Kinases signaling pathway. In situations where this pathway was activated by stress conditions evoked by a nitrosothiol, S-nitroso-N-acetylpenicillamine (SNAP), TRX-1 accumulated in the nuclear compartment due to nitrosylation of p21Ras and activation of downstream ERK1/2 MAP kinases. Presently, we demonstrate that ERK1/2 MAP Kinases activation and spatial distribution within cells trigger TRX-1 nuclear translocation through down-regulation of the physiological inhibitor of TRX-1, Thioredoxin Interacting Protein (TXNIP). Once activated by the oxidants, SNAP and H₂O₂, the ERK1/2 MAP kinases migrate to the nucleus. This is correlated with down-regulation of TXNIP. In the presence of the MEK inhibitors (PD98059 or UO126), or in cells transfected with the Protein Enriched in Astrocytes (PEA-15), a cytoplasmic anchor of ERK1/2 MAP kinases, TRX-1 nuclear migration and TXNIP down-regulation are no longer observed in cells exposed to oxidants. On the other hand, over-expression of TXNIP abolishes nuclear migration of TRX-1 under nitrosative/oxidative stress conditions, whereas gene silencing of TXNIP facilitates nuclear migration even in the absence of stress conditions. Studies based on the TXNIP promoter support this regulation. In conclusion, changes in TRX-1 compartmentalization under nitrosative/oxidative stress conditions are dependent on the expression levels of TXNIP, which are regulated by cellular compartmentalization and activation of the ERK1/2 MAP kinases.

Nitrosative/oxidative stress conditions regulate thioredoxin-interacting protein (TXNIP expression and thioredoxin-1 (TRX-1 nuclear localization.

Directory of Open Access Journals (Sweden)

Fernando Toshio Ogata

Full Text Available Thioredoxin (TRX-1 is a multifunctional protein that controls the redox status of other proteins. TRX-1 can be found in the extracellular milieu, cytoplasm and nucleus, and it has distinct functions in each environment. Previously, we studied the intracellular localization of TRX-1 and its relationship with the activation of the p21Ras-ERK1/2 MAP Kinases signaling pathway. In situations where this pathway was activated by stress conditions evoked by a nitrosothiol, S-nitroso-N-acetylpenicillamine (SNAP, TRX-1 accumulated in the nuclear compartment due to nitrosylation of p21Ras and activation of downstream ERK1/2 MAP kinases. Presently, we demonstrate that ERK1/2 MAP Kinases activation and spatial distribution within cells trigger TRX-1 nuclear translocation through down-regulation of the physiological inhibitor of TRX-1, Thioredoxin Interacting Protein (TXNIP. Once activated by the oxidants, SNAP and H₂O₂, the ERK1/2 MAP kinases migrate to the nucleus. This is correlated with down-regulation of TXNIP. In the presence of the MEK inhibitors (PD98059 or UO126, or in cells transfected with the Protein Enriched in Astrocytes (PEA-15, a cytoplasmic anchor of ERK1/2 MAP kinases, TRX-1 nuclear migration and TXNIP down-regulation are no longer observed in cells exposed to oxidants. On the other hand, over-expression of TXNIP abolishes nuclear migration of TRX-1 under nitrosative/oxidative stress conditions, whereas gene silencing of TXNIP facilitates nuclear migration even in the absence of stress conditions. Studies based on the TXNIP promoter support this regulation. In conclusion, changes in TRX-1 compartmentalization under nitrosative/oxidative stress conditions are dependent on the expression levels of TXNIP, which are regulated by cellular compartmentalization and activation of the ERK1/2 MAP kinases.

Effects of Reduced Sulfur Compounds on Pd-catalytic Hydrodechlorination of TCE in Groundwater by Cathodic H2 under Electrochemically-induced Oxidizing Conditions

Science.gov (United States)

Yuan, Songhu; Chen, Mingjie; Mao, Xuhui; Alshawabkeh, Akram N.

2014-01-01

Reduced sulfur compounds (RSCs) poison Pd catalysts for catalytic hydrodechlorination of contaminants in anoxic groundwater. This study investigates the effects of RSCs on Pd-catalytic hydrodechlorination of trichloroethylene (TCE) in oxic groundwater. Water electrolysis in an undivided electrolytic cell is used to produce H2 for TCE hydrodechlorination under oxidizing conditions. TCE is efficiently hydrodechlorinated to ethane, with significant accumulation of H2O2 under acidic conditions. Presence of sulfide at concentrations less than 93.8 μM moderately inhibits TCE hydrodechlorination and H2O2 production. Presence of sulfite at low concentrations (≤ 1 mM) significantly enhances TCE decay, while at high concentration (3 mM) inhibits initially and enhances afterwards when sulfite concentration declines to less than 1 mM. Using radical scavenging experiments and electron spin resonance assay, SO3•− which is generated from sulfite under oxidizing conditions is validated as the new reactive species contributing to the enhancement. This study reveals a distinct mechanism of effect of sulfite on TCE hydrodechlorination by Pd and H2 in oxic groundwater and presents an alternative approach to increasing resistance of Pd to RSCs poisoning. PMID:23962132

[Studies on high temperature oxidation of noble metal alloys for dental use. (III) On high temperature oxidation resistance of noble metal alloys by adding small amounts of alloying elements. (author's transl)].

Science.gov (United States)

Ohno, H

1976-11-01

The previous report pointed out the undesirable effects of high temperature oxidation on the casting. The influence of small separate additions of Zn, Mg, Si, Be and Al on the high temperature oxidation of the noble metal alloys was examined. These alloying elements were chosen because their oxide have a high electrical resistivity and they have much higher affinity for oxygen than Cu. The casting were oxidized at 700 degrees C for 1 hour in air. The results obtained were as follows: 1. The Cu oxides are not observed on the as-cast surface of noble metal alloys containing small amounts of Zn, Mg, Si, Be, and Al. The castings have gold- or silver-colored surface. 2. After heating of the unpolished and polished castings, the additions of Si, Be and Al are effective in preventing oxidation of Cu in the 18 carats gold alloys. Especially the golden surface is obtained by adding Be and Al. But there is no oxidation-resistance on the polished castings in the alloys containing Zn and Mg. 3. The zinc oxide film formed on the as-cast specimen is effective in preventing of oxidation Cu in 18 carats gold alloys. 4. It seems that the addition of Al is most available in dental application.

Array-type sensor to determine corrosive conditions in high temperature water under gamma rays irradiation

International Nuclear Information System (INIS)

Satoh, T.; Tsukada, T.; Uchida, S.; Katoh, C.

2010-01-01

One of the problems to determine electrochemical corrosion potential (ECP) in high temperature water under irradiation is to apply long-lived and reliable reference electrodes. In order to avoid troubles due to the reference electrode, a new concept to determine ECP without the reference electrode has been proposed. Several metal plates are applied as working electrodes and at the same time as the reference electrodes. Potential of the metal plates with stable oxide films on their surfaces show stable values in high temperature water. As a result of the combination of their potential values, ECP of each metal can be determined without any specific reference electrode. Array-type sensors consisting of several metal plates, e.g., Fe, Ni, Cr, Zr, Pt, Pd, Re, Ir, with well developed oxide films on their surface were prepared for ECP measurement in high temperature water under neutron/gamma ray irradiations. In order to confirm the feasibility of this concept, responses of the redox potentials of the pure metals to changes in the simulated BWR reactor water conditions were measured and the ECP was determined by the differences in potentials between a couple of metal plates. Major conclusions of the study are as follows: 1) The redox potentials of the Fe, Pt, Zr, Ir, Pd, and Re electrodes showed the different dependences on the changes in O 2 and H 2 O 2 concentrations. The redox potentials of the electrodes increased as the oxidant concentrations increased except for Zr electrode. The potential of the Zr electrode was kept the very low potential at the wide range of O 2 and H 2 O 2 concentrations differed form the other electrodes. 2) It was estimated that the redox potential of highly soluble metal may be increased, while that of low soluble metal may be decreased by an oxide film. The stable oxide film would cause the stable potential response of the electrode with oxide film. 3) The relationship between the oxidant concentrations and the redox potentials of the

Epitaxial heterojunctions of oxide semiconductors and metals on high temperature superconductors

Science.gov (United States)

Vasquez, Richard P. (Inventor); Hunt, Brian D. (Inventor); Foote, Marc C. (Inventor)

1994-01-01

Epitaxial heterojunctions formed between high temperature superconductors and metallic or semiconducting oxide barrier layers are provided. Metallic perovskites such as LaTiO3, CaVO3, and SrVO3 are grown on electron-type high temperature superconductors such as Nd(1.85)Ce(0.15)CuO(4-x). Alternatively, transition metal bronzes of the form A(x)MO(3) are epitaxially grown on electron-type high temperature superconductors. Also, semiconducting oxides of perovskite-related crystal structures such as WO3 are grown on either hole-type or electron-type high temperature superconductors.

Oxidative stability of krill oil (Euphausia superba)

DEFF Research Database (Denmark)

Lu, Henna Fung Sieng; Jacobsen, Charlotte; Bruheim, I.

Krill oil has been reported in many studies to have high oxidative stability when evaluated by peroxide value (PV) and anisidine value (AV). However, recent studies have shown that other compounds than primary and secondary oxidation products are formed when krill oil is exposed to oxidative...... conditions. These compounds include Strecker degradation compounds and pyrroles. Some of these compounds may have antioxidative effect. Commercial scale processing of krill prior to extraction may affect the oxidative stability of krill oil. Therefore, the main objective of this study was to compare lipid...... oxidation in krill oil produced in a commercial process and krill oil carefully extracted from frozen krill in the laboratory. Krill oil was incubated at different temperatures (20, 30 and 40 oC) for 1, 2, 3, 4 and 6 weeks, under conditions of constant stirring while being exposed to air. The oxidative...

High Temperature Strength of Oxide Dispersion Strengthened Aluminium

DEFF Research Database (Denmark)

Clauer, A.H.; Hansen, Niels

1984-01-01

constant (except for the material with the lowest oxide content). The high temperature values of the modulus-corrected yield stresses are approximately two-thirds of the low temperature value. During high temperature creep, there is a definite indication of a threshold stress. This threshold stress......The tensile flow stress of coarse-grained dispersion strengthened Al-Al2O3 materials were measured as a function of temperature (77–873 K) and volume fraction (0.19-0.92 vol.%) of aluminium oxide. For the same material, the creep strength was determined as a function of temperature in the range 573......–873 K. The modulus-corrected yield stress (0.01 offset) is found to be temperature independent at low temperature (195–472 K). Between 473 and 573 K, the yield stress starts to decrease with increasing temperature. At high temperatures (573–873 K), the modulus-corrected yield stress is approximately...

Graphene oxide and H2 production from bioelectrochemical graphite oxidation.

Science.gov (United States)

Lu, Lu; Zeng, Cuiping; Wang, Luda; Yin, Xiaobo; Jin, Song; Lu, Anhuai; Jason Ren, Zhiyong

2015-11-17

Graphene oxide (GO) is an emerging material for energy and environmental applications, but it has been primarily produced using chemical processes involving high energy consumption and hazardous chemicals. In this study, we reported a new bioelectrochemical method to produce GO from graphite under ambient conditions without chemical amendments, value-added organic compounds and high rate H2 were also produced. Compared with abiotic electrochemical electrolysis control, the microbial assisted graphite oxidation produced high rate of graphite oxide and graphene oxide (BEGO) sheets, CO2, and current at lower applied voltage. The resultant electrons are transferred to a biocathode, where H2 and organic compounds are produced by microbial reduction of protons and CO2, respectively, a process known as microbial electrosynthesis (MES). Pseudomonas is the dominant population on the anode, while abundant anaerobic solvent-producing bacteria Clostridium carboxidivorans is likely responsible for electrosynthesis on the cathode. Oxygen production through water electrolysis was not detected on the anode due to the presence of facultative and aerobic bacteria as O2 sinkers. This new method provides a sustainable route for producing graphene materials and renewable H2 at low cost, and it may stimulate a new area of research in MES.

Plasma electrolytic oxidation of Titanium Aluminides

International Nuclear Information System (INIS)

Morgenstern, R; Sieber, M; Lampke, T; Grund, T; Wielage, B

2016-01-01

Due to their outstanding specific mechanical and high-temperature properties, titanium aluminides exhibit a high potential for lightweight components exposed to high temperatures. However, their application is limited through their low wear resistance and the increasing high-temperature oxidation starting from about 750 °C. By the use of oxide ceramic coatings, these constraints can be set aside and the possible applications of titanium aluminides can be extended. The plasma electrolytic oxidation (PEO) represents a process for the generation of oxide ceramic conversion coatings with high thickness. The current work aims at the clarification of different electrolyte components’ influences on the oxide layer evolution on alloy TNM-B1 (Ti43.5Al4Nb1Mo0.1B) and the creation of compact and wear resistant coatings. Model experiments were applied using a ramp-wise increase of the anodic potential in order to show the influence of electrolyte components on the discharge initiation and the early stage of the oxide layer growth. The production of PEO layers with technically relevant thicknesses close to 100 μm was conducted in alkaline electrolytes with varying amounts of Na 2 SiO 3 ·5H 2 O and K 4 P 2 O 7 under symmetrically pulsed current conditions. Coating properties were evaluated with regard to morphology, chemical composition, hardness and wear resistance. The addition of phosphates and silicates leads to an increasing substrate passivation and the growth of compact oxide layers with higher thicknesses. Optimal electrolyte compositions for maximum coating hardness and thickness were identified by statistical analysis. Under these conditions, a homogeneous inner layer with low porosity can be achieved. The frictional wear behavior of the compact coating layer is superior to a hard anodized layer on aluminum. (paper)

Electrochemical characterization of oxide film formed at high temperature on Alloy 690

Energy Technology Data Exchange (ETDEWEB)

Abraham, Geogy J., E-mail: gja@barc.gov.in [Materials Science Division, BARC, Mumbai 400 085 (India); Bhambroo, Rajan [Deptt. of Metallurgical Engg. and Mat. Sci., IIT Bombay, Mumbai 400 076 (India); Kain, V. [Materials Science Division, BARC, Mumbai 400 085 (India); Shekhar, R. [CCCM, BARC, Hyderabad 500 062 (India); Dey, G.K. [Materials Science Division, BARC, Mumbai 400 085 (India); Raja, V.S. [Deptt. of Metallurgical Engg. and Mat. Sci., IIT Bombay, Mumbai 400 076 (India)

2012-02-15

Highlights: Black-Right-Pointing-Pointer GD-QMS studies of high temperature oxide film formed on Alloy 690. Black-Right-Pointing-Pointer Defect density reduced with increase in temperature. Black-Right-Pointing-Pointer Electrochemical behaviour of oxide film correlated to the Cr-content in oxide. - Abstract: High temperature passivation studies on Alloy 690 were carried out in lithiated water at 250 Degree-Sign C, 275 Degree-Sign C and 300 Degree-Sign C for 72 h. The passive films were characterized by glow discharge-quadrupole mass spectroscopy (GD-QMS) for compositional variation across the depth and micro laser Raman spectroscopy for oxide composition on the surface. The defect density in the oxide films was established from the Mott-Schottky analysis using electrochemical impedance spectroscopy. Electrochemical experiments at room temperature in chloride medium revealed best passivity behaviour by the oxide film formed at 300 Degree-Sign C for 72 h. The electrochemical studies were correlated to the chromium (and oxygen) content of the oxide films. Autoclaving at 300 Degree-Sign C resulted in the best passive film formation on Alloy 690 in lithiated water.

Kinetics of high-temperature oxidation of (Ti,Ta)(C,N)-based cermets

International Nuclear Information System (INIS)

Chicardi, E.; Córdoba, J.M.; Gotor, F.J.

2016-01-01

Highlights: • The kinetic of high-temperature oxidation of (Ti,Ta)(C,N)-Co cermets was studied. • A parabolic oxidation kinetic was determined in cermets between 700 °C and 1200 °C. • This parabolic kinetic behaviour is due to the existence of a protective layer. • The protective layer formed was a complex Ti_xTa_1_−_xO_2 oxide with rutile structure. • The oxidation rate is controlled by the Ti and O_2 diffusion through the Ti_xTa_1_−_xO_2. - Abstract: The kinetics of the high-temperature oxidation of titanium–tantalum carbonitride-based cermets with different Ti/Ta ratios was studied. Isothermal oxidation tests were conducted under static air for 48 h at temperatures between 700 °C and 1200 °C. The oxidation satisfied the parabolic kinetics, characteristic of the existence of a protective oxide layer. The apparent activation energy suggests the rate-controlling process during oxidation is the simultaneous inward and outward diffusion of oxygen and titanium, respectively, through the formed protective layer, consisting mainly of a rutile phase. A higher Ta(V) content in the rutile decreased the oxygen diffusivity due to the reduction of oxygen vacancy concentration.

Ultra-high temperature tensile properties of ODS steel claddings under severe accident conditions

Energy Technology Data Exchange (ETDEWEB)

Yano, Y., E-mail: yano.yasuhide@jaea.go.jp [Japan Atomic Energy Agency, 4002, Narita-cho, Oarai-machi, Ibaraki, 311-1393 (Japan); Tanno, T.; Oka, H.; Ohtsuka, S.; Inoue, T.; Kato, S.; Furukawa, T.; Uwaba, T.; Kaito, T. [Japan Atomic Energy Agency, 4002, Narita-cho, Oarai-machi, Ibaraki, 311-1393 (Japan); Ukai, S.; Oono, N. [Materials Science and Engineering, Faculty of Engineering, Hokkaido University, N13, W-8, Kita-ku, Sapporo, Hokkaido, 060-8628 (Japan); Kimura, A. [Institute of Advanced Energy, Kyoto University, Gokasho, Uji, Kyoto 611-0011 (Japan); Hayashi, S. [Tokyo Institute of Technology, 2-12-1, Ookayama, Meguro-ku, Tokyo 152-8550 (Japan); Torimaru, T. [Nippon Nuclear Fuel Development Co., Ltd., 2163, Narita-cho, Oarai-machi, Ibaraki, 311-1313 (Japan)

2017-04-15

Ultra-high temperature ring tensile tests were performed to investigate the tensile behavior of oxide dispersion strengthened (ODS) steel claddings and wrapper materials under severe accident conditions with temperatures ranging from room temperature to 1400 °C which is close to the melting point of core materials. The experimental results showed that the tensile strength of 9Cr-ODS steel claddings was highest in the core materials at ultra-high temperatures of 900–1200 °C, but there was significant degradation in the tensile strength of 9Cr-ODS steel claddings above 1200 °C. This degradation was attributed to grain boundary sliding deformation with γ/δ transformation, which is associated with reduced ductility. By contrast, the tensile strength of recrystallized 12Cr-ODS and FeCrAl-ODS steel claddings retained its high value above 1200 °C, unlike the other tested materials.

Ultra-high temperature tensile properties of ODS steel claddings under severe accident conditions

Science.gov (United States)

Yano, Y.; Tanno, T.; Oka, H.; Ohtsuka, S.; Inoue, T.; Kato, S.; Furukawa, T.; Uwaba, T.; Kaito, T.; Ukai, S.; Oono, N.; Kimura, A.; Hayashi, S.; Torimaru, T.

2017-04-01

Ultra-high temperature ring tensile tests were performed to investigate the tensile behavior of oxide dispersion strengthened (ODS) steel claddings and wrapper materials under severe accident conditions with temperatures ranging from room temperature to 1400 °C which is close to the melting point of core materials. The experimental results showed that the tensile strength of 9Cr-ODS steel claddings was highest in the core materials at ultra-high temperatures of 900-1200 °C, but there was significant degradation in the tensile strength of 9Cr-ODS steel claddings above 1200 °C. This degradation was attributed to grain boundary sliding deformation with γ/δ transformation, which is associated with reduced ductility. By contrast, the tensile strength of recrystallized 12Cr-ODS and FeCrAl-ODS steel claddings retained its high value above 1200 °C, unlike the other tested materials.

New Oxide Materials for an Ultra High Temperature Environment

Energy Technology Data Exchange (ETDEWEB)

Perepezko, John H. [Univ. of Wisconsin, Madison, WI (United States). Dept. of Materials Science and Engineering

2017-11-13

In this project, a new oxide material, Hf₆Ta₂O₁₇ has been successfully synthesized by the controlled oxidization of Hf-Ta alloys. This oxide exhibits good oxidation resistance, high temperature phase stability up to more than 2000°C, low thermal conductivity and thus could serve as a component or a coating material in an ultrahigh temperature environment. We have examined the microstructure evolution and phase formation sequence during the oxidation exposure of Hf-Ta alloys at 1500°C and identified that the oxidation of a Hf-26.7atomic %Ta alloy leads to the formation of a single phase adherent Hf₆Ta₂O₁₇ with a complex atomic structure i.e. superstructure. The overall reactive diffusion pathway is consistent with the calculated Hf-Ta-O ternary phase diagram. Besides the synthesis of Hf₆Ta₂O₁₇ superstructure by oxidizing Hf-Ta alloys, we have also developed a synthesis method based upon the reactive sintering of the correct ratios of mixed powders of HfO₂ and Ta₂O₅ and verified the low thermal conductivity of Hf₆Ta₂O₁₇ superstructure on these samples. We have completed a preliminary analysis of the oxidation kinetics for Hf₆Ta₂O₁₇, which shows an initial parabolic oxidation kinetics.

Nitrous oxide production by lithotrophic ammonia-oxidizing bacteria and implications for engineered nitrogen-removal systems.

Science.gov (United States)

Chandran, Kartik; Stein, Lisa Y; Klotz, Martin G; van Loosdrecht, Mark C M

2011-12-01

Chemolithoautotrophic AOB (ammonia-oxidizing bacteria) form a crucial component in microbial nitrogen cycling in both natural and engineered systems. Under specific conditions, including transitions from anoxic to oxic conditions and/or excessive ammonia loading, and the presence of high nitrite (NO₂⁻) concentrations, these bacteria are also documented to produce nitric oxide (NO) and nitrous oxide (N₂O) gases. Essentially, ammonia oxidation in the presence of non-limiting substrate concentrations (ammonia and O₂) is associated with N₂O production. An exceptional scenario that leads to such conditions is the periodical switch between anoxic and oxic conditions, which is rather common in engineered nitrogen-removal systems. In particular, the recovery from, rather than imposition of, anoxic conditions has been demonstrated to result in N₂O production. However, applied engineering perspectives, so far, have largely ignored the contribution of nitrification to N₂O emissions in greenhouse gas inventories from wastewater-treatment plants. Recent field-scale measurements have revealed that nitrification-related N₂O emissions are generally far higher than emissions assigned to heterotrophic denitrification. In the present paper, the metabolic pathways, which could potentially contribute to NO and N₂O production by AOB have been conceptually reconstructed under conditions especially relevant to engineered nitrogen-removal systems. Taken together, the reconstructed pathways, field- and laboratory-scale results suggest that engineering designs that achieve low effluent aqueous nitrogen concentrations also minimize gaseous nitrogen emissions.

Experimental and kinetic modeling study of C2H4 oxidation at high pressure

DEFF Research Database (Denmark)

Lopez, Jorge Gimenez; Rasmussen, Christian Lund; Alzueta, Maria

2009-01-01

of conditions (0.003-100 bar, 200-3000 K). The results indicate that at 60 bar and medium temperatures vinyl peroxide, rather than CH2O and HCO, is the dominant product. The experiments, involving C2H4/O-2 mixtures diluted in N-2, were carried out in a high pressure flow reactor at 600-900 K and 60 bar, varying......A detailed chemical kinetic model for oxidation of C2H4 in the intermediate temperature range and high pressure has been developed and validated experimentally. New ab initio calculations and RRKM analysis of the important C2H3 + O-2 reaction was used to obtain rate coefficients over a wide range...

A study on the improvement of oxidation resistance of OAE-added stainless steels for high temperature applications

International Nuclear Information System (INIS)

Kim, Dae Hwan; Kim, Gil Moo

1996-01-01

Since the manufacturing temperature of stainless steels is relatively high, oxidation at the elevated temperature becomes important. The chemical and physical properties of the protective oxide film which was formed on the stainless steels at high temperature for the oxidation resistance are important in determining the rate of oxidation and the life of equipment exposed to high temperature oxidizing environments. In this study, the oxidation behavior of STS 309S and STS 409L added by a small amount of oxygen active element(each + 0.5wt% Hf and Y) was studied to improve oxidation resistance. In the cyclic oxidation, while OAE-free specimens showed relatively poor oxidation resistance due to spallations and cracks of Cr-rich oxide layer, OAE-added specimens improved cyclic oxidation resistance assumably due to constant oxidation rate with stable oxide layers at high temperature. Especially Hf improved cyclic oxidation resistance by forming Cr-rich oxide layer preventing internal oxidation in STS 309S. (author)

Controlling the anodizing conditions in preparation of an nanoporous anodic aluminium oxide template

Science.gov (United States)

Nazemi, Azadeh; Abolfazl, Seyed; Sadjadi, Seyed

2014-12-01

Porous anodic aluminium oxide (AAO) template is commonly used in the synthesis of one-dimensional nanostructures, such as nanowires and nanorods, due to its simple fabrication process. Controlling the anodizing conditions is important because of their direct influence on the size of AAO template pores; it affects the size of nanostructures that are fabricated in AAO template. In present study, several alumina templates were fabricated by a two-step electrochemical anodization in different conditions, such as the time of first process, its voltage, and electrolyte concentration. The effect of these factors on pore diameters of AAO templates was investigated using scanning electron microscopy (SEM).

Native oxidation of ultra high purity Cu bulk and thin films

International Nuclear Information System (INIS)

Iijima, J.; Lim, J.-W.; Hong, S.-H.; Suzuki, S.; Mimura, K.; Isshiki, M.

2006-01-01

The effect of microstructure and purity on the native oxidation of Cu was studied by using angle-resolved X-ray photoelectron spectroscopy (AR-XPS) and spectroscopic ellipsometry (SE). A high quality copper film prepared by ion beam deposition under a substrate bias voltage of -50 V (IBD Cu film at V s = -50 V) showed an oxidation resistance as high as an ultra high purity copper (UHP Cu) bulk, whereas a Cu film deposited without substrate bias voltage (IBD Cu film at V s = 0 V) showed lower oxidation resistance. The growth of Cu 2 O layer on the UHP Cu bulk and both types of the films obeyed in principle a logarithmic rate law. However, the growth of oxide layer on the IBD Cu films at V s = 0 and -50 V deviated upward from the logarithmic rate law after the exposure time of 320 and 800 h, respectively. The deviation from the logarithmic law is due to the formation of CuO on the Cu 2 O layer after a critical time

The oxidation kinetics of zircaloy - 4 under isothermal conditions

International Nuclear Information System (INIS)

Santos, A.M.M. dos; Cardoso, P.E.

1982-01-01

The oxidation kinetics of zircaloy-4 tubes was studied by means of isothermal tests in the temperature interval 500 0 C to 900 0 C. Dry oxygen and water steam, were used as oxidant agents. The results show that the oxidation kinetics law exhibits a behaviour from cubic to parabolic in the range of the time and temperatures of the experiment. Dry oxygen shows a stronger oxidation effect than water steam. A special mechanical test to study the embrittlement effect in the small samples of zircaloy tubes was used. (Author) [pt

Fabrication of Electrochemically Reduced Graphene Oxide Modified Gas Diffusion Electrode for In-situ Electrochemical Advanced Oxidation Process under Mild Conditions

International Nuclear Information System (INIS)

Dong, Heng; Su, Huimin; Chen, Ze; Yu, Han; Yu, Hongbing

2016-01-01

With aim to develop an efficient heterogeneous metal-free cathodic electrochemical advance oxidation process (CEAOP) for persistent organic pollutants (POPs) removal from wastewater under mild conditions, electrochemically reduced graphene oxide (ERGO)-modified gas diffusion electrode (GDE) was prepared for oxygen-containing radicals production via electrochemical oxygen reduction reaction (ORR). A detailed physical characterization was carried out by SEM, Raman spectroscopy, XRD and XPS. The electrocatalytic behavior for ORR was investigated by electrochemical measurements and electrolysis experiments under constant current density. Bisphenol A (BPA) of 20 mg L −1 was used as a model of POPs to evaluate the performance of the CEAOP with ERGO-modified GDE. The results showed that the defects concentration and electrochemical active sites of the ERGO was increased as the reduction time (30 min, 60 min and 120 min), leading to different catalysis on ORR. ·O 2 generation via one-electron ORR was found under the electrocatalysis of ERGO (60 min and 120 min), contributing to a complete degradation of BPA within 20 min and a mineralization current efficiency (MCE) of 74.60%. An alternative metal-free CEAOP independent of Fenton reaction was established based on ERGO-modified GDE for POPs removal from wastewater under mild conditions.

HfO2 - rare earth oxide systems in the region with high content of rare earth oxide

International Nuclear Information System (INIS)

Shevchenko, A.V.; Lopato, L.M.

1982-01-01

Using the methods of annealing and hardenings (10 2 -10 4 deg/s cooling rate) and differential thermal analysis elements of state diagrams of HfO 2 - rare earth oxide (rare earths-La, Pr, Nd, Sm, Gd, Tb, Dy, Y, Er, Yb, Lu, Sc) systems from 1800 deg C up to melting in the range of 60-100 mol% rare earth oxide concentration were constructed. Regularities of HfQ 2 addition effect on high-temperature polymorphic transformations of rare earth oxides were studied. Results of investigation were discussed from viewpoint of crystal chemistry

Final Report for research grant "Development of Methods for High Specific Activity Labeling of Biomolecules Using Astatine-211 in Different Oxidation States"

Energy Technology Data Exchange (ETDEWEB)

Wilbur, D. Scott [Univ. of Washington, Seattle, WA (United States)

2011-12-14

The overall objective of this research effort was to develop methods for labeling biomolecules with higher oxidation state species of At-211. This was to be done in an effort to develop reagents that had higher in vivo stability than the present carbon-bonded At-211-labeled compounds. We were unsuccessful in that effort, as none of the approaches studied provided reagents that were stable to in vivo deastatination. However, we gained a lot of information about At-211 in higher oxidation states. The studies proved to be very difficult as small changes in pH and other conditions appeared to change the nature of the species that obtained (by HPLC retention time analyses), with many of the species being unidentifiable. The fact that there are no stable isotopes of astatine, and the chemistry of the nearest halogen iodine is quite different, made it very difficult to interpret results of some experiments. With that said, we believe that a lot of valuable information was obtained from the studies. The research effort evaluated: (1) methods for chemical oxidation of At-211, (2) approaches to chelation of oxidized At-211, and (3) approaches to oxidation of astatophenyl compounds. A major hurdle that had to be surmounted to conduct the research was the development of HPLC conditions to separate and identify the various oxidized species formed. Attempts to develop conditions for separation of iodine and astatine species by normal and reversed-phase TLC and ITLC were not successful. However, we were successful in developing conditions (from a large number of attempts) to separate oxidized forms of iodine ([I-125]iodide, [I-125]iodate and [I-125]periodate) and astatine ([At-211]astatide, [At-211]astatate, [At-211]perastatate, and several unidentified At-211 species). Information on the basic oxidation and characterization of At-211 species is provided under Objective 1. Conditions were developed to obtain new At-211 labeling method where At-211 is chelated with the DOTA and

Sulfonated reduced graphene oxide as a highly efficient catalyst for direct amidation of carboxylic acids with amines using ultrasonic irradiation.

Science.gov (United States)

Mirza-Aghayan, Maryam; Tavana, Mahdieh Molaee; Boukherroub, Rabah

2016-03-01

Sulfonated reduced graphene oxide nanosheets (rGO-SO3H) were prepared by grafting sulfonic acid-containing aryl radicals onto chemically reduced graphene oxide (rGO) under sonochemical conditions. rGO-SO3H catalyst was characterized by Fourier-transform infrared (FT-IR) spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy (XPS). rGO-SO3H catalyst was successfully applied as a reusable solid acid catalyst for the direct amidation of carboxylic acids with amines into the corresponding amides under ultrasonic irradiation. The direct sonochemical amidation of carboxylic acid takes place under mild conditions affording in good to high yields (56-95%) the corresponding amides in short reaction times. Copyright © 2015 Elsevier B.V. All rights reserved.

[Oxidation behavior and kinetics of representative VOCs emitted from petrochemical industry over CuCeOx composite oxides].

Science.gov (United States)

Chen, Chang-Wei; Yu, Yan-Ke; Chen, Jin-Sheng; He, Chi

2013-12-01

CuCeOx composite catalysts were synthesized via coprecipitation (COP-CuCeO,) and incipient impregnation (IMP-CuCeOx) methods, respectively. The physicochemical properties of the samples were characterized by XRD, low-temperature N2 sorption, H2-TPR and O2-TPD. The influences of reactant composition and concentration, reaction space velocity, O2 content, H2O concentration, and catalyst type on the oxidation behaviors of benzene, toluene, and n-hexane emitted from petrochemical industry were systematically investigated. In addition, the related kinetic parameters were model fitted. Compared with IMP-CuCeOx, COP-CuCeOx had well-dispersed active phase, better low-temperature reducibility, and more active surface oxygen species. The increase of reactant concentration was unfavorable for toluene oxidation, while the opposite phenomenon could be observed in n-hexane oxidation. The inlet concentration of benzene was irrelevant to its conversion under high oxidation rate. The introduction of benzene obviously inhibited the oxidation of toluene and n-hexane, while the presence of toluene had a positive effect on beuzene conversion. The presence of n-hexane could promote the oxidation of toluene, while toluene had a negative influence on e-hexane oxidation. Both low space velocity and high oxygen concentration were beneficial for the oxidation process, and the variation of oxygen content had negligible effect on n-hexane and henzene oxidation. The presence of H2O noticeably inhibited the oxidation of toluene, while significantly accelerated the oxidation procedure of henzene and n-hexane. COP-CuCeOx had superior catalytic performance for toluene and benzene oxidation, while IMP-CuCeOx showed higher n-hexane oxidation activity under dry condition. The oxidation behaviors under different conditions could be well fitted and predicted by the pseudo first-order kinetic model.

Investigation of Zircaloy-2 oxidation model for SFP accident analysis

Energy Technology Data Exchange (ETDEWEB)

Nemoto, Yoshiyuki, E-mail: nemoto.yoshiyuki@jaea.go.jp [Japan Atomic Energy Agency, 2-4 Shirakata, Ohaza, Tokai-mura, Naka-gun, Ibaraki, 319-1195 (Japan); Kaji, Yoshiyuki; Ogawa, Chihiro; Kondo, Keietsu [Japan Atomic Energy Agency, 2-4 Shirakata, Ohaza, Tokai-mura, Naka-gun, Ibaraki, 319-1195 (Japan); Nakashima, Kazuo; Kanazawa, Toru; Tojo, Masayuki [Global Nuclear Fuel – Japan Co., Ltd., 2-3-1, Uchikawa, Yokosuka-shi, Kanagawa, 239-0836 (Japan)

2017-05-15

The authors previously conducted thermogravimetric analyses on Zircaloy-2 in air. By using the thermogravimetric data, an oxidation model was constructed in this study so that it can be applied for the modeling of cladding degradation in spent fuel pool (SFP) severe accident condition. For its validation, oxidation tests of long cladding tube were conducted, and computational fluid dynamics analyses using the constructed oxidation model were proceeded to simulate the experiments. In the oxidation tests, high temperature thermal gradient along the cladding axis was applied and air flow rates in testing chamber were controlled to simulate hypothetical SFP accidents. The analytical outputs successfully reproduced the growth of oxide film and porous oxide layer on the claddings in oxidation tests, and validity of the oxidation model was proved. Influence of air flow rate for the oxidation behavior was thought negligible in the conditions investigated in this study. - Highlights: •An oxidation model of Zircaloy-2 in air environment was developed. •The oxidation model was validated by the comparison with oxidation tests using long cladding tubes in hypothetical spent fuel pool accident condition. •The oxidation model successfully reproduced the typical oxidation behavior in air.

Comparison of different test methods to assess thermal stresses of metal oxide surge arresters under pollution conditions

International Nuclear Information System (INIS)

Bargigia, A.; de Nigris, M.; Pigini, A.; Sironi, A.

1992-01-01

The report deals with the research conducted by ENEL, the Italian Electricity Board, to assess the performance of zinc oxide surge arresters under pollution condition, with special reference to the consequent thermal stress on internal active parts which can affect the energy handling capabality of the arrester and may lead, in particular conditions, even to thermal runaway

Experimental study and modeling of high-temperature oxidation and phase transformation of cladding-tubes made in zirconium alloy

International Nuclear Information System (INIS)

Mazeres, Benoit

2013-01-01

One of the hypothetical accident studied in the field of the safety studies of Pressurized light Water Reactor (PWR) is the Loss-Of-Coolant-Accident (LOCA). In this scenario, zirconium alloy fuel claddings could undergo an important oxidation at high temperature (T≅ 1200 C) in a steam environment. Cladding tubes constitute the first confinement barrier of radioelements and then it is essential that they keep a certain level of ductility after quenching to ensure their integrity. These properties are directly related to the growth kinetics of both the oxide and the αZr(O) phase and also to the oxygen diffusion profile in the cladding tube after the transient. In this context, this work was dedicated to the understanding and the modeling of the both oxidation phenomenon and oxygen diffusion in zirconium based alloys at high temperature. The numerical tool (EKINOX-Zr) used in this thesis is based on a numerical resolution of a diffusion/reaction problem with equilibrium-conditions on three moving boundaries: gas/oxide, oxide/αZr(O), αZr(O)/βZr. EKINOX-Zr kinetics model is coupled with ThermoCalc software and the Zircobase database to take into account the influence of the alloying elements (Sn, Fe, Cr, Nb) but also the influence of hydrogen on the solubility of oxygen. This study focused on two parts of the LOCA scenario: the influence of a pre-oxide layer (formed in-service) and the effects of hydrogen. Thanks to the link between EKINOX-Zr and the thermodynamic database Zircobase, the hydrogen effects on oxygen solubility limit could be considered in the numerical simulations. Thus, simulations could reproduce the oxygen diffusion profiles measured in pre-hydrided samples. The existence of a thick pre-oxide layer on cladding tubes can induce a reduction of this pre-oxide layer before the growth of a high-temperature one during the high temperature dwell under steam. The first simulations performed using the numerical tool EKINOX-Zr showed that this particular

Study on Oxidation or Reduction Behavior of Cs-Te-O System with Gas Conditions of Voloxidation Process

International Nuclear Information System (INIS)

Park, Byung Heung

2013-01-01

Pyroprocessing has been developed for the purpose of resolving the current spent nuclear fuel management issue and enhancing the recycle of valuable resources. Pyroprocessing has been developed with the dry technologies which are performed under high temperature conditions excluding any aqueous processes. Pyro-processes which are based on the electrochemical principles require pretreatment processes and a voloxidation process is considered as a pretreatment step for an electrolytic reduction process. Various kinds of gas conditions are applicable to the voloxidation process and the understanding of Cs behavior during the process is of importance for the analyses of waste characteristics and heat load on the overall pyroprocessing. In this study, the changes of chemical compounds with the gas conditions were calculated by analyzing gas-solid reaction behavior based on the chemical equilibria on a Cs-Te-O system. Cs 2 TeO 3 and Cs 2 TeO 4 were selected after a Tpp diagram analysis and it was confirmed that they are relatively stable under oxidizing atmospheres while it was shown that Cs and Te would be removed by volatilization under reducing atmosphere at a high temperature. This work provided basic data for predicting Cs behavior during the voloxidation process at which compounds are chemically distributed as the first stage in the pyroprocessing and it is expected that the results would be used for setting up material balances and related purposes

Effects of different roasting conditions on the nutritional value and oxidative stability of high-oleic and yellow-seeded Brassica napus oils

Directory of Open Access Journals (Sweden)

Rękas, A.

2015-09-01

Full Text Available This study was conducted to evaluate the possibility of enhancing the nutritional value and oxidative stability of rapeseed oil obtained from seeds subjected to thermal treatment prior to pressing. The yellowseeded and high-oleic B. napus lines, harvested in Poland, were roasted prior to pressing for 1 h at 100 and 150 °C. This study highlighted how rapeseed breeding lines affect the quality profile of the oils obtained both before and after the roasting process. In principle, the high-oleic B. napus was accompanied by a nearly 2-fold increase in oxidative stability compared to the yellow-seeded B. napus, most likely due to a higher content of oxidation-resistant oleic fatty acids (~74.24% vs. ~60.76% and a decreased concentration of oxidizable PUFAs (~16.32% vs. ~31.09%. Similar to the case of roasting black-seeded rapeseed, the thermal pre-treatment of yellow-seeded and high-oleic B. napus prior to pressing did not alter the composition of their fatty acids. Based on the results obtained in this study, it can be concluded that roasting seeds prior to pressing does not reduce the amount of tocopherols in the oil; moreover, a slight increase in γ-tocopherol content was observed.Este estudio se realizó para evaluar la posibilidad de aumentar el valor nutritivo y la estabilidad oxidativa del aceite de colza obtenido a partir de semillas sometidas a tratamiento térmico antes del prensado. Las líneas de B. napus sembrados amarillos y alto oleico, cosechadas en Polonia, fueron tostadas antes de ser prensadas durante 1 hora a 100 y 150 °C. Este estudio pone de relieve cómo las líneas de colza mejoradas ven afectado el perfil de calidad de los aceites obtenidos antes y después del proceso de tostado. En principio, el alto oleico B. napus aumenta casi 2 veces la estabilidad a la oxidación en comparación con semilla amarilla B. napus, muy probablemente debido a un mayor contenido de ácido graso oleico resistente a la oxidación (~74,24% vs

Highly Sensitive Sensors Based on Metal-Oxide Nanocolumns for Fire Detection

Directory of Open Access Journals (Sweden)

Kwangjae Lee

2017-02-01

Full Text Available A fire detector is the most important component in a fire alarm system. Herein, we present the feasibility of a highly sensitive and rapid response gas sensor based on metal oxides as a high performance fire detector. The glancing angle deposition (GLAD technique is used to make the highly porous structure such as nanocolumns (NCs of various metal oxides for enhancing the gas-sensing performance. To measure the fire detection, the interface circuitry for our sensors (NiO, SnO2, WO3 and In2O3 NCs is designed. When all the sensors with various metal-oxide NCs are exposed to fire environment, they entirely react with the target gases emitted from Poly(vinyl chlorides (PVC decomposed at high temperature. Before the emission of smoke from the PVC (a hot-plate temperature of 200 °C, the resistances of the metal-oxide NCs are abruptly changed and SnO2 NCs show the highest response of 2.1. However, a commercial smoke detector did not inform any warning. Interestingly, although the NiO NCs are a p-type semiconductor, they show the highest response of 577.1 after the emission of smoke from the PVC (a hot-plate temperature of 350 °C. The response time of SnO2 NCs is much faster than that of a commercial smoke detector at the hot-plate temperature of 350 °C. In addition, we investigated the selectivity of our sensors by analyzing the responses of all sensors. Our results show the high potential of a gas sensor based on metal-oxide NCs for early fire detection.

High-temperature steam oxidation kinetics of the E110G cladding alloy

International Nuclear Information System (INIS)

Király, Márton; Kulacsy, Katalin; Hózer, Zoltán; Perez-Feró, Erzsébet; Novotny, Tamás

2016-01-01

In the course of recent years, several experiments were performed at MTA EK (Centre for Energy Research, Hungarian Academy of Sciences) on the isothermal high-temperature oxidation of the improved Russian cladding alloy E110G in steam/argon atmosphere. Using these data and designing additional supporting experiments, the oxidation kinetics of the E110G alloy was investigated in a wide temperature range, between 600 °C and 1200 °C. For short durations (below 500 s) or high temperatures (above 1065 °C) the oxidation kinetics was found to follow a square-root-of-time dependence, while for longer durations and in the intermediate temperature range (800–1000 °C) it was found to approach a cube-root-of-time dependence rather than a square-root one. Based on the results a new best-estimate and a conservative oxidation kinetics model were created. - Highlights: • Steam oxidation kinetics of E110G was studied at MTA EK based on old and new data. • New best-estimate and conservative steam oxidation kinetics were proposed for E110G. • The exponent of oxidation time changed depending on oxidation temperature. • A simple exponential curve was used instead of Arrhenius-type curve for the factor.

Evolution of oxidation in soybean oil and its biodiesel under the conditions of the oxidation stability test

Directory of Open Access Journals (Sweden)

Pereira, G. G.

2013-12-01

Full Text Available The objective of this study was to know the evolution of the oxidation of soybean oil and biodiesel under the conditions of the oxidation stability test (110 °C using the Rancimat apparatus. Samples were analyzed at different periods of time until the end of the induction period. The analytical determinations related to the changes in oxidation include peroxide value, anisidine value, natural tocopherols and polar compounds. Acid value, kinematic viscosity, polymers and ester content were also analyzed because of their relevance in the evaluation of biodiesel quality. Results showed that only peroxide value and the group of polar compounds including hydroperoxides, i.e. oxidized monomeric TAG in the oil and oxidized monomeric FAME in the biodiesel increased significantly during the early oxidation stage. The end of the induction period was marked by a rapid increase in polymerization compounds and the exhaustion of tocopherols. Significant changes in acid value, viscosity and ester content were only observed after the end of the induction period.El objetivo de este estudio fue conocer la evolución de la oxidación del aceite de soja y de su biodiesel a 110 °C en las condiciones del método estándar para la determinación de la estabilidad oxidativa, usando el aparato Rancimat. Las muestras se analizaron en diferentes períodos de tiempo hasta que el período de inducción fue sobrepasado. Se determinaron los índices de peróxidos y anisidina, los tocoferoles y los compuestos polares cuyos cambios están relacionados con el desarrollo de la alteración oxidativa. Además, fueron determinados el índice de acidez, la viscosidad y el contenido en ésteres, de interés en el análisis de la calidad del biodiesel. Los resultados indicaron que sólo el índice de peróxidos y el grupo de compuestos polares que incluye los hidroperóxidos (triglicéridos oxidados monómeros en el aceite y ésteres metílicos oxidados monómeros en el biodiesel

Development of Creep-Resistant and Oxidation-Resistant Austenitic Stainless Steels for High Temperature Applications

Science.gov (United States)

Maziasz, Philip J.

2018-01-01

Austenitic stainless steels are cost-effective materials for high-temperature applications if they have the oxidation and creep resistance to withstand prolonged exposure at such conditions. Since 1990, Oak Ridge National Laboratory (ORNL) has developed advanced austenitic stainless steels with creep resistance comparable to Ni-based superalloy 617 at 800-900°C based on specially designed "engineered microstructures" utilizing a microstructure/composition database derived from about 20 years of radiation effect data on steels. The wrought high temperature-ultrafine precipitate strengthened (HT-UPS) steels with outstanding creep resistance at 700-800°C were developed for supercritical boiler and superheater tubing for fossil power plants in the early 1990s, the cast CF8C-Plus steels were developed in 1999-2001 for land-based gas turbine casing and diesel engine exhaust manifold and turbocharger applications at 700-900°C, and, in 2015-2017, new Al-modified cast stainless steels with oxidation and creep resistance capabilities up to 950-1000°C were developed for automotive exhaust manifold and turbocharger applications. This article reviews and summarizes their development and their properties and applications.

3-D laser confocal microscopy study of the oxidation of NdFeB magnets in atmospheric conditions

International Nuclear Information System (INIS)

Meakin, J.P.; Speight, J.D.; Sheridan, R.S.; Bradshaw, A.; Harris, I.R.; Williams, A.J.; Walton, A.

2016-01-01

Highlights: • Room temperature atmospheric oxidation behaviour of sintered NdFeB. • 3D laser confocal microscopy measurement of oxide phase growth. • Significant height increase of oxide phase only observed at triple points. • Raman spectroscopy identified oxide phase to be Nd 2 O 3 . • Diffusion coefficient determined to be 4 × 10 −13 cm 2 /s. - Abstract: Neodymium iron boron (NdFeB) magnets are used in a number of important applications, such as generators in gearless wind turbines, motors in electric vehicles and electronic goods (e.g.— computer hard disk drives, HDD). Hydrogen can be used as a processing gas to separate and recycle scrap sintered Nd-Fe-B magnets from end-of-life products to form a powder suitable for recycling. However, the magnets are likely to have been exposed to atmospheric conditions prior to processing, and any oxidation could lead to activation problems for the hydrogen decrepitation reaction. Many previous studies on the oxidation of NdFeB magnets have been performed at elevated temperatures; however, few studies have been formed under atmospheric conditions. In this paper a combination of 3-D laser confocal microscopy and Raman spectroscopy have been used to assess the composition, morphology and rate of oxidation/corrosion on scrap sintered NdFeB magnets. Confocal microscopy has been employed to measure the growth of surface reaction products at room temperature, immediately after exposure to air. The results showed that there was a significant height increase at the triple junctions of the Nd-rich grain boundaries. Using Raman spectroscopy, the product was shown to consist of Nd 2 O 3 and formed only on the Nd-rich triple junctions. The diffusion coefficient of the triple junction reaction product growth at 20 °C was determined to be approximately 4 × 10 −13 cm 2 /sec. This value is several orders of magnitude larger than values derived from the diffusion controlled oxide growth observations at elevated

3-D laser confocal microscopy study of the oxidation of NdFeB magnets in atmospheric conditions

Energy Technology Data Exchange (ETDEWEB)

Meakin, J.P., E-mail: jxm764@bham.ac.uk; Speight, J.D.; Sheridan, R.S.; Bradshaw, A.; Harris, I.R.; Williams, A.J.; Walton, A.

2016-08-15

Highlights: • Room temperature atmospheric oxidation behaviour of sintered NdFeB. • 3D laser confocal microscopy measurement of oxide phase growth. • Significant height increase of oxide phase only observed at triple points. • Raman spectroscopy identified oxide phase to be Nd{sub 2}O{sub 3}. • Diffusion coefficient determined to be 4 × 10{sup −13} cm{sup 2}/s. - Abstract: Neodymium iron boron (NdFeB) magnets are used in a number of important applications, such as generators in gearless wind turbines, motors in electric vehicles and electronic goods (e.g.— computer hard disk drives, HDD). Hydrogen can be used as a processing gas to separate and recycle scrap sintered Nd-Fe-B magnets from end-of-life products to form a powder suitable for recycling. However, the magnets are likely to have been exposed to atmospheric conditions prior to processing, and any oxidation could lead to activation problems for the hydrogen decrepitation reaction. Many previous studies on the oxidation of NdFeB magnets have been performed at elevated temperatures; however, few studies have been formed under atmospheric conditions. In this paper a combination of 3-D laser confocal microscopy and Raman spectroscopy have been used to assess the composition, morphology and rate of oxidation/corrosion on scrap sintered NdFeB magnets. Confocal microscopy has been employed to measure the growth of surface reaction products at room temperature, immediately after exposure to air. The results showed that there was a significant height increase at the triple junctions of the Nd-rich grain boundaries. Using Raman spectroscopy, the product was shown to consist of Nd{sub 2}O{sub 3} and formed only on the Nd-rich triple junctions. The diffusion coefficient of the triple junction reaction product growth at 20 °C was determined to be approximately 4 × 10{sup −13} cm{sup 2}/sec. This value is several orders of magnitude larger than values derived from the diffusion controlled oxide growth

Safety analysis of switching between reductive and oxidative conditions in a reaction coupling reverse flow reactor.

NARCIS (Netherlands)

van Sint Annaland, M.; Kuipers, J.A.M.; van Swaaij, Willibrordus Petrus Maria

2001-01-01

A new reverse flow reactor is developed where endothermic reactants (propane dehydrogenation) and exothermic reactants (fuel combustion) are fed sequentially to a monolithic catalyst, while periodically alternating the inlet and outlet positions. Upon switching from reductive to oxidative conditions

The accelerated oxidation of zircaloy-4 at 700∼900 .deg. C in high pressure steam

International Nuclear Information System (INIS)

Kim, K. P.; Park, K. H.

1999-01-01

To find the effect of pressure on the high temperature oxidation of zircaloy-4, an autoclave capable of measuring the degree of oxidation at high temperatures and high pressure was manufactured. The specimens used in experiments are commercially available Zircaloy-4 used in Kori nuclear power plants. All the measurements were done at 700∼900 .deg. C in steam. Pressure effects were noticed. The oxide thickness was much thicker in high pressure steam, comparing to that in the 1 atm steam. And, the higher is the steam pressure, the thicker becomes the oxide. The enhancement of oxide growth rate at 700∼900 .deg. C in high pressure steam is approximately propotion to the power of 1.0∼1.6 of the ratio of experimental steam pressure to critical steam pressure. There is a critical steam pressure above that the oxidation rate enhances. The critical steam pressure was measured as 30∼40 bar. The enhanced oxidation seems from the oxide cracking due to the tetragonal to monoclinic phase transformation at high pressure steam

One pot synthesis of multi-functional tin oxide nanostructures for high efficiency dye-sensitized solar cells

Energy Technology Data Exchange (ETDEWEB)

Wali, Qamar; Fakharuddin, Azhar; Yasin, Amina; Ab Rahim, Mohd Hasbi; Ismail, Jamil; Jose, Rajan, E-mail: rjose@ump.edu.my

2015-10-15

Photoanode plays a key role in dye sensitized solar cells (DSSCs) as a scaffold for dye molecules, transport medium for photogenerated electrons, and scatters light for improved absorption. Herein, tin oxide nanostructures unifying the above three characteristics were optimized by a hydrothermal process and used as photoanode in DSSCs. The optimized morphology is a combination of hollow porous nanoparticles of size ∼50 nm and micron sized spheres with BET surface area (up to 29 m{sup 2}/g) to allow large dye-loading and light scattering as well as high crystallinity to support efficient charge transport. The optimized morphology gave the highest photovoltaic conversion efficiency (∼7.5%), so far achieved in DSSCs with high open circuit voltage (∼700 mV) and short circuit current density (∼21 mA/cm{sup 2}) employing conventional N3 dye and iodide/triiodide electrolyte. The best performing device achieved an incident photon to current conversion efficiency of ∼90%. The performance of the optimized tin oxide nanostructures was comparable to that of conventional titanium based DSSCs fabricated at similar conditions. - Graphical abstract: Tin oxide hollow nanostructure simultaneously supporting improved light scattering, dye-loading, and charge transport yielded high photovoltaic conversion efficiency in dye-sensitized solar cells. - Highlights: • Uniformly and bimodelly distributed tin oxide hollow nanospheres (HNS) are synthesized. • Uniform HNS are of size ∼10 nm; bimodel HNS has additional size up to ∼800 nm. • They are evaluated as photoelectrodes in dye-sensitized solar cells (DSSCs). • The uniform HNS increase dye-loading and the larger increase light scattering in DSSCs. • Photo conversion efficiency ∼7.5% is achieved using bimodel HNS.

Highly Efficient, Durable Regenerative Solid Oxide Stack, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — Precision Combustion, Inc. (PCI) proposes to develop a highly efficient regenerative solid oxide stack design. Novel structural elements allow direct internal...

New perovskite-related oxides having high dielectric constant ...

Indian Academy of Sciences (India)

Unknown

static and dynamic random access memories, the static dielectric constant of the material. ¶Dedicated to .... 1100°C. It is also observed from the SEM pictures that the materials are highly dense .... Both these oxides merit attention for their.

Nanoscale analysis of the influence of pre-oxidation on oxide formation and wetting behavior of hot-dip galvanized high strength steel

International Nuclear Information System (INIS)

Arndt, M.; Duchoslav, J.; Steinberger, R.; Hesser, G.; Commenda, C.; Samek, L.; Arenholz, E.

2015-01-01

Highlights: • Pre-oxidized hot-dip galvanized advanced high strength steel was examined. • The interface was analyzed in detail via high energy resolution Auger spectra. • Evidence for an aluminothermic reduction of the Mn oxide was found. • A new model for galvanizing high manganese steel was developed. - Abstract: Hot-dip galvanized (HDG) 2nd generation advanced high strength steel (AHSS), nano-TWIP (twinning induced plasticity) with 15.8 wt.% Mn, 0.79 wt.% C, was analyzed at the interface between steel and zinc by scanning Auger electron microscopy (AES) in order to confirm and improve an existing model of additional pre-oxidation treatment before annealing and immersion into the hot zinc bath. Furthermore these steel samples were fractured in the analysis chamber of the AES and analyzed without breaking vacuum. In these measurements the results of an aluminothermic reduction of the manganese and iron surface oxides on the steel could be confirmed by AES

Effects of surface condition on aqueous corrosion and environmental embrittlement of iron aluminides

Energy Technology Data Exchange (ETDEWEB)